Ternary Alloy Systems Phase Diagrams, Crystallographic and ...

Landolt-Börnstein 

Numerical Data and Functional Relationships in Science and Technology 

New Series / Editor in Chief: W. Martienssen 

Group IV: Physical Chemistry 

Volume 11 

Ternary Alloy Systems 

Phase Diagrams, Crystallographic and 

Thermodynamic Data 

critically evaluated by MSIT ® 

Subvolume D 

Iron Systems 

Part 5 

Selected Systems from Fe-N-V to Fe-Ti-Zr 

Editors 

G. Effenberg and S. Ilyenko 

Authors 

Materials Science and International Team, MSIT ®

ISSN 1615-2018 (Physical Chemistry) 

ISBN 978-3-540-70885-8 Springer Berlin Heidelberg New York 

Library of Congress Cataloging in Publication Data 

Zahlenwerte und Funktionen aus Naturwissenschaften und Technik, Neue Serie 

Editor in Chief: W. Martienssen 

Vol. IV/11D5: Editors: G. Effenberg, S. Ilyenko 

At head of title: Landolt-Börnstein. Added t.p.: Numerical data and functional relationships in science and technology. 

Tables chiefly in English. 

Intended to supersede the Physikalisch-chemische Tabellen by H. Landolt and R. Börnstein of which the 6th ed. began publication in 1950 under title: 

Zahlenwerte und Funktionen aus Physik, Chemie, Astronomie, Geophysik und Technik. 

Vols. published after v. 1 of group I have imprint: Berlin, New York, Springer-Verlag 

Includes bibliographies. 

1. Physics--Tables. 2. Chemistry--Tables. 3. Engineering--Tables. 

I. Börnstein, R. (Richard), 1852-1913. II. Landolt, H. (Hans), 1831-1910. 

III. Physikalisch-chemische Tabellen. IV. Title: Numerical data and functional relationships in science and technology. 

QC61.23 502'.12 62-53136 

This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, 

reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in other ways, and storage in data banks. Duplication of this 

publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and 

permission for use must always be obtained from Springer-Verlag. Violations are liable for prosecution act under German Copyright Law. 

Springer is a part of Springer Science+Business Media 

springeronline.com 

© Springer-Verlag Berlin Heidelberg 2009 

Printed in Germany 

The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, 

that such names are exempt from the relevant protective laws and regulations and therefore free for general use. 

Product Liability: The data and other information in this handbook have been carefully extracted and evaluated by experts from the original literature. 

Furthermore, they have been checked for correctness by authors and the editorial staff before printing. Nevertheless, the publisher can give no 

guarantee for the correctness of the data and information provided. In any individual case of application, the respective user must check the correctness 

by consulting other relevant sources of information. 

Cover layout: Erich Kirchner, Heidelberg 

Typesetting: Materials Science International Services GmbH, Stuttgart 

Printing and Binding: AZ Druck, Kempten/Allgäu 

SPIN: 1221 0152 63/3020 - 5 4 3 2 1 0 – Printed on acid-free paper

Editors: Günter Effenberg 

Svitlana Ilyenko 

Associate Editor: Oleksandr Dovbenko 

MSI, Materials Science International Services GmbH 

Postfach 800749, D-70507, Stuttgart, Germany 

http://www.matport.com 

Authors: Materials Science International Team, MSIT ® 

The present series of books results from collaborative evaluation programs performed by MSI and 

authored by MSIT ® . In this program data and knowledge are contributed by many individuals and 

accumulated over almost twenty years, now. The content of this volume is a subset of the ongoing MSIT ® 

Evaluation Programs. Authors of this volume are: 

Nataliya Bochvar, Moscow, Russia Marina 

Bulanova, Kyiv, Ukraine Gabriele 

Cacciamani, Genova, Italy Hailin Chen, 

Changsha, China Gautam Ghosh, Evanston, 

USA Lesley Cornish, Randburg, South 

Africa Damian M. Cupid, Freiberg, Germany 

Yong Du, Changsha, China Olga 

Fabrichnaya, Freiberg, Germany Yulia 

Fartushna, Kyiv, Ukraine Baiyun Huang, 

Changsha, China Volodymyr Ivanchenko, 

Kyiv, Ukraine Jozefien De Keyzer, Heverlee, 

Belgium Natalia Kol’chugina, Moscow, 

Russia Kostyantyn Korniyenko, Kyiv, 

Ukraine Artem Kozlov, Clausthal-Zellerfeld, 

Germany Viktor Kuznetsov, Moscow, Russia 

Shuhong Liu, Changsha, China 

Hans Leo Lukas, Stuttgart, Germany 

Pankaj Nerikar, Gainesville, USA Pierre 

Perrot, Lille, France Tatiana Pryadko, 

Kyiv, Ukraine Peter Rogl, Vienna, Austria 

Lazar Rokhlin, Moscow, Russia Hans 

Jürgen Seifert, Freiberg, Germany Elena 

Semenova, Kyiv, Ukraine Weihua Sun, 

Changsha, China Jean-Claude Tedenac, 

Montpellier, France Vasyl Tomashik, 

Kyiv, Ukraine Lyudmilla Tretyachenko, 

Kyiv, Ukraine Tamara Velikanova, Kyiv, 

Ukraine Andy Watson, Leeds, U.K. Wei 

Xiong, Changsha, China Honghui Xu, 

Changsha, China Chao Zhang, Changsha, 

China Lijun Zhang, Changsha, China 

Weiwei Zhang, Changsha, China

Institutions 

The content of this volume is produced by MSI, Materials Science International Services GmbH and the 

international team of materials scientists, MSIT ® . Contributions to this volume have been made from the 

following institutions: 

The Baikov Institute of Metallurgy, Academy of 

Sciences, Moscow, Russia 

Central South University, Research Institute of 

Powder Metallurgy, State Key Laboratory for 

Powder Metallurgy, Changsha, China 

I.M. Frantsevich Institute for Problems of 

Materials Science, National Academy of Sciences, 

Kyiv, Ukraine 

Institute for Semiconductor Physics, National 

Academy of Sciences, Kyiv, Ukraine 

Katholieke Universiteit Leuven, Department 

Metaalkunde en Toegepaste Materiaalkunde, 

Heverlee, Belgium 

G.V. Kurdyumov Institute for Metal Physics, 

National Academy of Sciences, Kyiv, Ukraine 

Max-Planck-Institut für Metallforschung, 

Institut für Werkstoffwissenschaft, 

Pulvermetallurgisches Laboratorium, Stuttgart, 

Germany 

Moscow State University, Department of General 

Chemistry, Moscow, Russia 

Northwestern University, Department of 

Materials Science and Engineering, Evanston, 

USA 

School of Chemical and Metallurgical 

Engineering, The University of the 

Witwatersrand, DST/NRF Centre of Excellence 

for Strong Material, South Afrika 

Technische Universität Bergakademie Freiberg, 

Institut für Werkstoffwissenschaft, Freiberg, 

Germany 

Technische Universität Clausthal, Metallurgisches 

Zentrum, Clausthal-Zellerfeld, Germany 

Universita di Genova, Dipartimento di Chimica, 

Genova, Italy 

Universität Wien, Institut für Physikalische 

Chemie, Wien, Austria 

Universite de Lille I, Laboratoire de Métallurgie 

Physique, Villeneuve d’ASCQ, France 

Universite de Montpellier II, Laboratorie de 

Physico-chimie de la Materiere Montpellier, 

France 

University of Florida, Department of Materials 

Science and Engineering, Gainesville, USA 

University of Leeds, Department of Materials, 

School of Process, Environmental and Materials 

Engineering, Leeds, UK

Preface 

The sub-series Ternary Alloy Systems of the Landolt-Börnstein New Series provides reliable and 

comprehensive descriptions of the materials constitution, based on critical intellectual evaluations of all 

data available at the time and it critically weights the different findings, also with respect to their 

compatibility with today’s edge binary phase diagrams. Selected are ternary systems of importance to 

alloy development and systems which gained in the recent years otherwise scientific interest. In one 

ternary materials system, however, one may find alloys for various applications, depending on the chosen 

composition. 

Reliable phase diagrams provide scientists and engineers with basic information of eminent 

importance for fundamental research and for the development and optimization of materials. So 

collections of such diagrams are extremely useful, if the data on which they are based have been 

subjected to critical evaluation, like in these volumes. Critical evaluation means: there where 

contradictory information is published data and conclusions are being analyzed, broken down to the firm 

facts and re-interpreted in the light of all present knowledge. Depending on the information available this 

can be a very difficult task to achieve. Critical evaluations establish descriptions of reliably known phase 

configurations and related data. 

The evaluations are performed by MSIT ® , Materials Science International Team, a group of scientists 

working together since 1984. Within this team skilled expertise is available for a broad range of methods, 

materials and applications. This joint competence is employed in the critical evaluation of the often 

conflicting literature data. Particularly helpful in this are targeted thermodynamic and atomistic 

calculations for individual equilibria, driving forces or complete phase diagram sections. 

Conclusions on phase equilibria may be drawn from direct observations e.g. by microscope, from 

monitoring caloric or thermal effects or measuring properties such as electric resistivity, electro-magnetic 

or mechanical properties. Other examples of useful methods in materials chemistry are massspectrometry, 

thermo-gravimetry, measurement of electro-motive forces, X-ray and microprobe analyses. 

In each published case the applicability of the chosen method has to be validated, the way of actually 

performing the experiment or computer modeling has to be validated as well and the interpretation of the 

results with regard to the material’s chemistry has to be verified. Therefore insight in materials 

constitution and phase reactions is gained from many distinctly different types of experiments, 

calculation and observations. Intellectual evaluations which interpret all data simultaneously reveal the 

chemistry of the materials system best. 

An additional degree of complexity is introduced by the material itself, as the state of the material 

under test depends heavily on its history, in particular on the way of homogenization, thermal and 

mechanical treatments. All this is taken into account in an MSIT ® expert evaluation. 

To include binary data in the ternary evaluation is mandatory. Each of the three-dimensional ternary 

phase diagrams has edge binary systems as boundary planes; their data have to match the ternary data 

smoothly. At the same time each of the edge binary systems A-B is a boundary plane for many other 

ternary A-B-X systems. Therefore combining systematically binary and ternary evaluations increases 

confidence and reliability in both ternary and binary phase diagrams. This has started systematically for 

the first time here, by the MSIT ® Evaluation Programs applied to the Landolt-Börnstein New Series. The 

degree of success, however, depends on both the nature of materials and scientists! 

The multitude of correlated or inter-dependant data requires special care. Within MSIT ® an evaluation 

routine has been established that proceeds knowledge driven and applies both, human based expertise and 

electronically formatted data and software tools. MSIT ® internal discussions take place in almost all 

evaluation works and on many different specific questions the competence of a team is added to the work 

of individual authors. In some cases the authors of earlier published work contributed to the knowledge

ase by making their original data records available for re-interpretation. All evaluation reports published 

here have undergone a thorough review process in which the reviewers had access to all the original data. 

In publishing we have adopted a standard format that presents the reader with the data for each ternary 

system in a concise and consistent manner, as applied in the “MSIT ® Workplace Phase Diagrams 

Online”. The standard format and special features of the Landolt-Börnstein compendium are explained in 

the Introduction to the volume. 

In spite of the skill and labor that have been put into this volume, it will not be faultless. All criticisms 

and suggestions that can help us to improve our work are very welcome. Please contact us via 

effenberg@msiwp.com. We hope that this volume will prove to be as useful for the materials scientist 

and engineer as the other volumes of Landolt-Börnstein New Series and the previous works of MSIT ® 

have been. We hope that the Landolt Börnstein Sub-series, Ternary Alloy Systems will be well received 

by our colleagues in research and industry. 

On behalf of the participating authors we want to thank all those who contributed their comments and 

insight during the evaluation process. In particular we thank the reviewers - Pierre Perrot, 

Tamara Velikanova, Hans Leo Lukas, Marina Bulanova, Mikhail Turchanin, Nataliya Bochvar, 

Olga Fabrichnaya and Viktor Kuznetsov. 

We all gratefully acknowledge the dedicated scientific desk editing by Oleksandra Berezhnytska, 

Mariya Saltykova and Oleksandr Rogovtsov. 

Günter Effenberg, Svitlana Ilyenko and Oleksandr Dovbenko Stuttgart, March 2008

Foreword 

Can you imagine a world without iron and steel? No? I can’t either. 

The story of mankind is intimately linked to the discovery and successful use of metals and their 

alloys. Amongst them iron and steel - we could define steel as ‘a generally hard, strong, durable, 

malleable alloy of iron and carbon, usually containing between 0.2 and 1.5 percent carbon, often with 

other constituents such as manganese, Chromium, nickel, molybdenum, copper, tungsten, Cobalt, or 

silicon, depending on the desired alloy properties, and widely used as a structural material’, have shaped 

our material world. 

The story of iron takes us back to the period of the Hittite Empire around 1300 BC, when iron started 

to replace bronze as the chief metal used for weapons and tools. Until today the story remains 

uncompleted and the social and economic impact of the iron and steel industry is now beyond 

imagination. In the year 2005 1.13 billion tons of crude steel were produced. Compared to 2004 this is an 

increase of 6.8%. That same year the steel production in China increased from 280.5 to almost 350 

million tons. Concerning stainless steel: according to the International Stainless Steel Forum (ISSF), the 

global production forecast for 2006 now stands at 27.8 million metric tons of stainless crude steel, up 

14.3% compared to 2005. 

An English poem from the 19 th century tells us 

Gold is for the mistress 

Silver for the maid 

Copper for the craftsman 

Cunning at his trade 

Good said the baron 

Sitting in his hall 

But iron, cold iron 

Is master of them all 

It is still actual and true. 

The list of different steel grades and related applications is impressive and still growing: low carbon 

strip steels for automotive applications, low carbon structural steels, engineering steels, stainless steels, 

cast irons, and, more recently: dual phase steels, TRIP-steels, TWIP-steels, maraging steels, … 

The list of applications seems endless: a wide range of properties from corrosion resistance to high 

tensile strength is covered. These properties depend on the percentage of carbon, the alloying elements, 

and increasingly on the thermo-mechanical treatments that aim at optimizing the microstructure. 

Yet many potential improvements remain unexplored, also due to the increasing complexity of the 

new steel grades. For instance, a recently patent protected new die steel for hot deformation has the 

following composition specifications: C 0.46 – 0.58; Si 0.18 – 0.40; Mn 0.45 – 0.75, Cr 0.80 – 1.20; Ni 

1.30 – 1.70; Mo 0.35 – 0.65; V 0.18 – 0.25; Al 0.01 – 0.04; Ti 0.002 – 0.04; B 0.001 – 0.003; Zr 0.02 – 

0.04; Fe remaining.

Although many properties of steel are directly related to non-equilibrium states, it remains a fact that 

the equilibrium state creates the reference frame for all changes that might occur in any material - and 

consequently would effect its properties in use - that is actually not in its thermodynamic equilibrium 

state. This is what these volumes in the Landolt-Börnstein series stand for: they have collected the most 

reliable data on the possible phase equilibria in ternary iron based alloys. Therefore this first volume of 

data, as well as the other ones in a series of four to appear, is of immeasurable value for metallurgists and 

materials engineers that improve the properties of existing steels and develop new and more complex 

steel grades. It is about materials, it is about quality of life. 

The well-recognized quality label of MSIT ® , the Materials Science International Team, also applies to 

the present volume of the Landolt-Börnstein series. It should be available for every materials engineer, 

scientist and student. 

Prof. Dr. ir. Patrick Wollants 

Chairman - Department of Metallurgy and Materials Engineering 

Katholieke Universiteit Leuven 

Belgium

Contents 

IV/11D5 Ternary Alloy Systems 

Phase Diagrams, Crystallographic and Thermodynamic Data 

Subvolume D Iron Systems 

Part 5 Selected Systems from Fe-N-V to Fe-Ti-Zr 

Introduction 

Data Covered.......................................................................................................................................XIII 

General ................................................................................................................................................XIII 

Structure of a System Report..............................................................................................................XIII 

Introduction.................................................................................................................................XIII 

Binary Systems ...........................................................................................................................XIII 

Solid Phases ................................................................................................................................XIV 

Quasibinary Systems....................................................................................................................XV 

Invariant Equilibria......................................................................................................................XV 

Liquidus, Solidus, Solvus Surfaces ............................................................................................. XV 

Isothermal Sections......................................................................................................................XV 

Temperature – Composition Sections .........................................................................................XV 

Thermodynamics..........................................................................................................................XV 

Notes on Materials Properties and Applications.........................................................................XV 

Miscellaneous ..............................................................................................................................XV 

References................................................................................................................................XVIII 

General References .............................................................................................................................XIX 

Ternary Systems 

Fe–N–V (Iron – Nitrogen – Vanadium)..................................................................................................1 

Fe–Na–O (Iron – Sodium – Oxygen)....................................................................................................14 

Fe–Nb–Ni (Iron – Niobium – Nickel)...................................................................................................33 

Fe–Nb–P (Iron – Niobium – Phosphorus) ............................................................................................43 

Fe–Nb–Si (Iron – Niobium – Silicon)...................................................................................................55 

Fe–Nb–Zr (Iron – Niobium – Zirconium).............................................................................................69 

Fe–Nd–Si (Iron – Neodynium – Silicon)..............................................................................................82 

Fe–Ni–P (Iron – Nickel – Phosphorus).................................................................................................96 

Fe–Ni–S (Iron – Nickel – Sulfur)........................................................................................................113 

Fe–Ni–Sb (Iron – Nickel – Antimony) ...............................................................................................155 

Fe–Ni–Si (Iron – Nickel – Silicon) .....................................................................................................171 

Fe–Ni–Ti (Iron – Nickel – Titanium)..................................................................................................188 

Fe–Ni–V (Iron – Nickel – Vanadium) ................................................................................................212 

Fe–Ni–W (Iron – Nickel – Tungsten) .................................................................................................225 

Fe–Ni–Zn (Iron – Nickel – Zinc) ........................................................................................................245 

Fe–Ni–Zr (Iron – Nickel – Zirconium) ...............................................................................................256

Fe–O–Pb (Iron – Oxygen – Lead).......................................................................................................268 

Fe–O–Si (Iron – Oxygen – Silicon) ....................................................................................................281 

Fe–O–U (Iron – Oxygen – Uranium)..................................................................................................322 

Fe–O–W (Iron – Oxygen – Tungsten) ................................................................................................330 

Fe–O–Y (Iron – Oxygen – Yttrium) ...................................................................................................346 

Fe–O–Zr (Iron – Oxygen – Zirconium) ..............................................................................................359 

Fe–P–Si (Iron – Phosphorus – Silicon)...............................................................................................375 

Fe–S–Ti (Iron – Sulfur – Titanium) ....................................................................................................393 

Fe–Si–Ti (Iron – Silicon – Titanium)..................................................................................................410 

Fe–Si–V (Iron – Silicon – Vanadium) ................................................................................................428 

Fe–Si–Zr (Iron – Silicon – Zirconium) ...............................................................................................447 

Fe–Sm–Ti (Iron – Samarium – Titanium) ..........................................................................................458 

Fe–Sn–Zr (Iron – Tin – Zirconium) ....................................................................................................480 

Fe–Ti–V(Iron – Titanium – Vanadium)..............................................................................................493 

Fe–Ti–Y (Iron – Titanium – Yttrium).................................................................................................504 

Fe-Ti-Zr (Iron – Titanium – Zirconium).............................................................................................518

Introduction 

Iron Systems: Phase Diagrams, Crystallographic and Thermodynamic Data 

Data Covered 

The series focuses on light metal ternary systems and includes phase equilibria of importance 

for alloy development, processing or application, reporting on selected ternary systems of 

importance to industrial light alloy development and systems which gained otherwise scientific 

interest in the recent years. 

General 

The series provides consistent phase diagram descriptions for individual ternary systems. 

The representation of the equilibria of ternary systems as a function of temperature results 

in spacial diagrams whose sections and projections are generally published in the literature. 

Phase equilibria are described in terms of liquidus, solidus and solvus projections, isothermal 

and quasibinary sections; data on invariant equilibria are generally given in the form 

of tables. 

The world literature is thoroughly and systematically searched back to the year 1900. 

Then, the published data are critically evaluated by experts in materials science and 

reviewed. Conflicting information is commented upon and errors and inconsistencies 

removed wherever possible. It considers those, and only those data, which are firmly established, 

comments on questionable findings and justifies re-interpretations made by the 

authors of the evaluation reports. 

In general, the approach used to discuss the phase relationships is to consider changes 

in state and phase reactions which occur with decreasing temperature. This has influenced 

the terminology employed and is reflected in the tables and the reaction schemes 

presented. 

The system reports present concise descriptions and hence do not repeat in the text facts 

which can clearly be read from the diagrams. For most purposes the use of the compendium is 

expected to be self-sufficient. However, a detailed bibliography of all cited references is given to 

enable original sources of information to be studied if required. 

Structure of a System Report 

Introduction 1 

The constitutional description of an alloy system consists of text and a table/diagram section 

which are separated by the bibliography referring to the original literature (see Fig. 1). The 

tables and diagrams carry the essential constitutional information and are commented on in 

the text if necessary. 

Where published data allow, the following sections are provided in each report: 

Landolt‐Börnstein 

New Series IV/11D5 

MSIT 1 

DOI: 10.1007/978-3-540-70890-2_1 

ß Springer 2009 

1

2 1 

Introduction 

. Fig. 1 

Structure of a system report 

Introduction 

The opening text reviews briefly the status of knowledge published on the system and outlines 

the experimental methods that have been applied. Furthermore, attention may be drawn to 

questions which are still open or to cases where conclusions from the evaluation work 

modified the published phase diagram. 

Binary Systems 

Where binary systems are accepted from standard compilations reference is made to these 

compilations. In other cases the accepted binary phase diagrams are reproduced for the 

convenience of the reader. The selection of the binary systems used as a basis for the evaluation 

of the ternary system was at the discretion of the assessor. 

DOI: 10.1007/978-3-540-70890-2_1 Landolt‐Börnstein 

ß Springer 2009 New Series IV/11D5 

MSIT 1

Solid Phases 

The tabular listing of solid phases incorporates knowledge of the phases which is necessary or 

helpful for understanding the text and diagrams. Throughout a system report a unique phase 

name and abbreviation is allocated to each phase. 

Phases with the same formulae but different space lattices (e.g. allotropic transformation) 

are distinguished by: 

– small letters (h), high temperature modification (h2 >h1) (r), room temperature modification 

(1), low temperature modification (l1 >l2) – Greek letters, e.g., ε, ε’ 

– Roman numerals, e.g., (I) and (II) for different pressure modifications. 

In the table “Solid Phases” ternary phases are denoted by * and different phases are 

separated by horizontal lines. 

Quasibinary Systems 

Quasibinary (pseudobinary) sections describe equilibria and can be read in the same way as 

binary diagrams. The notation used in quasibinary systems is the same as that of vertical 

sections, which are reported under “Temperature – Composition Sections”. 

Invariant Equilibria 

The invariant equilibria of a system are listed in the table “Invariant Equilibria” and, where 

possible, are described by a constitutional “Reaction Scheme” (Fig. 2). 

The sequential numbering of invariant equilibria increases with decreasing temperature, 

one numbering for all binaries together and one for the ternary system. 

Equilibria notations are used to indicate the reactions by which phases will be 

– decomposed (e- and E-type reactions) 

– formed (p- and P-type reactions) 

– transformed (U-type reactions) 

For transition reactions the letter U (Übergangsreaktion) is used in order to reserve the 

letter T to denote temperature. The letters d and D indicate degenerate equilibria which do not 

allow a distinction according to the above classes. 

Liquidus, Solidus, Solvus Surfaces 


The phase equilibria are commonly shown in triangular coordinates which allow a reading of 

the concentration of the constituents in at.%. In some cases mass% scaling is used for better 

data readability (see Figs. 3 and 4). 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_1 


3

4 1 

Introduction 

. Fig. 2 

Typical reaction scheme 



MSIT 1

. Fig. 3 

Hypothetical liqudus surface showing notation employed 

In the polythermal projection of the liquidus surface, monovariant liquidus grooves 

separate phase regions of primary crystallization and, where available, isothermal lines contour 

the liquidus surface (see Fig. 3). 

Isothermal Sections 

Phase equilibria at constant temperatures are plotted in the form of isothermal sections (see 

Fig. 4). 

Temperature – Composition Sections 


Non-quasibinary T-x sections (or vertical sections, isopleths, polythermal sections) show the 

phase fields where generally the tie lines are not in the same plane as the section. The notation 

employed for the latter (see Fig. 5) is the same as that used for binary and quasibinary phase 

diagrams. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_1 


5

6 1 

Introduction 

. Fig. 4 

Hypotheticcal isothermal section showing notation employed 

Thermodynamics 

Experimental ternary data are reported in some system reports and reference to thermodynamic 

modeling is made. 

Notes on Materials Properties and Applications 

Noteworthy physical and chemical materials properties and application areas are briefly 

reported if they were given in the original constitutional and phase diagram literature. 

Miscellaneous 

In this section noteworthy features are reported which are not described in preceding paragraphs. 

These include graphical data not covered by the general report format, such as lattice 

spacing – composition data, p-T-x diagrams, etc. 



MSIT 1

. Fig. 5 

Hypothetical vertical section showing notation employed 

References 


The publications which form the bases of the assessments are listed in the following manner: 

[1974Hay] Hayashi, M., Azakami, T., Kamed, M., “Effects of Third Elements on the 

Activity of Lead in Liquid Copper Base Alloys” (in Japanese), Nippon Kogyo Kaishi, 90, 51- 

56 (1974) (Experimental, Thermodyn., 16) 

This paper, for example, whose title is given in English, is actually written in Japanese. It 

was published in 1974 on pages 51- 56, volume 90 of Nippon Kogyo Kaishi, the Journal of the 

Mining and Metallurgical Institute of Japan. It reports on experimental work that leads to 

thermodynamic data and it refers to 16 cross-references. 

Additional conventions used in citing are: 

# to indicate the source of accepted phase diagrams 

* to indicate key papers that significantly contributed to the understanding of the system. 

Standard reference works given in the list “General References” are cited using their 

abbreviations and are not included in the reference list of each individual system. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_1 


7

8 1 

Introduction 

General References 

[C.A.] Chemical Abstracts - pathways to published research in the world’s journal and patent literature - 

http://www.cas.org/ 

[Curr.Cont.] Current Contents - bibliographic multidisciplinary current awareness Web resource - http://www. 

isinet.com/products/cap/ccc/ 

[E] Elliott, R.P., Constitution of Binary Alloys, First Supplement, McGraw-Hill, New York (1965) 

[G] Gmelin Handbook of Inorganic Chemistry, 8th ed., Springer-Verlag, Berlin 

[H] Hansen, M. and Anderko, K., Constitution of Binary Alloys, McGraw-Hill, New York (1958) 

[L-B] Landolt-Boernstein, Numerical Data and Functional Relationships in Science and Technology (New 

Series). Group 3 (Crystal and Solid State Physics), Vol. 6, Eckerlin, P., Kandler, H. and Stegherr, A., 

Structure Data of Elements and Intermetallic Phases (1971); Vol. 7, Pies, W. and Weiss, A., Crystal 

Structure of Inorganic Compounds, Part c, Key Elements: N, P, As, Sb, Bi, C (1979); Group 4: 

Macroscopic and Technical Properties of Matter, Vol. 5, Predel, B., Phase Equilibria, Crystallographic 

and Thermodynamic Data of Binary Alloys, Subvol. a: Ac-Au … Au-Zr (1991); Springer-Verlag, 

Berlin. 

[Mas] Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, ASM, Metals Park, Ohio (1986) 

[Mas2] Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, 

Ohio (1990) 

[P] Pearson, W.B., A Handbook of Lattice Spacings and Structures of Metals and Alloys, Pergamon Press, 

New York, Vol. 1 (1958), Vol. 2 (1967) 

[S] Shunk, F.A., Constitution of Binary Alloys, Second Supplement, McGraw-Hill, New York (1969) 

[V-C] Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, 

ASM, Metals Park, Ohio (1985) 

[V-C2] Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, 

2nd edition, ASM, Metals Park, Ohio (1991) 



MSIT 1

Index of Alloy Systems 


Index of Ternary Iron Alloy Systems Fe-N-V to Fe-Ti-Zr 

Fe–N–V (Iron – Nitrogen – Vanadium) 

Fe–Na–O (Iron – Sodium – Oxygen) 

Fe–Nb–Ni (Iron – Niobium – Nickel) 

Fe–Nb–P (Iron – Niobium – Phosphorus) 

Fe–Nb–Si (Iron – Niobium – Silicon) 

Fe–Nb–Zr (Iron – Niobium – Zirconium) 

Fe–Nd–Si (Iron – Neodynium – Silicon) 

Fe–Ni–P (Iron – Nickel – Phosphorus) 

Fe–Ni–S (Iron – Nickel – Sulfur) 

Fe–Ni–Sb (Iron – Nickel – Antimony) 

Fe–Ni–Si (Iron – Nickel – Silicon) 

Fe–Ni–Ti (Iron – Nickel – Titanium) 

Fe–Ni–V (Iron – Nickel – Vanadium) 

Fe–Ni–W (Iron – Nickel – Tungsten) 

Fe–Ni–Zn (Iron – Nickel – Zinc) 

Fe–Ni–Zr (Iron – Nickel – Zirconium) 

Fe–O–Pb (Iron – Oxygen – Lead) 

Fe–O–Si (Iron – Oxygen – Silicon) 

Fe–O–U (Iron – Oxygen – Uranium) 

Fe–O–W (Iron – Oxygen – Tungsten) 

Fe–O–Y (Iron – Oxygen – Yttrium) 

Fe–O–Zr (Iron – Oxygen – Zirconium) 

Fe–P–Si (Iron – Phosphorus – Silicon) 

Fe–S–Ti (Iron – Sulfur – Titanium) 

Fe–Si–Ti (Iron – Silicon – Titanium) 

Fe–Si–V (Iron – Silicon – Vanadium) 

Fe–Si–Zr (Iron – Silicon – Zirconium) 

Fe–Sm–Ti (Iron – Samarium – Titanium) 

Fe–Sn–Zr (Iron – Tin – Zirconium) 

Fe–Ti–V (Iron – Titanium – Vanadium) 

Fe–Ti–Y (Iron – Titanium – Yttrium) 

Fe-Ti-Zr (Iron – Titanium – Zirconium) 



MSIT 1 

Index of Alloy Systems 2 

DOI: 10.1007/978-3-540-70890-2_2 


1

Iron – Nitrogen – Vanadium 


Pierre Perrot 

Introduction 

Vanadium has a strong affinity for N and forms fine nitrides and carbonitrides in steels which 

improve their strength and the toughness by pinning the grain growth to a considerable extent. 

Experimental investigations on phase equilibria and thermodynamics, mainly related to the 

nitrogen solubilities in liquid, α and γ phases are gathered in Table 1. Few experimental 

information exists in the ternary phase diagram [1978ElS] and Calphad assessments 

[1991Oht2] are useful to get an insight to the equilibria between phases. A review on the 

phase equilibria in the Fe-N-V system may be found in [1983Rag, 1984Rag, 1987Rag1, 

1993Rag]. A Calphad assessment of the Fe-N-V system has been carried out by [1991Oht2]. 


The Fe-V has been carefully reviewed by [1984Smi] and the thermodynamic assessment 

proposed by [1991Kum] reproduces well the accepted diagram. According to new experimental 

works [2005Ust1, 2005Ust2], the σ phase would be unstable and a phase separation would 

be observed below 650˚C. A further confirmation is needed to accept this new version of the 

Fe-V diagram at low temperatures. The Fe-N phase diagram in the solid state is accepted from 

the review of [1987Wri]. The Calphad assessment carried out by [1991Fri] and justified by the 

model proposed by [1994Fer] gives an insight on the phase equilibria under high nitrogen 

pressures. The N-V phase diagram in the solid state given by [Mas2] is reproduced from the 

extensive review of [1989Car]. A Calphad assessment of the N-V system has been carried out 

by [1991Oht1], then updated by [1997Du]. These assessments do not take into account the 

δ’V 32N 26 phase but agree to propose for the nitrides V 2N and VN incongruent melting points 

under 0.1 MPa N2 higher than those accepted by [Mas2]. The N-V diagram accepted in the 

present report is that proposed by [1997Du]. 


Fe–N–V 3 

The solid phases are shown in Table 2. Three vanadium nitrides are stable. The most stable, 

easily precipitated in steels is VN which presents a large non stoichiometry and may be 

obtained under very low nitrogen potential. The hexagonal subnitride V2N, exhibits a 

structure εFe 3N like, but no solid solutions have been reported between these two phases. 

The iron nitride γ’Fe 4N is characterized by a high saturation magnetization and a low 

coercitivity and many efforts has been devoted to enhance its magnetic properties by metallic 

substitution. Many metastable phases of the type Fe 4–xM xN have been prepared by mechanical 

alloying, but no report seems to exist in which M stands for V. Despite this, self-consistent 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_3 


1

2 3 

Fe–N–V 

band structure calculations were performed for the V 4N, V 3FeN and VFe 3N materials 

[2006San]. They were found non magnetic and their crystal structure calculated at 752.9, 

742.7 and 704.9 pm respectively, whereas twice lattice parameter for Fe 4N gives 757.4 pm. 

[2006San] reports for γ’Fe 4N a lattice parameter of 717.1 pm. 


The nitrogen solubility in liquid (Fe,V) alloys has been considerably investigated as shown in 

Table 1, and was shown to increase with the V content, but the increase of the nitrogen 

dissolved in the melt may be limited by the precipitation of VN for high V content of the alloy. 

A useful empirical expression of the N solubility in liquid alloys at 1580˚C has been proposed 

by [1963Kor]: 

ðmass% NÞ ¼0:043 þ 0:0185 ðmass% VÞþ0:00113 ðmass% VÞ 2 ð< 6 mass% VÞ 

The precipitation is observed when the solubility product (mass% V)(mass% N) is 

reached. As liquid Fe can dissolve a large amount of V before precipitating as VN, the 

solubility product cannot be precisely represented by the product of concentrations, but by 

the product of the activities. Another problem concerns the composition of the VN nitride in 

equilibrium with the liquid alloy. [1965Eva] considers that its composition is V1.41N whereas 

most authors consider that it is VN. The lattice parameter measurement carried out by 

[1987Mor] identifies the precipitated nitride as VN. It is probable that VN in equilibrium 

with iron rich (Fe,V) alloys and that the V content of the nitride increases with that of the 

alloy. According to [1963ElT], a Fe-8V (mass%) alloy precipitates VN once the N content 

reaches 0.20 mass% at 1600˚C under 8 kPa of N2 pressure; a Fe-15V (mass%) alloy precipitates 

VN once the N content reaches 0.27 mass% at 1600˚C under 77 kPa of N2 pressure. 

The nitrogen solubility in liquid alloys seems independent on the temperature for the Fe-1V 

(mass%) [1958Kas]. Below 1 mass% V in the alloy, it decreases when the temperature raises, 

above 1 mass% V in the alloy, it increases with the temperature [1987Mor]. 

The solubility of nitrogen generated by H2-NH3 atmospheres at 400-600˚C on α(Fe,V) 

alloys up to 0.05 mass% V [1955Tur] seems independent on the V content of the alloy. The 

formation of VN is not observed at nitrogen potentials under which iron nitrides are not 

formed. The V content of the alloy was probably too small and the nitrogen solubility 

measured in α and γ alloys [1958Fou, 1962Kor2] up to 1 mass% V was shown to increase 

with the V concentration. 

The solubility product of VN in α and γ alloys has been evaluated by [1962Kor2] and 

accepted by [2004Ked] to model the nitrogen diffusion profile during nitriding: 

In a ðFe; VÞ alloys : log10ðmass% VÞðmass% NÞ ¼2:45 ð7830=TÞ 

In g ðFe; VÞ alloys : log10ðmass% VÞðmass% NÞ ¼2:27 ð7070=TÞ 

At 700˚C, the solubility product of VN in (αFe) is 2.5 · 10 –6 which is in agreement with 

the formation of VN observed by [1973Gul] in an alloy Fe-0.18 mass% V-0.04 mass% N. At 

1350˚C, the solubility product of VN in (γFe) is 0.0082 which is in agreement with the 

observation of [1973Gul] that pure iron may absorb up to 0.2 mass% VN. The solubility 

product of VN in (αFe) has been measured at 5.3 · 10 –6 and 1.7 · 10 –5 at 700 and 800˚C, 

respectively, by [1973Koy] using internal friction measurements. The N solubility under 



MSIT 1

0.1 MPa of N 2 pressure in iron rich alloys (< 2 mass% V) at 1200˚C (α and γ solid alloys) and 

1600˚C (liquid alloy) is shown in Fig. 1. 

Due to the lack of experimental information with the exception of the nitrogen solubilities 

in α, γ and liquid phases, the isothermal sections have been calculated. The isothermal sections 

at 1200 and 1600˚C, presented in Figs. 2 and 3 respectively, are mainly from [1991Oht2] 

slightly modified to take into account the non stoichiometry of the binary compounds and the 

solubility of N into (γFe) according to the accepted Fe-N diagram. Although a partial 

solubility is probable, it has never been measured. 


The vertical section through the Fe-N-V diagram at 3 mass% V calculated by [1991Oht2], is 

shown in Fig. 4. The original figure has been slightly modified in order to remove the very 

improbable shrinkage present at 900 and 1400˚C in the three-phase field α+γ+VN. It looks like 

the binary Fe-N phase diagram calculated by [1991Fri] with an enlarged α domain. The 

isobaric curves have not been calculated, but the nitrogen potentials (0.1 MPa at 1600˚C 

and 0.044 mass% N) increase strongly with the N content. Below 800˚C, they may be obtained 

with H2-NH3 atmospheres, but above this temperature, there is no known mean to impose 

such high nitrogen potentials. The vertical section along the Fe-VN path (< 1 mass% VN) is 

shown in Fig. 5. The easy precipitation of VN in the α and γ solid phases appears clearly in 

both Figs. 4 and 5. In the liquid phase at 1600˚C, VN precipitates under 0.1 MPa N 2 for a V 

content in the alloys higher than 10 mass%. 


Fe–N–V 3 

The interaction coefficient between N and V in liquid iron calculated by [1960Mae] from 

solubility measurements was found e N (V) =(∂ log10 f N / ∂ mass% V) = – 0.11 at 1600-1750˚C, 

where f N = (mass% N in pure Fe) / (mass% N in the alloy). Such a value, is in a very good 

agreement with that calculated from the data of [1958Kas] (–0.095 at 1600˚C) and with 

the later measurements carried out by [1960Peh] (–0.10 at 1606˚C), [1961Rao] (–0.094 at 

1700˚C), [1962Kor1] (–0.106 at 1580˚C), [1963ElT] (–0.094 at 1600˚C), [1965Eva] (–0.093 

at 1600˚C and –0.079 at 1750˚C), [1975Pom] (–0.12 at 1600˚C, –0.099 at 1800˚C and –0.093 at 

1900˚C), [1981Wad] (–0.10 at 1600˚C, –0.087 at 1700˚C and –0.076 at 1800˚C) and [1987Mor] 

(–0.107 at 1600˚C). [1963Kor] proposes a more precise expression of the interaction parameter 

at 1580˚C, which may be used up to 6 mass% V in the alloy: e N (V) = –0.159 + 0.016 

(mass% V), which agrees with the preceding values. [1963ElT] proposes, in the temperature 

range 1600-1740˚C the following expression: e N (V) = 0.075 – 317 / T, which is more representative 

in a wide temperature range than more recent expressions [1981Wad, 1987Mor]. This 

expression, extrapolated at 2200˚C leads to e N (V) = – 0.052 which agrees well with the 

experimental value of –0.062 obtained by [1968Uda] at 2140-2240˚C by arc melting or 

levitation melting under N 2 atmospheres and with the experimental value of – 0.05 obtained 

by [1969Wad] with the same method. 

The interaction coefficient may be expressed in mole fractions. At 1600˚C [1966Sch, 

1987Mor]: ε N (V) =(∂ ln γN / ∂ x V) = – 20 at 1600˚C, where γ N =(x N pure Fe / x N in the 

alloy). For higher V content of the alloy, the preceding primary interaction coefficients cannot 

be used and it is necessary to define secondary and sometimes ternary interaction coefficients 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_3 


3

4 3 

Fe–N–V 

and to take into account the auto-interaction coefficient [2001Hut]. Indeed, under high 

nitrogen pressure (> 0.1 MPa) and high V content (> 6 mass%), N has a strong effect on its 

own activity coefficient. So, [2003Hut] describes the nitrogen solubility in (Fe,V) alloys up to 

45 mass% V between 1800 and 2000˚C by using interaction coefficients of high order. 

The interaction coefficients between N and V in α and γ iron have been calculated by 

[1958Fou] from solubility measurements and found eN (V) = – 2.2, –1.0, –0.47, –0.33 and –0.18 

at 750, 850, 950, 1050 and 1200˚C respectively. The slope of the curve does not seem present a 

break at the α/γ transition of the alloy. These values are confirmed by the measurements of 

[1962Kor2] which proposes e N (V) = – 0.4 at 1000˚C. 

A general discussion on the interaction parameters in alloys may be found in [1966Sch]. 

A method of calculation based on equivalent carbon concentration was developed by 

[1967Sch]. 

Table 3 presents the Gibbs energy of dissolution of N 2 in liquid Fe-V alloys measured by 

[1975Pom]. The enthalpy of dissolution of N2, positive for pure Fe, decreases when the V 

content in the alloy increases, passes through zero for Fe-1V (mass%) then becomes more and 

more negative. The nitrogen solubility in the Fe-1V (mass%) does not change with temperature, 

an observation already made by [1958Kas]. 


Main experimental investigations are gathered in Table 4. Vanadium, which in the liquid state 

absorbs readily nitrogen, greatly increases its solubility in Fe base alloys without VN precipitation. 

By solidification, these alloys precipitate VN, leading to a structural hardening of the 

steel and an improvement of its tribological behavior, mechanical properties, especially under 

fatigue loading and of its corrosion resistance. The easy absorption of N by (Fe,V) liquid alloys 

without VN precipitation allows the preparation of HNS (High Nitrogen Steels, that are steels 

with more than 0.5 mass% N) by using high nitrogen pressures. For instance, a Fe-12 mass% 

Valloy at 1700˚C may absorb 0.503, 0.674, 0.847 and 1.400 mass% N under nitrogen pressures 

of 0.372, 0.743, 1.86 and 2.27 MPa, respectively [2003Siw]. 

Vanadium and nitrogen cosegregation towards the surface has been observed on a Fe-3 

mass% V annealed at 570-740˚C under a N 2-H 2 atmosphere (1 to 10 Pa N 2) leading to a 

nitrogen content of 4 to 30 ppm inside the alloy [1995Ueb]. N segregation gives a twodimensional 

surface compound whose composition is VN 1.0 ±0.1. VN precipitates were also 

observed by nitriding Fe-V alloys up to 3.3 at.% in a salt bath at 570˚C [2003Gou]. VN 

precipitates as platelets, forming tweed structures, typical of a Guinier-Preston zone, due to a 

tetragonal distortion of the matrix. 

Miscellaneous 

The nitrogen diffusion was investigated in the solid [1966Koe, 1973Bel, 1977Bor] and liquid 

[1981Ers] alloys. In solid and liquid alloys, V has for effect to decrease the nitrogen diffusion 

coefficient and to increase the activation energy of the diffusion. In pure αFe, the N diffusion 

coefficient is given by: 

DN /cm 2 ·s –1 = 0.005 exp(–9260 / T), which corresponds to an activation energy of 

77 kJ·mol –1 . In a V added with 0.75 mass% V, the N diffusion coefficient is given by: 



MSIT 1

D N /cm 2 ·s –1 = 0.0066 exp(–13 300 / T), which corresponds to an activation energy of 

110.9 kJ·mol –1 . Using the positron annihilation technique, [1990Wan] observes, on dilute 

Fe-V alloys (0.29 mass% V) annealed at 500˚C under a 80H 2-20NH 3 atmosphere, the formation 

of VN clusters inside the Fe matrix. As V does not diffuse in Fe at so low temperature, it is 

clear that N greatly enhances the V diffusion in Fe. 

The nitrogen diffusion profile during the nitriding of a Fe-Valloy (0.5 and 1.0 mass% V) at 

550-580˚C has been modeled by [2000Gou, 2004Ked]. The increase of the V content affects the 

thickness of the nitrided layer, due to the formation of VN precipitates. After 70 h of diffusion 

at 570˚C, the nitrided layer is 72 μm thick for pure Fe and 215 μm thick for Fe added with 

1 mass% V. [2005Kam] presents a trapping model and points out that a realistic diffusion 

model must take into account both precipitation and trapping. 

The morphologies of the nitrided layers at 580˚C under H 2-NH 3 atmospheres were 

compared by [2005Hos] on two Fe-V alloys (2 and 4 mass% V). The difference observed 

was caused by a discontinuous coarsening reaction occurring on the Fe-4%V alloy, caused by 

an uptake of excess nitrogen in the nitrided zone. It was observed, on the Fe-2V (mass%) 

[2006Hos] that the hydrogen uptake was larger than that necessary to precipitate V as VN and 

to saturate the ferrite matrix. Three types of nitrogen were recognized: nitrogen in the 

stoichiometric VN, nitrogen adsorbed at the (αFe)/VN interface and nitrogen dissolved 

interstitially in the ferrite matrix. The excess nitrogen uptake is partly due to the immobile 

nitrogen at the interface (αFe)/VN and partly due to the mobile nitrogen supersaturated in the 

(αFe) matrix. The supersaturation of the ferrite is due to the misfit stress field surrounding the 

nitride precipitates. The excess nitrogen dissolved at the interface (αFe)/VN was shown to 

decrease with increasing temperature [2007Hos]. 

The presence of V in liquid Fe at 1600˚C was shown to increase the rate of dissolution of 

N 2 by comparison with pure Fe [1995Ono]. 

. Table 1 

Investigations of the Fe-N-V Phase Relations, Structures and Thermodynamics 

Reference Method/Experimental Technique 

[1955Tur] Nitrogen solubility in α(Fe,V) alloys, 

sampling method 

[1958Fou] Nitrogen solubility in α and γ(Fe,V) 

alloys, Sievert’s method 

[1958Kas] Nitrogen solubility in liquid (Fe,V) alloys, 

Sievert’s method 

[1960Mae] Nitrogen solubility in liquid (Fe,V) alloys, 

Sampling method 

[1960Peh] Nitrogen solubility in liquid (Fe,V) alloys, 


[1961Rao] Nitrogen solubility in liquid (Fe,V) alloys, 




MSIT 1 

Fe–N–V 3 

Temperature/Composition/Phase Range 

Studied 

500-600˚C, < 0.05 mass% V, H 2-NH 3 

atmospheres 

750-120˚C, < 0.5 mass% V, < 0.1 MPa of 

N 2 pressures 

1600˚C, < 10 mass% V, < 0.1 MPa of N2 

pressure 

1600-1750˚C, < 8 mass% V, 0.1 MPa of N 2 

pressure 

1606˚C, < 12 mass% V, < 0.1 MPa of N 2 

pressure 

1687-1760˚C, < 20 mass% V, < 0.1 MPa of 

N 2 pressure 

DOI: 10.1007/978-3-540-70890-2_3 


5

6 3 

Fe–N–V 

. Table 1 (continued) 


[1962Kor1] Nitrogen solubility in liquid (Fe,V) alloys, 


[1962Kor2] VN solubility in α (Fe,V) alloys, Sievert’s 

method 

[1963ElT] Nitrogen solubility in liquid (Fe,V) alloys, 


[1963Kor] VN solubility in liquid (Fe,V) alloys, 


[1965Eva] Nitrogen solubility in liquid (Fe,V) alloys, 


[1968Uda] Nitrogen solubility in liquid (Fe,V) arcand 

levitation melted alloys 

[1969Wad] Nitrogen solubility in liquid (Fe,V) 


[1973Gul] VN solubility in α and γFe, phase analysis 

by electron microscopy 

[1973Koy] VN solubility in αFe, internal friction, 

chemical analysis 

[1975Pom] Nitrogen solubility in liquid (Fe,V) 

melted by plasma 

[1978ElS] XRD, Metallography, Electron Probe 

Microanalysis (EPMA) 

[1981Wad] Nitrogen solubility in liquid (Fe,V) 


[1987Mor] Solubility if VN in liquid (Fe,V), XRD, 


[2001Hut] Nitrogen solubility in liquid (Fe,V) 

Levitation melted alloys 

[2003Hut] Nitrogen solubility in liquid (Fe,V) 


[2003Siw] Nitrogen solubility in liquid (Fe,V) 



Studied 

1580˚C, < 12 mass% V, 0.1 MPa of N 2 

pressure 

900-1300˚C, < 1 mass% V, 0.1 MPa of N 2 

pressure 

1600-1750˚C, < 20 mass% V, < 0.1 MPa of 

N 2 pressure 

900-1300˚C, < 1 mass% V, 0.1 MPa of 

N 2 pressure 

1600-1750˚C, < 16 mass% V, 0.1 MPa of 

N 2 pressure 

2140-2240˚C, < 6 mass% V, < 0.1 MPa of 

N 2 pressure 

1800-2200˚C, < 50 mass% V, < 0.1 MPa of 

N 2 pressure 

700-1350˚C, < 0.18 mass% V, 

< 0.04 mass% V 

700-800˚C, < 0.12 mass% V, 

< 0.024 mass% N 

1790-2150˚C, < 11 mass% V, < 0.4 mass% N, 

< 0.1 MPa of N 2 pressure 

1100-1200˚C, Fe-N-V constitution diagram 

(~1 mPa N 2) 

1600-1800˚C, < 15 mass% V, < 0.1 MPa of 

N2 pressure 

1600-1700˚C, < 25 mass% V, < 0.35 mass% 

N, < 0.1 MPa of N 2 pressure 

1900˚C, < 12.2 mass% V, 0.1 to 2.1 MPa of 

N 2 pressure 

1800-2000˚C, < 45 mass% V, 1 kPa to 2.5 

MPa of N 2 pressure 

1700˚C, < 12 mass% V, < 0.4 MPa of N 2 

pressure, < 1.4 mass% N 



MSIT 1

. Table 2 

Crystallographic Data of Solid Phases 

Phase/ 

Temperature 

Range [˚C] 

Pearson Symbol/ 

Space Group/ 

Prototype 

Fe–N–V 3 

Lattice Parameters 

[pm] Comments/References 

α, (αFe,αV,δFe) cI2 

(αV) Im3m a = 302.40 at 25˚C [Mas2] 

< 1910 W dissolves 13 at.% N at 1959˚C 

[1997Du] 

(δFe) 

1538 - 1394 

a = 293.15 [Mas2] 

(αFe) a = 286.65 pure Fe at 20˚C [Mas2] 

< 912 dissolves up to 0.4 at.% N at 590˚C 

α(Fe0.5V0.5) a = 292.0 [1984Smi] 

(γFe) cF4 a = 364.67 at 915˚C [Mas2, V-C2] 

1394 - 912 Fm3m dissolves up to 10.3 at.% N at 650˚C 

Cu [1987Wri] and 1.4 at.% V at 1150˚C 

[1984Smi] 

(εFe) hP2 a = 246.8 at 25˚C, 13 GPa [Mas2] 

P63/mmc Mg 

c = 396.0 triple point α-γ-ε at 8.4 GPa, 430˚C 

σ, VFe tP30 29.6 to 60.1 at.% V 

< 1252 P42/mnm a = 886.5 at 29.6 at.% V [1984Smi] 

σCrFe c = 460.5 

a = 895.0 

c = 462.0 

at 50 at.% V [1984Smi] 

a = 901.5 

c = 464.2 

at 60 at.% V [1984Smi] 

α”Fe16N2 tI* a = 572 ordered fcc structure, metastable 

I4/mmn c = 629 

[1987Wri] 

γ’, Fe4N cP5 a = 378.7 19.4 to 20.6 at.% N. Ordered fcc 

< 680 Pm3m 

Fe4N 

structure [1987Rag2] 

ε, Fe3N hP10 15.8 to 33.2 at.% N [1987Rag2] 

< 580 P6322 a = 469.96 ± 0.03 εFe3NatRT[1999Lei] Fe3N c = 438.04 ± 0.03 

a = 471.8 εFe3N1.10 [2001Lei] 

c = 438.8 Lattice parameters decrease 

slightly with decrease in nitrogen 

content [2001Lei] 

a = 479.1 

c = 441.9 

εFe3N1.39 [2001Lei] 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_3 


7

8 3 

Fe–N–V 



Temperature 

Range [˚C] 


Space Group/ 

Prototype 



ζFe2N oP12 a = 551.2 at 25˚C [1987Rag2] 

< 500 Pbcn b = 482.0 

Fe2N c = 441.6 

βV2N hP3 24.2 to 32.9 at.% N [1984Rag] 

< 2409 P63/mmc a = 283.68 to 284.08 [1984Rag] 

(under 0.1 MPa N2) Fe3N c=454.21 to 455.01 

δVN cF8 33 to 50 at.% N [Mas2] 

< 2119 Fm3m 

(under 0.1 MPa N2) NaCl 

< 3000 

a = 406.62 at 42 at.% N [1984Rag] 

(under 1 GPa N2) a = 413.98 at 50 at.% N [1984Rag] 

δ’V32N26 tP* - 43 to 46 at.% N [Mas2] 

< 520 P42/nmc - 

. Table 3 

Thermodynamic Data of Reaction or Transformation 

Reaction or Transformation 

Temperature 

[˚C] 

Quantity, per mol of 

atoms [J, mol, K] Comments 

½N2 Ð {N} (in Liquid Fe) 2000 ΔrH˚ = + 5600 [1975Pom] 

½N2 Ð {N} (in Liquid Fe + 1 mass% V) 1790-2130 ΔrG˚ = – 340 + 23.0 T [1975Pom] 

½N2 Ð {N} (in Liquid Fe + 2 mass% V) 1790-2110 ΔrG˚ = – 7660 + 25.7 T [1975Pom] 

½N2 Ð {N} (in Liquid Fe + 5.2 mass% V) 1810-2110 ΔrG˚ = – 28700 + 29.7 T [1975Pom] 

½N2 Ð {N} (in Liquid Fe + 7.4 mass% V) 1830-2150 ΔrG˚ = – 42100 + 32.5 T [1975Pom] 

½N2Ð {N} (in Liquid Fe + 11.1 mass% V) 1830-2150 ΔrG˚ = – 61100 + 37.3 T [1975Pom] 

VN Ð {V} + {N} (Ref: 1 mass% in liquid Fe) 1600-1700 ΔrG˚ = 167000 – 83.7 T [1987Mor] 



MSIT 1

. Table 4 

Investigations of the Fe-N-V Materials Properties 

Reference Method / Experimental Technique Type of Property 

[1966Koe] Damping capacity, diffusion coefficient < 800˚C, < 4 mass% V, < 0.4 mass% N 

[1973Bel] X-Ray and electron diffraction, MEB, 

hardness measurements 

[1977Bor] XRD, micrography, thickness and 

hardness measurements 

[1977Kra] XRD, electron microscopy, crystal 

parameters 

[1981Ers] Diffusion coefficient of N in liquid alloys, 

volumetric method 

[1990Wan, 

1993Wan] 

Positron annihilation spectroscopy, 

observation of VN clusters 

400-700˚C, < 9 mass% V, diffusion layer 

formation 

500-900˚C, < 15.6 mass% V, H 2-NH 3 

atmospheres, layer growth kinetics 

< 800˚C, < 2 at.% V, < 3 at.% N, H 2-NH 3 

atmospheres, local atomic arrangements 

1600˚C, < 8 mass% V, 0.1 MPa of N 2 

pressure 

500˚C, Fe + 0.29 mass% V, 80H 2-20NH 3 

atmosphere 

[1995Ono] Isotopic exchange reaction 1600-1750˚C, 0.1 MPa of N 2 pressure, 

kinetics of dissolution 

[1995Ueb] Auger Electron Spectroscopy (AES), low 

energy electron diffraction 

[2003Gou] XRD, TEM, Electron Microprobe 

Microanalysis (EPMA) 

[2005Hos] XRD, SEM, EPMA, hardness 

measurements 


measurements 


measurements 



MSIT 1 

Fe–N–V 3 

570-740˚C, Fe-3 mass% V-N (4 to 30 ppm 

N), 1 to 10 Pa of N 2 pressure, 

Fe-V (< 3.3 at.% V) nitridized at 570˚C in 

a nitriding fused salt bath. VN formation. 

580˚C, 2 and 4 mass% V, H 2-NH 3 

atmospheres, morphology 

580˚C, 2 mass% V, H 2-NH 3 atmospheres, 

excess N uptake 

520-600˚C, 2 mass% V, 9H2-91NH3 

atmospheres, excess N uptake 

DOI: 10.1007/978-3-540-70890-2_3 


9

10 3 

Fe–N–V 

. Fig. 1 

Fe-N-V. The Fe rich corner at 1200 and 1600˚C under 0.1 MPa of N 2 pressure 



MSIT 1

. Fig. 2 

Fe-N-V. Isothermal section at 1200˚C 



MSIT 1 

Fe–N–V 3 

DOI: 10.1007/978-3-540-70890-2_3 


11

12 3 

Fe–N–V 

. Fig. 3 

Fe-N-V. Isothermal section at 1600˚C 



MSIT 1

. Fig. 4 

Fe-N-V. Partial vertical section at 3 mass% V 



MSIT 1 

Fe–N–V 3 

DOI: 10.1007/978-3-540-70890-2_3 


13

14 3 

Fe–N–V 

. Fig. 5 

Fe-N-V. Calculated Fe-VN partial vertical section 



MSIT 1

References 

Fe–N–V 3 

[1955Tur] Turkdogan, E.T., Ignatowicz, S., Pearson, J., “The Effect of Alloying Elements on the Solubility of 

Nitrogen in Iron. II. The Solubility of Nitrogen in α-Iron Containing up to 0.051% Vanadium”, J. Iron 

Steel Inst., 181, 227–231 (1955) (Experimental, Phase Relations, 22) 

[1958Fou] Fountain, R.W., Chipman, J., “Solubility and Precipitation of Vanadium Nitride in α- and γ-Iron”, 

Trans. Met. Soc. AIME, 212, 737–748 (1958) (Experimental, Phase Relations, Thermodyn., 29) 

[1958Kas] Kashyap, V.C., Parlee, N., “Solubility of Nitrogen in Liquid Iron and Iron Alloys”, Trans. Met. Soc. 

AIME, 212, 86–91 (1958) (Experimental, Phase Relations, Thermodyn., 19) 

[1960Mae] Maekawa, S., Nakagawa, Y., “Solubility of Nitrogen in Liquid Iron and Iron Alloys. II. Effect of Nickel, 

Cobalt, Molybdenum, Chromium and Vanadium on the Solubility in Liquid Iron” (in Japanese), Tetsu 

to Hagane, 46(9), 972–976 (1960) (Experimental, Phase Relations, Thermodyn., 8) 

[1960Peh] Pehlke, R.D., Elliott, J.F., “Solubility of Nitrogen in Liquid Iron Alloys. I. Thermodynamics”, Trans. 

Metall. Soc. AIME, 218, 1088–1101 (1960) (Experimental, Phase Relations, Thermodyn., 32) 

[1961Rao] Rao, M.M., Parlee, N., “The Solubility of N in Liquid Fe-V and Fe-Ti Alloys and the Equilibrium in 

Reaction xTi + N = δTi xN” (in French), Mem. Sci. Rev. Met., 58(1), 52–60 (1961) (Experimental, Phase 

Relations, Thermodyn., 6) 

[1962Kor1] Korolev, L.G., Morozov, A.N., “Solubility of N in Liquid Fe-V Alloys” (in Russian), Izv. Vyss. Uchebn. 

Zaved., Chern. Metall., 5(7), 27–30 (1962) (Experimental, Phase Relations, 5) 

[1962Kor2] Korolev, L.G., Morozov, A.N., “Equilibrium of N with V in γFe” (in Russian), Izv. Vyss. Uchebn. Zaved., 

Chern. Metall., 5(9), 39–42 (1962) (Experimental, Phase Relations, Thermodyn., 4) 

[1963ElT] El Tayeb, N.M., Parlee, N.A.D., “The Solubility of Nitrogen and the Precipitation of Vanadium Nitride 

in Liquid Iron-Vanadium Alloys”, Trans. Met. Soc. AIME, 227, 929–934 (1963) (Experimental, Phase 


[1963Kor] Korolev, L.G., Morozov, A.N., “Formation of V Nitride in Liquid Fe” (in Russian), Izv. Vyss. Uchebn. 

Zaved., Chern. Metall., 6(4), 45–49 (1963) (Experimental, Phase Relations, Thermodyn, 3) 

[1965Eva] Evans, D.B., Pehlke, R.D., “Equilibria of Nitrogen with Refractory Metals Titanium, Zirconium, 

Columbium, Vanadium, and Tantalum in Liquid Iron”, Trans. Met. Soc. AIME, 233, 1620–1624 (1965) 

(Experimental, Phase Relations, Thermodyn., 14) 

[1966Koe] K̅ster, W., Horn, W., “Damping Investigation on Nitrided Iron-Molybdenum and Iron-Vanadium 

Alloys” (in German), Arch. Eisenhuettenwes., 37, 245–252 (1966) (Experimental, Morphology, Mechan. 

Prop., Transport Phenomena, 22) 

[1966Sch] Schenck, H., Steinmetz, E., “Activity, Standart Condition and Coeffitient of Activity” (in German), 

Stahleisen-Sonderberichte, Düsseldorf: Verlag Stahleisen, (7), 1–36 (1966) (Thermodyn., Review, 161) 

[1967Sch] Schεrmann, E., Kunze, H.D., “Equivalent Interaction Parameters fort he N and S Solubilities, Activities 

and Activity Coefficients in Three- and Multicomponent Alloys at 1600˚C” (in German), Giessereiforschung, 

19, 101–108 (1967) (Theory, Calculation, Thermodyn., 10) 

[1968Uda] Uda, M., Wada, T., “Solubility of Nitrogen in Arc-Melted and Levitation-Melted Iron and Iron Alloys”, 

Trans. Nat. Res. Inst. Met. (Jpn.), 10(2), 79–91 (1968) (Experimental, Phase Relations, Thermodyn., 40) 

[1969Wad] Wada, H., “Solubility of Nitrogen in Molten Fe-V Alloy”, Trans. Iron Steel Inst. Jpn., 9, 399–403 (1969), 

translated from J. Jpn Inst. Met., 33, 720 (1969) (Experimental, Morphology, Phase Relations, Thermodyn., 

8) 

[1973Bel] Belotskiy, A.V., Marchevskaya, E.I., Permyakov, V.G., “Nitride-Phase Formation in Fe-V-N System”, 

Russ. Metall., (3), 103–105 (1973) (Experimental, Phase Relations, Transport Phenomena, 8) 

[1973Gul] Gulyaev, A.P., Anashenko, V.N., Karchevskaya, N.I., Larina, O.D., Matrosov, Yu.I., “Solubility of 

Vanadium and Niobium Nitrides in Iron”, Met. Sci. Heat Treat., 15(8), 643–645 (1973), translated from 

Metalloved. Term. Obrab. Met., (8), 6-8 (1973) (Experimental, Kinetics, Morphology, Phase Relations, 4) 

[1973Koy] Koyama, S., Ishii, T., Narita, K., “Solubility of Vanadium Carbide and Nitride in Ferritic Fe” (in 

Japanese), J. Jpn. Inst. Met., 37(2), 191–196 (1973) (Experimental, Phase Relations, 23) 

[1975Pom] Pomarin, Yu.M., Grigorenko, G.M., Lakomskiy, V.I., “Solubility of Nitrogen in Liquid Iron Alloys with 

Vanadium or Niobium”, Russ. Metall., (5), 61–65 (1975), translated from Izv. Akad. Nauk SSSR, Met., 

(5), 74-77 (1975) (Experimental, Phase Relations, Thermodyn., 15) 

[1977Bor] Bor, S., Atasoy, Ö.E., “The Nitriding of Fe-V Alloys”, Metall. Trans. A, 8A(6), 975–979 (1977) (Experimental, 

Morphology, Kinetics, Surface Phenomena, 14) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_3 


15

16 3 

Fe–N–V 

[1977Kra] Krawitz, A., “X-Ray Studies of Fe-Mo and Fe-V Alloys Nitrided by Constant Activity Aging”, Scr. 

Metall., 11(2), 117–122 (1977) (Crys. Structure, Experimental, 17) 

[1978ElS] El-Shahat, M.F., Holleck, H., “The Constitution of the Systems V-(Fe,Co,Ni,)-N” (in German), 

Monatsh. Chem., 109(1), 193–207 (1978) (Crys. Structure, Experimental, Morphology, Phase Diagram, 

Phase Relations, 14) 

[1981Ers] Ershov, G.S., Kasatkin, A.A., “Influence of Alloying Elements on the Diffusion of Nitrogen in Liquid 

Iron”, Russ. Metall., (3), 24–27 (1981) (Experimental, Transport Phenomena, 13) 

[1981Wad] Wada, H., Pehlke, R.D., “Nitrogen Solubility in Liquid Fe-V and Fe-Cr-Ni-V Alloys”, Metall. Trans. B, 

12B, 333–339 (1981) (Experimental, Phase Relations, Thermodyn., 10) 

[1983Rag] Raghavan, V., “The Fe-N-V (Iron-Nitrogen-Vanadium) System”, Trans. Ind. Inst. Met., 36(4/5), xviixxiii 

(1983) (Crys. Structure, Phase Diagram, Phase Relations, Review, 36) 

[1984Rag] Raghavan, V., “The Fe-N-V (Iron-Nitrogen-Vanadium) System”, Bull. Alloy Phase Diagrams, 5(2), 

194–198 (1984) (Crys. Structure, Phase Diagram, Phase Relations, Review, 36) 

[1984Smi] Smith, J.P., “The Fe-V (Iron-Vanadium) System”, Bull. Alloy Phase Diagrams, 5(2), 184–194 (1984) 

(Crys. Structure, Phase Diagram, Review, Thermodyn., 99) 

[1987Mor] Morita, Z., Tanaka, T., Yanai, T., “Equilibria of Nitride Forming Reactions in Liquid Iron Alloys”, 

Metall. Trans. B, 18B, 195–202 (1987) (Crys. Structure, Experimental, Phase Relations, Thermodyn., 29) 

[1987Rag1] Raghavan, V., “The Fe-N-V (Iron-Nitrogen-Vanadium) System” in “Phase Diagrams of Ternary Iron 

Alloys”, Ind. Inst. Techn., Delhi, 1, 211–216 (1987) (Crys. Structure, Phase Diagram, Phase Relations, 

Review, 32) 

[1987Rag2] Raghavan, V., “The Fe-N (Iron-Nitrogen) System” in “Phase Diagrams of Ternary Iron Alloys”, Ind. Inst. 

Techn., Delhi, 1, 143–144 (1987) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 7) 

[1987Wri] Wriedt, H.A., Gokcen, N.A., Nafziger, R.H., “The Fe-N (Iron-Nitrogen) System”, Bull. Alloy Phase 

Diagams, 8(4), 355–377 (1987) (Crys. Structure, Phase Diagrams, Phase Relations, Thermodyn., 

Review, *, #, 126) 

[1989Car] Carlson, O.N., Smith, J.F., Nafziger, R.H., “The V-N (Vanadium-Nitrogen) System” in “Phase Diagams 

of Binary Vanadium Alloys”, ASM Int., Materials Park, OH, 148–158 (1989) (Phase Diagram, Phase 

Relations, Crys. Strucrure, Thermodyn., Review, 59) 

[1990Wan] Wang, X.-G., Zhang, H., “A Vacancy Complex in the Dilute Fe-V-N Alloy Identified by Positron 

Annihilation Spectroscopy”, Phys. Status Solidi A, 119(1), K15-K19 (1990) (Crys. Structure, Experimental, 

Transport Phenomena, 7) 

[1991Fri] Frisk, K., “A Thermodynamic Evaluation of the Fe-Ni-N System”, Z. Metallkd., 82, 59–66 (1991) (Phase 

Diagram, Assessment, Thermodyn., 36) 

[1991Kum] Kumar, K.C.H., Raghavan, V., “A Thermodynamic Reassessment of the Fe-V System”, Calphad, 15(3), 

307–314 (1991) (Phase Diagram, Thermodyn., Assessment, 24) 

[1991Oht1] Ohtani, H., Hillert, M., “A Thermodynamic Assessment of the V-N System”, Calphad, 15(1), 11–24 

(1991) (Phase Diagram, Assessment, Thermodyn., 27) 

[1991Oht2] Ohtani, H., Hillert, M., “A Thermodynamic Assesment of the Fe-N-V System”, Calphad, 15(1), 25–39 

(1991) (Calculation, Experimental, Phase Diagram, Phase Relations, Thermodyn., 24) 

[1993Rag] Raghavan, V., “Fe-N-V (Iron-Nitrogen-Vanadium)”, J. Phase Equilib., 14(5), 631–632 (1993) (Phase 

Diagram, Phase Relations, Review, 7) 

[1993Wan] Wang, X.-G., Zhang, H., “Precipitation in Dilute Fe-V-N Alloy”, Acta Metall. Sin., 29(5), A199-A202 

(1993) (Crys. Structure, Experimental, Transport Phenomena, 12) 

[1994Fer] Fernandez-Guillermet, A., Du, H., “Thermodynamic Analysis of the Fe-N System Using the 

Compound-Energy Model with Prediction of the Vibrational Entropy”, Z. Metallkd., 85(3), 154–163 

(1994) (Phase Diagrams, Theory, Assessment, 75) 

[1995Ono] Ono, H., Morita, K., Sano, N., “Effect of Ti, Zr, V and Cr on the Rate of Nitrogen Dissolution 

into Molten Iron”, Met. Mat. Trans. B, 26B(5), 991–995 (1995) (Experimental, Kinetics, Surface 

Phenomena, 11) 

[1995Ueb] Uebing, C., “Cosegregation-Induced Phase Transition on Fe-3%V-N (110): The Formation of a VN 

Surface Compound”, Surf. Sci., 341(1-2), L1125–L1130 (1995) (Experimental, Interface Phenomena, 


[1997Du] Du, Y., Schmid-Fetzer, R., Ohtani, H., “Thermodynamic Assessment of the V-N System”, Z. Metallkd., 

88(7), 545–556 (1997) (Assessment, Experimental, Phase Relations, Review, Thermodyn., 72) 



MSIT 1

Fe–N–V 3 

[1999Lei] Leineweber, A., Jacobs, H., Hüning, F., Lueken, H., Schilder, H., Kockelmann, W., “ε-Fe 3N: 

Magnetic Structure, Magnetization and Temperature Dependent Disorder of Nitrogen”, J. Alloys 

Compd., 288(1-2), 79–87 (1999) (Experimental, Crys. Structure, 40) 

[2000Gou] Goune, M., Belmonte, T., Fiorani, J.M., Michel, H., “Modelling of Diffusion-Precipitation in Nitrided 

Alloyed Iron”, Thin Solid Films, 377, 543–549 (2003) (Calculation, Interface Phenomena, Phase Relations, 

27) 

[2001Hut] Hutny, A., Siwka, J., “Investigation of Nitrogen Solubility in Liquid Fe-V Alloy with the Use of 

Levitation Technique”, Arch. Metall., 46(2), 197–206 (2001) (Experimental, Phase Relations, Thermodyn., 

12) 

[2001Lei] Leineweber, A., Jacobs, H., Hünning, F., Luecken, H., Kockelmann, W., “Nitrogen Ordering and 

Ferromagnetic Properties of ε-Fe3N1+x (0.10 < x < 0.39) and ε-Fe3(N0.80C0.20)1.38”, J. Alloys Compd., 316, 

21–38 (2001) (Experimental, Crys. Structure, 47) 

[2003Gou] Goune, M., Belmonte, T., Redjaimia, A., Weisbecker, P., Fiorani, J.M., Mochel, H., “Thermodynamic 

and Structure Studies on Nitrided Fe-1.62%Mn and Fe-0.56%V Alloys”, Mater. Sci. Eng. A, 351, 23–30 

(2003) (Crys. Structure, Experimental, Interface Phenomena, Phase Diagram, Phase Relations, 22) 

[2003Hut] Hutny, A., Siwka, J., “The Dependence of Activity Coefficient on Intensive Thermodynamic Parameters 

in a Liquid Fe-N-V Alloy”, Mater. Sci. Forum, 426-432, 963–968 (2003) (Experimental, Phase Relations, 

Thermodyn., 10) 

[2003Siw] Siwka, J., Kaputkina, L.M., Shaidurova, E.S., Hutny, A., “The Crystallization, Structure and Work 

Hardening of Casting Fe-N-V Alloys”, Mater. Sci. Forum, 426-432, 4405–4410 (2003) (Experimental, 

Mechan. Prop., Phase Relations, 15) 

[2004Ked] Keddam, M., Djeghlal, M.E., Barrallier, L., Hadjadj, R., “A Computer Simulation of Nitrogen Profiles in 

Fe-V-N Ternary System”, J. Alloys Compd., 378(1-2), 163–166 (2004) (Calculation, Transport Phenomena, 

Kinetics, 10) 

[2005Hos] Hosmani, S.S., Schacherl, R.E., Mittemeijer, E.J., “Nitriding Behavior of Fe-4 wt% V and Fe-2 wt% V 

Alloys”, Acta Mater., 53(7), 2069–2079 (2005) (Experimental, Interface Phenomena, Mechan. Prop., 

Morphology, 31) 

[2005Kam] Kamminga, J.D., Janssen, G.C.A.M., “Calculation of Nitrogen Depth Profiles in Nitrided Fe-Mn and 

Fe-V”, Surf. Coat. Technol., 200(1-4), 909–912 (2005) (Calculation, Transport Phenomena, Kinetics, 10) 

[2005Ust1] Ustinovshchikov, Yu.I., Pushrarev, B.E., Sapegina, I.V., “Mechanism of Sigma-Phase Formation in the 

Fe-V System”, Inorg. Mater. (Engl. Trans.), 41(8), 822–826 (2005), translated from Neorg. Mater., 41(8), 

938-943 (2005) (Crystal Structure, Experimental, Mechan. Prop., Morphology, Phase Diagram, Phase 

Relations, 12) 

[2005Ust2] Ustinovshikov, Y., Pushkarev, B., Sapegina, I., “Phase Transformations in Alloys of the Fe-V System”, 

J. Alloys Compd., 398(1-2), 133–138 (2005) (Crystal Structure, Experimental, Mechan. Prop., Phase 

Diagram, Phase Relations, 9) 

[2006Hos] Hosmani, S.S., Schacherl, R.E., Mittemeijer, E.J., “Nitrogen Uptake by an Fe-V Alloy: Quantitative 

Analysis of Excess Nitrogen”, Acta Mater., 54(10), 2783–2792 (2006) (Experimental, Interface Phenomena, 

Kinetics, Morphology, 38) 

[2006San] Dos Santos, A.V., Krause, J.C., Kuhnen, C.A., “Electronic Structure Calculations and Ground State 

Properties of V 4N, FeV 3N and VFe 3N Nitrides and Ordered FeV 3 and VFe 3 Compounds”, Physica B, 382 

(1-2), 290–299 (2006) (Crys. Structure, Electronic Structure, Calculation, 43) 

[2007Hos] Hosmani, S.S., Schacherl, R.E., Mittemeijer, E.J., “Kinetics of Nitriding Fe-2 wt% V Alloy: Mobile and 

Immobile Excess Nitrogen”, Metall. Mater. Trans. A, 38A(1), 7–16 (2007) (Experimental, Kinetics, 28) 

[Mas2] Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio 

(1990) 

[V-C2] Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, 2nd 

edition, ASM, Metals Park, Ohio (1991) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_3 


17

Iron – Sodium – Oxygen 


Kostyantyn Korniyenko, Hans Leo Lukas 

Introduction 

Knowledge of the phase equilibria in the iron-sodium-oxygen system and free energies of 

formation of sodium ferrites at elevated temperatures is necessary, in the first instance, with a 

view to analyze the corrosion behavior of sodium in nuclear reactors and to address the problem 

of scabbing and scaffolding in blast furnaces that is due to high alkali content. Information about 

phase relations in the Fe-Na-O system is presented in literature by the Fe 3O 4-NaFeO 2 quasibinary 

section [1984Dai2], liquidus surface of the partial FeO-Fe 2O 3-NaFeO 2 system [1984Dai2], 

isothermal sections and phase relations at different temperatures and composition ranges 

[1975Cla, 1976Bal2, 1977Kni, 1981Lin, 1984Dai2, 1986Igu, 1993Sri, 1999Kal, 2003Hua2, 

2003Lyk] and temperature-composition sections [1940Kni, 1960The, 1962The, 1984Dai1, 

1984Dai2]. Crystal structure data obtained by powder- or single crystal X-ray diffraction are 

published by [1959Col, 1960The, 1962Roo, 1962The, 1963Sch, 1967Rom, 1970Gro, 1971Tsc, 

1974Bar, 1974Rie, 1975Cla, 1975Kol, 1976Bal1, 1976Bal2, 1977Bra, 1977Kni, 1978Bra1, 

1978Bra2, 1978Bra3, 1980Kes, 1981Kes, 1981Oka, 1985Fru, 1986Igu, 1997Ded, 2002Ama, 

2003Sob1, 2003Sob2]. Thermodynamic aspects of the Fe-Na-O system are reflected in 

[1970Gro, 1977Kni, 1977Sha, 1981Lin, 1984Ban, 1984Dai1, 1984Dai2, 1985Ban1, 1985Ban2, 

1987Yam, 1988Bha, 1996Zha, 1999Kal, 2003Hua1, 2003Hua2, 2003Lyk]. The applied experimental 

techniques as well as the studied temperature and composition ranges are listed in 

Table 1. Reviews of literature data present information concerning phase equilibria and crystal 

structures [1989Rag], thermodynamics [1981Lin, 1999Kal] as well as systematics of crystal 

structures of the Fe-Na-O phases [1978Zve, 1982Bau, 1998Wu, 2000Mat, 2003Mue]. 

In future further studies are desirable on the liquidus and solidus surfaces in the area FeO- 

Na 2O-NaO 3-Fe 2O 3 as well as on invariant equilibria. More details of isothermal sections at 

different temperatures would be useful. New informations may help to find new practical 

applications of sodium ferrites. 


The Fe-Na, Fe-O and Na-O binary systems are accepted as compiled in [Mas2]. The assessment 

of the Na-O system is published with more details by [1987Wri]. 


Fe–Na–O 4 

Crystallographic data of all known unary, binary and ternary solid phases are compiled in 

Table 2. Compositions of the all reported ternary phases, except the τ 9 and τ 12 phases, lie along 

the Na 2O-FeO or Na 2O-Fe 2O 3 sections. The composition of the τ 6 phase, established by 

[1959Col, 1962The, 1999Kal] as“Na 10Fe 16O 29”, was later refined by [1962Roo, 1967Rom, 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_4 


1

2 4 

Fe–Na–O 

1987Yam, 1996Zha, 1999Kal]tobe“Na 3Fe 5O 9”. For the τ 2 phase the standard Gibbs energy of 

formation was determined by [1984Dai1] using emf, but no crystal structure data are known. 

For many of the ternary phases the temperature range of stability is not known, except the 

temperature of preparation. The crystal structures of the phases τ 11, τ 12 and τ 13 also are 

unknown and need further experimental clarification. 


The section Fe 2O 3-Na 2O is quasibinary, at least in solid state at lower temperatures. In the 

range Fe 2O 3-NaFeO 2 [1940Kni, 1984Dai1] assume a simple eutectic near 1150˚C and Na/(Na 

+Fe) = 0.36, whereas [1960The, 1962The] found in solid state the τ 6 phase, stable between 

1100 and 755˚C. Additionally they found a metastable solid solution of Na 2OinγFe 2O 3, 

decomposing on heating above 650˚C. The pure Fe2O3 before melting decomposes into Fe3O4 

and O2 gas. Thus the two-phase field L + Fe2O3 must end before it reaches the Fe2O3 side of the 

section. The liquidus temperature of NaFeO 2 is assumed as 1330˚C [1940Kni, 1984Dai1]. 

Between NaFeO 2 (τ 1´´´-τ 1´) and Na 2O there are at least five more phases in this quasibinary 

section, well established by the determination of their crystal structures: Na 4Fe 2O 5 (τ 4), 

Na 14Fe 6O 16 (τ 8), Na 3FeO 3 (τ 10), Na 8Fe 2O 7 (τ 5) and Na 5FeO 4 (τ 7). On the temperature ranges 

of stability and on equilibria with melt no experimental data are published for these phases. A 

further phase, τ 13, between τ 6 and τ 1´, postulated by [1981Lin], was denied by [1962The, 

1999Kal]. In Fig. 1 the Fe rich part of this section is constructed. The equilibria between gas, 

liquid, Fe2O3 and Fe3O4 must be taken as tentative only. The Fe rich liquid, due to Fe +2 ions 

does not reach the section and Na rich liquid may dissolve more O than corresponding to the 

section, due to peroxide or ozonide ions known in the binary Na-O liquid. On the transition 

between both cases data are lacking. 

The section FeO-Na 2O is quasibinary in the range Na 2FeO 2-Na 2O[1984Dai1, 1984Dai2]. 

Between Na 2FeO 2 and FeO it is clearly a not quasibinary isopleth, Fig. 2. At lower temperatures 

also the range Na 2OtoNa 4FeO 3 looses the quasibinary character. [2003Hua2] calculated 

an invariant reaction: Na(liq) + Na4FeO3 Ð Na2O+(αFe) at 421˚C. This temperature may be 

a reasonable estimate. [1993Sri] found this reaction experimentally and located it somewhere 

between 353 and 487˚C. 

The Fe 3O 4-NaFeO 2 section is approximately quasibinary. The Fe 3O 4 phase has some 

homogeneity range towards a composition NaFe 5O 8, corresponding to the spinel structure 

of γFe 3O 4, in which the divalent Fe +2 ions may be replaced by 0.5(Fe +3 +Na +1 ). Due to the 

difference between this direction and the section plane the tie lines of the two-phase fields 

containing γFe 3O 4 are slightly outside the section plane. Contrary to a strictly quasibinary 

section all these fields contain a trace of FeO and thus are three-phase fields. Figure 3 shows 

this approximately quasibinary section as published by [1984Dai2] with correction of a typing 

error. The horizontal lines at ca. 1150 and 980˚C correspond to the invariant four-phase 

equilibria L Ð γFe 3O 4 + αFeO + τ 1´´´ and τ 1´´´ Ð τ 1´´, γFe 3O 4, αFeO, respectively. 


[1984Dai2] constructed the liquidus surface of the FeO-Fe2O3-NaFeO2 partial system. These 

authors mention four invariant four-phase reactions. In Fig. 4 the corresponding reaction 



MSIT 1

scheme is tentatively constructed. It covers the area Fe-Na 2FeO 2-NaFeO 2-Fe 2O 3. The τ 6 phase 

is tentatively included, assuming no participation in an invariant equilibrium. The three-phase 

equilibria of the quasibinary part Na 2O-Na 2FeO 2 can be approximated as degenerate fourphase 

equilibria with Fe in equilibrium. By this consideration the congruent melting point of 

Na 2FeO 2 in the quasibinary part of the Na 2O-FeO section is also a degenerate maximum of the 

three-phase equilibrium L + Fe + Na 2FeO 2. Thus only the formation of the three-phase 

equilibrium L + τ1 + τ2 remains unsolved in the reaction scheme. The compositions of liquid 

in the invariant equilibria are too unprecise to justify a tabulation. In Fig. 4 the polymorphic 

transformations of (Fe) and NaFeO 2 (τ 1) are neglected. As at both compositions all phases are 

nearly stoichiometric, all these transformations are degenerate with the equations (δFe) Ð 

(γFe), (γFe) Ð (αFe), τ 1´´´ Ð τ 1´´ or τ 1´´ Ð τ 1´. All other phases participating remain in 

equilibrium at higher and lower temperatures without taking part at the reactions. Phase τ 12 

was not mentioned by [1984Dai2] and is not implemented in Fig. 4. 

Outside the range of Fig. 4 the existence of the invariant four-phase equilibrium 

L(Na) + Na4FeO3 Ð (Fe) +Na2O is well established, its temperature is inside the interval 

487-353˚C [1993Sri], but could not be located more precisely. 

Liquidus, Solidus and Solvus Surfaces 

The liquidus surface projection of the partial FeO-Fe 2O 3-NaFeO 2 system is shown in Fig. 5, 

based on [1984Dai2]. Isotherms at the temperatures of 1300, 1400 and 1500˚C are plotted. No 

data concerning solidus or solvus surfaces were found in literature. 


Fe–Na–O 4 

The isothermal section of the partial Fe-Fe 2O 3-NaFeO 2 system at 1000˚C is shown in Fig. 6,as 

constructed by [1986Igu], based on experimental studies of the FeO-Na 2O solid solution in 

equilibrium with Ar-H 2-H 2O mixtures. The shapes of the single phase fields of the FeO-Na 2O 

and Fe3O4-Na2O solid solutions agree well with the findings of [1975Cla, 1976Bal2, 2003Lyk], 

except, that [1976Bal2, 2003Lyk] postulate the existence of τ12, which is not mentioned by 

[1975Cla, 1984Dai2, 1986Igu]. [1986Igu] also ignored the τ 6 phase, which is reported to be 

stable at 1000˚C [1962The, 1999Kal]. 

Participation of the τ 6 phase in equilibria at 1000˚C was also reported in the works of 

[1960The] and [1962The, 1999Kal] devoted to constitution of the NaFeO 2-Fe 2O 3 temperature-composition 

section. The partial isothermal section at 1000˚C in the FeO-Fe 3O 4- 

NaFe 5O 8-NaFeO 2 range was also experimentally constructed by [2003Lyk]. These authors 

report the τ13 phase, but do not show the τ6 phase. In general, their data conform to the data of 

[1986Igu] satisfactorily. In their studies of corrosion of steel by liquid Na [1977Kni] found at 

650˚C the τ 3 phase in equilibrium with (αFe) and liquid sodium, while at 400˚C the tie line Naτ 

3 is replaced by an equilibrium between Na 2O and (αFe). In the calculations of [2003Hua2] 

the corresponding four-phase reaction was located at 421˚C. [1993Sri] experimentally confirmed 

this four-phase reaction to happen between 353 and 487˚C. [1981Lin] used the 

SOLGAMIX-PV computer program to calculate phase equilibria in the temperature range 

from 447 to 607˚C in the partial Na-Na 2O-Fe 2O 3-Fe system. They reported the ternary phases 

τ1, τ2, τ3, τ5, τ6, τ7, τ10 and τ13 to take part in equilibria in this temperature interval. However, 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_4 


3

4 4 

Fe–Na–O 

they do not mention the eutectoid decomposition of FeO at 570˚C, due to which FeO should 

not take part in equilibria far below 570˚C. The 595˚C isothermal section, constructed by 

[1984Dai2] from their experimental data (Fig. 7), differs as far as the three iron oxides FeO, 

Fe 3O 4 and Fe 2O 3 all are in equilibrium with NaFeO 2 (τ 1), whereas [1981Lin] show them in 

equilibrium with Na 3Fe 5O 9 (τ 6)orNa 4Fe 6O 11 (τ 13). [1984Dai2] left the phases τ 4, τ 8, τ 10, τ 5 

and τ7 outside their investigated range. [2003Hua2] published six calculated isothermal 

sections between 25 and 727˚C. In this calculation they did not include the phases τ2, τ4, τ6, 

τ 8, τ 9, τ 11, τ 12 and τ 13. The thermodynamic dataset used for the calculation is published. Apart 

from the excluded phases these sections agree well with Fig. 7. The phase τ 5 appears to be 

stable only above 364˚C and the invariant reaction L(Na) + Na 4FeO 3 Ð Fe +Na 2O is located at 

421˚C. Some of the dashed lines in the O rich part of Fig. 7 may be replaced by equilibria with 

Na- and O rich liquid. 


Besides the partially or approximately quasibinary sections shown in Figs. 1 to 3 the temperature-composition 

section NaFeO 2-FeO is shown in Fig. 8 based on data of [1984Dai1, 

1984Dai2]. The authors qualify this section as qualitative representation of the phases in 

this section. 


Information about thermodynamic properties of the Fe-Na-O alloys is widely represented in 

the literature. Data concerned the reactions are listed in Table 3. The chemical equilibria of 

gas-slag reactions have been studied by [1984Ban, 1985Ban1, 1985Ban2] to clarify the effect of 

soda on the thermodynamic properties of slags in the hot metal treatment. The FeO-Na 2O 

slags were studied at 1610˚C being equilibrated with p CO2 = 1.013 bar by using a platinum 

crucible. The influence of slag composition on the activity of iron oxide and the Fe 3+ /Fe 2+ 

ratios has been determined. It has been clarified, that the results can be expressed in terms of 

the Lumsden’s regular solution model over a wide range of compositions. [1984Dai1], besides 

the results presented in Table 3, also have estimated the standard Gibbs energies of formation 

of the compounds Na 2FeO 4,Na 2FeO 2 and Na 4FeO 3 referred to the pure elements iron, sodium 

and oxygen. 

Table 4 presents results of vapor pressure measurements. The oxygen and sodium partial 

pressures were calculated by [1984Dai1] from the Gibbs energy functions. [1984Dai2] 

obtained an expression for the oxygen partial pressure of the three-phase equilibrium α + 

(Fe) + Na2Fe2O4 in the temperature range 760 to 910˚C. Oxygen and sodium potential ranges 

at 650˚C for the stability of selected equilibria in the Fe-Na-O system were determined by 

[1977Kni]. 

[2003Lyk] proposed a thermodynamic model for solid solutions of sodium in the α phase, 

that provides a possibility to establish a relation between the equiliubrium oxygen pressure, 

composition of the α phase and temperature. 

Thermodynamic calculations of isothermal sections of the Fe-Na-O system at the temperatures 

up to 727˚C were carried out by [2003Hua2] using the Thermo-Calc code. Thermodynamic 

data of the ternary phases Na4FeO3(s), Na3FeO3(s), Na5FeO4(s) and Na8Fe2O7(s) 



MSIT 1

have been assessed and compiled to a database by reviewing literature data together with DSC 

and vapor pressure measurements conducted by the authors themselves. 


Sodium ferrites have been used, in particular, as reference electrodes in conjunction with 

sodium-iron-conducting solid electrolytes and, more recently, in sodium and antimony 

sensors, because of their good electronic conductivity [1996Kal, 1996Zha, 1999Kal], which 

produces a rapid response of the sensor. Literature data about properties of the Fe-Na-O alloys 

concern mainly the magnetic properties (Table 5). The magnetic interaction in the structural 

units {Fe 2O 7} 8– , built of two corner-sharing FeO 4 tetrahedra, in the τ 5 phase was studied by 

[1981Kes] in the temperature range from 4.2 to 500 K (–269 to 227˚C). The hypothesis of 

magnetically isolated {Fe 2O 7} 8 groups was corroborated by Mössbauer spectroscopy between 

1.5 and 77 K (–271.7 and –196˚C). Authors of [1967Rom] have determined that the τ6 phase 

crystals possess antiferromagnetic properties and a possible arrangement of magnetic spins 

was discussed. Magnetic properties of the τ 7 phase are reported in [1980Kes] and [1985Fru]. 

The susceptibility obeys a Curie-Weiss law down to 4.2 K, within experimental error, with 

effective magnetic moment μ eff = 5.83·μ B, very close to the spin-only value 5.92·μ B, and the 

Curie temperature is θ = –13 K. At low temperature the magnetic ordering takes place (the 

Néel temperature T N = 5.40 K). Authors of [1975Cla] and [1976Bal2] have investigated 

magnetic properties of alloys from the Fe-Fe 2O 3-NaFeO 2 partial system annealed at 1000˚C. 

It was established, in particular, that with increasing sodium content of the alloys the Néel 

temperature values decrease. In opinion of [1997Ded], the Fe-Na-O system is prospective for 

the study of derivatives of iron in higher oxidation states. The use of oxidizer in abundance in 

solid-state oxidation synthesis can get novel information about valent possibilities of transition 

metals. For the first time the data about quadrupole and magnetic interactions of iron in 

higher oxidation state in the Fe-Na-O system (the Na 2O 2-Fe 2O 3 section) were obtained by 

[1997Ded]. 

Miscellaneous 

Fe–Na–O 4 

The mechanism of iron transport by liquid sodium in non-isothermal loop system was studied 

by [1975Kol]. The loop system was constructed from an AISI Type 316 steel. The sodium was 

heated from 400˚C to 700˚C in the heated zone of the system and cooled down reversibly in the 

cooled zone. In the cooled zone four specimen holders were invariably mounted, the exposition 

temperatures being 650, 600, 500 and 400˚C. Based on the obtained results a model for 

the transport of iron from the heated zone to the cooled zone was proposed. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_4 


5

6 4 

Fe–Na–O 

. Table 1 

Investigations of the Fe-Na-O Phase Relations, Structures and Thermodynamics 


[1940Kni] as 

quoted by 

[1984Dai1] 

Temperature/Composition/Phase 

Range Studied 

Thermal analysis The NaFeO 2-Fe 2O 3 section 

[1960The] X-ray diffraction 300-700˚C, NaFeO2-Fe2O3 section 

[1962Roo] as 

quoted by 

[1999Kal] 

Crystal structure studies Na3Fe5O9 [1962The] Dilatometry, X-ray diffraction ≤ 1300˚C, NaFeO2-Fe2O3 section 

[1963Sch] X-ray diffraction, solubility tests Room temperature, NaFeO2-Fe2O3 section 

[1967Rom] X-ray diffraction (single crystals, 

Weissenberg goniometer), Patterson 

methods, heavy-atom technique 

1100˚C, room temperature, 

complete crystal structure of 

Na3Fe5O9 

[1970Gro] X-ray diffraction, solution calorimetry 500-600˚C, ΔH of Na 4FeO 3 

[1971Tsc] X-ray diffraction 450˚C, 650˚C, three phases in the 

Na2O-NaFeO2 section 

[1974Bar] X-ray diffraction > 600˚C, Na4FeO3 as corrosion 

product of Na steel 

[1974Rie] Guinier X-ray diffraction Crystal structure of Na4FeO3 [1975Cla] X-ray diffraction, chemical analysis 1000˚C, Fe-Fe2O3-NaFeO2 partial 

system 

[1976Bal1] as 

quoted by 

[2003Lyk] 

Crystal structure studies NaFe2O3 [1976Bal2] X-ray diffraction, chemical analysis 1000˚C, the Fe-Fe2O3-NaFeO2 partial system 

[1977Bra] X-ray diffraction Crystal structure of Na4Fe2O5 [1977Kni] Bendix “time of flight” mass 

spectrometer vapor pressure 

measurements (Knudsen cell unit 

attachment) 

[1977Sha] as 

quoted by 

[1981Lin, 1999Kal] 

Partial pressures of Na and O, 350- 

600˚C, 0 to 60 at.% O 

Emf 522-775˚C, NaFeO 2 

[1978Bra1] X-ray Guinier-Simon diffraction 

technique (single crystals) 

Crystal structure of Na 5FeO 4 



MSIT 1



[1978Bra2] X-ray diffraction (rotation of single 

crystal, Weissenberg, precision filming 

techniques) 

[1978Bra3] X-ray Guinier-Simon diffraction 

technique (single crystals) 

[1981Oka] X-ray diffraction, kinetics of 

transformation 


Range Studied 

Crystal structure of Na 14Fe 6O 16 

Crystal structure of Na 8Fe 2O 7 

NaFeO 2 

[1984Ban] Slag-iron equilibria studies FeO-Fe2O3-Na2O partial system 

[1984Dai1] Emf, acid-solution calorimetry 500-1400˚C, whole range of 

compositions 

[1984Dai2] X-ray diffraction, DTA, high-temperature 

microscopy, emf 

500-1400˚C, whole range of 

compositions, phase diagram and 

thermodynamics 

[1985Ban1] Gas-slag reactions studying 1610˚C, FeO-Fe2O3-Na2O partial 

system 

[1985Ban2] Gas-slag reactions studying 1610˚C, FeO-Fe2O3-Na2O partial 

system 

[1985Fru] Magnetic structure by neutron 

diffraction 

≤ –173˚C, Na5FeO4 

[1986Igu] Reduction and fire flame techniques 1000˚C, FeO-Fe2O3-Na2O partial 

system 

[1987Yam] Emf 577-1227˚C, Fe2O3-Na2O section 

[1988Bha] Emf 350-600˚C, Na4FeO3 [1993Sri] Pseudo-isopiestic equilibrations, insodium 

equilibrations, DTA, solid state 

reactions, X-ray diffraction 

[1996Zha] as 

quoted by 

[1999Kal] 

< 700˚C, 0 to 60 at.% O 

Emf ≤ 1050˚C, Fe 2O 3-Na 3Fe 5O 9 section 

[1997Ded] Mössbauer spectroscopy, EPR, X-ray 

diffraction 

[1999Kal] Emf, isothermal equilibration, X-ray 

diffraction 

[2002Ama] X-ray diffraction (rotation of single 

crystal) 



MSIT 1 

≤ 480˚C, Na 2O 2-Fe 2O 3 section 

NaFeO 2-Fe 2O 3 section 

Na 9Fe 2O 7 

Fe–Na–O 4 

DOI: 10.1007/978-3-540-70890-2_4 


7

8 4 

Fe–Na–O 



[2003Hua1] High temperature mass spectrometry 

(Knudsen effusion), X-ray diffraction 


Range Studied 

25-447˚C, Na 4FeO 3 

[2003Lyk] Emf 827-1027˚C, FeO-Fe3O4-NaFeO2 partial system 

[2003Sob1] X-ray diffraction (single crystal) Na3FeO3 [2003Sob2] X-ray diffraction (single crystal) Complete crystal structure of 

Na 3FeO 3 

. Table 2 



Temperature 

Range [˚C] 


Space Group/ 

Prototype 

Lattice 

Parameters 


(δFe) (h2) cI2 a = 293.15 T = 1390˚C [Mas2], 

1538 - 1394 Im3m 

W 

dissolves 0.029 at.% O at 1528˚C 

(γFe) (h1) cF4 a = 364.67 T = 915˚C [Mas2], 

1394 - 912 Fm3m 

Cu 

dissolves 0.0098 at.% O at 1392˚C 

(αFe) (r) cI2 a = 286.65 T = 25˚C [Mas2], dissolves 

< 912 Im3m 

W 

0.00008 at.% O at 912˚C 

(εFe) (I) hP2 a = 246.8 T = 25˚C [Mas2] 

> 1.3·10 5 bar P63/mmc Mg 

c = 396 High pressure phase 

(βNa) (r) cI2 a = 428.865 T = 25˚C [1987Wri] 

97.8 - (–233) Im3m 

W 

(αNa) (l) hP2 a = 376.7 T = −268˚C [1987Wri] 

< –233 P63/mmc 

Mg 

c = 615.4 



MSIT 1



Temperature 

Range [˚C] 


Space Group/ 

Prototype 

Lattice 

Parameters 


α, Fe1–xOx (wüstite) 

cF8 x = 0.5126 to 0.5457 [Mas2], dissolves 

1424 - 570 Fm3m 

NaCl 

8 at.% Na (as Na2O) at 1000˚C [1976Bal] 

a = 430.88 Fe48.5O51.5, 20˚C [E] 

a = 428.00 Fe47.2O52.8, 20˚C [E] 

a = 431 Fe47.35O52.65, 1000˚C, 

pO2 = 1.2·10 –15 bar [1975Cla] 

Nay(Fe1–xOx) 1–y a = 433 x = 0.5265, y = 0.0537, T = 1000˚C, 

pO2 = 1.2·10 –15 bar [1975Cla] 

a = 434.5 x = 0.5265, y = 0.1020, T = 1000˚C, 

pO2 = 1.2·10 –15 bar [1975Cla] 

γFe3O4 (h) cF56 57.1 to 58.02 at.% O [Mas2] 

1596 - 580 Fd3m a = 843.96 at 25˚C [V-C2] 

MgAl2O4 Fe replaced by 0 to 3.5 at.% Na, at 1000˚C in 

equilibrium with Ar-H2-H2O mixture 

[1986Igu] 

βFe3O4 (r) mC224 - ~57.1 at.% O [Mas2] 

< 580 Cc 

βFe3O4 αFe3O4 (hp) m*14 - ~57.1 at.% O [Mas2] 

> 2.5·10 5 bar High pressure phase 

β, Fe2O3 hR30 a = 503.42 59.82 to ~60 at.% O [Mas2] 

< 1457 R3c c = 1374.73 p = 1 bar [V-C2] 

Al2O3 a = 503.5 

c = 1372 

[1981Oka] 

ε (Fe-O) c** - metastable; ~51.3 to ~53.5 at.% O [Mas2]; 

labelled as “P´ (wüstite)” [Mas2] 

η (Fe-O) mP500? - metastable; ~52 to ~54 at.% O [Mas2]; 

P21/m labelled as “P´´ (wüstite)” [Mas2] 

κ (Fe-O) hR6 - metastable; 51.3 to 53.2 at.% O [Mas2]; 

R3 

NiO (l) 

Fe–Na–O 4 

labelled as “wüstite (low-temperature)” 

[Mas2] 

λ (Fe-O) cI80 - metastable; ~60 at.% O; labelled as 

Ia3 

Mn2O3 “βFe2O3”[Mas2] γFe2O3 tP60 metastable; ~60 at.% O; labelled also as 

P43212 μ (Fe-O) 

a = c = 833 [1981Oka] 

a = c = 833.9 T = 300˚C [1960The] 

a = c = 840.7 T = 380˚C [1960The] 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_4 


9

10 4 

Fe–Na–O 



Temperature 

Range [˚C] 


Space Group/ 

Prototype 

Lattice 

Parameters 


ν (Fe-O) m*100 metastable; ~60 at.% O; labelled as “εFe2O3” [Mas2] 

a = 1299 

b = 1021 

c = 844 

β = 95.33˚ 

[S] 

γ, Na2O cF12 33.3 at.% O [Mas2] 

< 1134 ± 4 Fm3m 

CaF2 a = 556 [E] 

βNa2O2 (h) cF12 ~50 at.% O; labelled as “Na2O2-II” [Mas2] 

675 - (~512) Fm3m 

CaF2 a = 666 

c = 993 

[1989Rag] 

αNa2O2 (r) hP9 ~50 at.% O; labelled as “Na2O2-I” [Mas2] 

≲ 512 P62m 

Fe2 P a = 620.7 

c = 447.1 

[E] 

a = 620.8 

c = 446.9 

[1989Rag] 

γNaO2 (r) cF8 ~66.7 at.% O; labelled as “NaO2 (I)” [Mas2] 

552 - (–50) Fm3m 

NaCl a = 549 T = 25˚C [E] 

βNaO2 (l1) cP12 ~66.7 at.% O; labelled as “NaO2 (II)” [Mas2] 

(–50) - (–77) Pa3 

FeS2 (pyrite) a = 546 T = –70˚C [E] 

αNaO2 (l2) oP6 ~66.7 at.% O; labelled as “NaO2 (III)” [Mas2] 

< –77 Pnnm 

FeS2 (marcasite) a = 426 

b = 554 

c = 344 

T = –100˚C [E] 

θ (Na-O) oP6 - metastable; ~50 at.% O; labelled as “Na2O2- < –77 Pnnm 

FeS2 (marcasite) 

Q” [Mas2] 

ρ, NaO3 tI* ~75 at.% O [Mas2] 

I4/mmm a = 1043 

c = 688 

[1962Kuz] 

a = 1165 

c = 766 

[1964Kuz] 



MSIT 1



Temperature 

Range [˚C] 


Space Group/ 

Prototype 

Fe–Na–O 4 

Lattice 

Parameters 


τ1´´´, NaFeO2 (h2) - - by dilatometry distinguished from τ1´´ 1330 - 1010 

[1962The] 

τ1´´, βNaFeO2 (h1) oP16 a = 567.2 [1981Oka] 

1010 - 760 Pna21 b = 731.6 

c = 537.7 

τ1´, αNaFeO2 (r) hR12 a = 301.9 [1981Oka] 

< 760 R3m c = 1593.4 

CsICl2 a = 302.5 

c = 1609.4 

[2000Mat] 

τ2,Na2FeO2 < 801 

- - [1984Dai1] 

τ3,Na4FeO3 mC32 a = 1096 single crystals prepared at 630˚C, 10 d 

Cc b = 582 [1974Rie] 

Na4FeO3 c = 822 

β = 114˚ 

τ4,Na4Fe2O5 mP44 a = 1187 single crystals prepared at 600˚C, 6 d 

P21/n b = 567 [1977Bra] 

Na4Fe2O5 c = 917 

β = 104.5˚ 

τ5,Na8Fe2O7 mP68 a = 872 [1977Bra] 

P21/c b = 1102 

Na8Ga2O7 c = 1010 

β = 107.7˚ 

a = 870 single crystals prepared at 600˚C, 7 d 

b = 1101 

c = 1009 

β = 107.6˚ 

[1978Bra1] 

τ6,Na3Fe5O9 mC68 a = 1339 single crystals prepared at 1100˚C 

1100 - 755 C2/c b = 1207 [1967Rom] 

Na3Fe5O9 c = 529 

β = 89.17˚ labelled as “Na10Fe16O29” [1959Col, 

1962The, 1999Kal] 

τ7,Na5FeO4 oP80 a = 1033 single crystals prepared at 650˚C, 7 d 

Pbca b = 597 [1978Bra2] 

Na5FeO4 c = 1808 

a = 1026.7 

b = 591.3 

c = 1780 

T = –173˚C [1985Fru] 

a = 1027.9 

b = 592.3 

c = 1791.4 

T = –270.5˚C [1985Fru] 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_4 


11

12 4 

Fe–Na–O 



Temperature 

Range [˚C] 


Space Group/ 

Prototype 

Lattice 

Parameters 


τ8,Na14Fe6O16 aP36 a = 1142 single crystals prepared at 650˚C, 7 d 

P1 b = 827 [1978Bra3] 

Na14Fe6O16 c = 595 

α = 109.3˚ 

β = 87.7˚ 

γ = 111.4˚ 

τ9,Na9Fe2O7 oP72 a = 956.2 single crystals prepared at 450˚C 

Pca21 b = 999.1 [2002Ama] 

Na9Fe2O7 c = 1032.3 

τ10, Na3FeO3 mP28 a = 579.9 single crystals prepared at 650˚C, 14 d, no 

P21/n b = 1265.9 single phase product available [2003Sob1, 

Na3FeO3 c = 582.8 

β = 116.02˚ 

2003Sob2] 

τ11, NaFe5O8 cF56 ? - [1975Cla, 1976Bal2, 1986Igu]. Inside 

Fd3m ? 

metastable solid solution of γFe2O3 after 

MgAl2O4 ? 

[1960The] 

τ12, NaFe2O3 < 1047 

- - [1976Bal1, 2003Lyk] 

τ13, Na4Fe6O11 - - [1981Lin]. Phase does not exist after 

[1999Kal] 

. Table 3 

Thermodynamic Data of Reactions or Transformations 


FeO(s) + 2Na2O(s) → 

Na4FeO3(s) 3Na2O(s) + Fe(s) → Na4FeO3(s) + 2Na(l) 

Na4FeO3(s) → NaFeO2(s) + 

Na2O(s) + Na(l) 

Ca(s) + 2NaF(s) + 2FeO(s) → 

Na2FeO2(s) + CaF2(s) + Fe(s) 

Temperature 

[˚C] 

Quantity, per mole of 

atoms [kJ, mol, K] Comments 

25˚C ΔH = – 13.12 ± 0.3 

kJ·mol –1 

[1970Gro] acid solution 

calorimetry 

500-600 ΔG = 49.89 – 0.07·T [1970Gro] derived from 

acid solution calorimetry 

500-600 ΔG = 93.02 – 0.01·T [1970Gro] derived from 

acid solution calorimetry 

522-775 ΔG = –776.6 + 0.208·T [1977Sha, 1981Lin, 

1999Kal] emf 



MSIT 1



Na 2O(s) + Fe 2O 3(s) → 

Na 2Fe 2O 4(s) 

FeO(s) + Na2O(s) → 

Na2FeO2(s) 

FeO(s) + 2Na2O(s) → 

Na4FeO3(s) 1/2 {5Fe2O3(s) + 3Na2O(s)} → 

Na3Fe5O9(s) 4Na(l) + Fe(s) + 3/2O 2(g) → 

Na 4FeO 3(s) 

Na 4FeO 3(s) → Na 3FeO 3(s) + 

Na(g) 



Temperature 

[˚C] 

Quantity, per mole of 

atoms [kJ, mol, K] Comments 

522-775 ΔG = –171.970 – 

0.009456·T 

500-1400 ΔG = –86 – 

61.89·10 –3 ·T 

657-774 ΔG = –160.2 – 

0.003909·10 –3 ·T 

774-1005 ΔG = –157.2 – 

1.332·10 –3 ·T 

1005-1132 ΔG = –147.3 – 

13.37·10 –3 ·T 

362-512 ΔG = –237.425 + 

83.1·10 –3 ·T 

561-731 ΔG = –247.086 + 

89.435·10 –3 ·T 

657-725 ΔG = –232.582 + 

69.61·10 –3 ·T 

500-1400 ΔG = –119.106 + 

0.114·T 

500-1400 ΔG = –147.998 + 

0.165·T 

< 1132 ΔG = –(248.6 ± 1.1) – 

(2.447 ± 1.188)·10 –3 ·T 

752-864 ΔG = –153.978 + 

32.32·10 –3 ·T 

450-600 ΔG = –1212.202 + 

0.3511·T 

317-444 ΔG (Na 4FeO 3)= 

–11168.629 + 

0.33834·T 

MSIT 1 

Fe–Na–O 4 

[1977Sha, 1999Kal] emf 

[1984Dai1] emf 

[1987Yam] emf 

[1987Yam] emf 

[1987Yam] emf 

[1996Zha, 1999Kal] emf 

[1996Zha, 1999Kal] emf 

[1999Kal] emf 

[1984Dai1] acid-solution 

calorimetry 

[1984Dai1] acid-solution 

calorimetry 

[1987Yam] emf 

[1999Kal] emf 

[1988Bha] emf 

[2003Hua1] Knudsen cell 

effusion 

DOI: 10.1007/978-3-540-70890-2_4 


13

14 4 

Fe–Na–O 

. Table 4 

Vapor Pressure Measurements 

Phase(s) Temperature [˚C] Pressure [bar] Comments 

Fe(s), FeO(s), Na2Fe2O4(s) 600 log10 (pO2) = –25.27 [1984Dai1] tabulated 

600 log10 (pNa) = –7.14 

data 

900 log10 (pO2) = –19.6 

900 log10 (pNa) = –1.24 

Fe(s), Na2Fe2O4(s), Na2FeO2(s) 600 log10 (pO2) = –29.85 

600 log10 (pNa) = –2.56 

Fe(s), Na2FeO2(s), Na4FeO3(s) 600 log10 (pO2) = –29.95 

log10 (pNa) = –2.50 

Na2Fe2O4(s), Na4FeO3(s), 600 log10 (pO2) = –29.69 

Na2FeO2(s) 

log10 (pNa) = –2.56 

Fe(s), Na(l), Na4FeO3(s) 600 log10 (pO2) = –32.55 

log10 (pNa) = –1.53 

. Table 5 

Investigations of the Fe-Na-O Materials Properties 

Reference Method/Experimental Technique Type of Property 

[1967Rom] Magnetic property studies, 

Mössbauer spectroscopy 

Magnetic susceptibility, magnetic ordering of the 

τ 6 phase 

[1975Cla] Faraday magnetic technique Magnetic susceptibility of the Fe-Fe2O3-NaFeO2 partial system phases 

[1976Bal2] Faraday magnetic technique Magnetic susceptibility of the Fe-Fe2O3-NaFeO2 partial system phases 

[1980Kes] Magnetic property studies, 


[1981Kes] Magnetic property studies, 



τ 7 phase 


τ 5 phase 

[1985Fru] Neutron diffraction Magnetic structure of the τ7 phase 

[1997Ded] Mössbauer spectroscopy Magnetic structure of Na2O2-Fe2O3 section 

phases, quadrupol interactions 



MSIT 1

. Fig. 1 

Fe-Na-O. The partially quasibinary section NaFeO 2 -Fe 2O 3 



MSIT 1 

Fe–Na–O 4 

DOI: 10.1007/978-3-540-70890-2_4 


15

16 4 

Fe–Na–O 

. Fig. 2 

Fe-Na-O. The partially quasibinary section Na 2O – FeO 



MSIT 1

. Fig. 3 

Fe-Na-O. The approximately quasibinary section Fe 3O 4-NaFeO 2 



MSIT 1 

Fe–Na–O 4 

DOI: 10.1007/978-3-540-70890-2_4 


17

18 4 

. Fig. 4 

Fe-Na-O. Reaction scheme of the partial system Fe-Fe2O3-NaFeO2-Na2FeO2. The phases (αFe), (γFe) and (δFe) are not distinguished and called Fe. 

Also τ 1’, τ 1’’ and τ 1’’’ are not distinguished and called NaFeO2 Fe–Na–O 



MSIT 1

. Fig. 5 

Fe-Na-O. Liquidus surface projection of the partial FeO-Fe 2O 3-NaFeO 2 system 



MSIT 1 

Fe–Na–O 4 

DOI: 10.1007/978-3-540-70890-2_4 


19

20 4 

Fe–Na–O 

. Fig. 6 

Fe-Na-O. Isothermal section of the partial Fe-Fe 2O 3-NaFeO 2 system at 1000˚C; equilibrated with 

Ar-H 2-H 2O mixtures 



MSIT 1

. Fig. 7 

Fe-Na-O. Isothermal section at 595˚C 



MSIT 1 

Fe–Na–O 4 

DOI: 10.1007/978-3-540-70890-2_4 


21

22 4 

Fe–Na–O 

. Fig. 8 

Fe-Na-O. Temperature - composition section NaFeO 2-FeO 



MSIT 1

References 

Fe–Na–O 4 

[1940Kni] Knick, R., Kohlmeyer, E.J., “About the Melting Properties of the Soda-Iron Oxide Mixtures” (in 

German), Z. Anorg. Allg. Chem., 244, 67–84 (1940) (Phase Diagram, Experimental, *) as quoted by 

[1984Dia1] 

[1959Col] Collonques, R., Thery, J., “Preparation and Properties of Sodium Ferrites”, Bull. Soc. Chim. Fr., 1959, 

1141–1144 (1959) (Crys. Structure, Experimental) as quoted by [1999Kal] 

[1960The] Thery, J., Collongues, R., “The Fe 2O 3-Na 2O System” (in French), Compt. Rend., 250, 1070–1072 (1960) 

(Crys. Structure, Phase Diagram, Experimental, *, 9) 

[1962Kuz] Kuznetsov, V.G., Tokareva, S.A., Dobrolyubova, M.S., “X-ray Diffraction Investigation of the Sodium 

Ozonide NaO 3” (in Russian), Zh. Neorg. Khim., 7(5), 967–970 (1962) (Crys. Structure, Experimental, 7) 

[1962Roo] Rooymans, C.J.M., “New Compound in the Na 2O-Fe 2O 3 System”, J. Phys. Soc. Jpn., 17, 722–723 (1962) 

(Crys. Structure, Experimental) as quoted by [1999Kal] 

[1962The] Thery, J., “Alkali Metal Ferrates and Their Hydrolysis Products”, Ann. Chim. (Paris), 7, 207–238 (1962) 

(Crys. Structure, Phase Diagram, Experimental, 42) 

[1963Sch] Scholder, R., Mansmann, M., “Compounds of the So-Called β-Alumina Type” (in German), Z. Anorg. 

Allg. Chem., 321(5-6), 246–261 (1963) (Crys. Structure, Experimental, 19) 

[1964Kuz] Kuznetsov, V.G., Bakulina, V.M., Tokareva, S.A., Zimina, A.N., “X-ray Diffraction Investigation of the 

Sodium Ozonide NaO 3” (in Russian), Zh. Struct. Khim., 5(1), 142–144 (1964) (Crys. Structure, 

Experimental, 8) 

[1967Rom] Romers, C., Rooymans, C.J.M., de Graaf, R.A.G., “The Preparation, Crystal Structure and Magnetic 

Properties of Na 3Fe 5O 9”, Acta Cryst., 22(6), 766–771 (1967) (Crys. Structure, Experimental, Review, 

Magn. Prop., 21) 

[1970Gro] Gross, P., Wilson, G.L., “Composition and Heat of Combination of a Double Oxide of Iron and 

Sodium”, J. Chem. Soc. (A), 11, 1913–1916 (1970) (Crys. Structure, Phase Relations, Thermodyn., 


[1971Tsc] Tschudy, A., Kessler, H., “The Na 2O-NaFeO 2 System. Characterization of Three Ternary Compounds” 

(in French), Compt. Rend., Ser. C., 273(21), 1435–1437 (1971) (Crys. Structure, Experimental, 4) 

[1974Bar] Barker, M.G., Wood, D.J., “The Corrosion of Chromium, Iron and Stainless Steel in Liquid Sodium”, 

J. Less-Com. Met., 35, 315–323 (1974) (Crys. Structure, Morphology, Phase Relations, Experimental, 16) 

[1974Rie] Rieck, H., Hoppe, R., “The First Oxoferrate (II): Na 4{FeO 3}” (in German), Naturwissenschaften, 61(3), 

126–127 (1974) (Crys. Structure, Experimental, 9) 

[1975Cla] Claude, J.M., El Balkhi, A.M., Jeannot, F., Gleitzer, C., Aubry, J., “The Fe-Fe 2O 3-NaFeO 2 System. I. The 

Solubility of Na in Wustite at p O2 = 1.2·10 –15 bar and 1000˚C” (in French), Mem. Sci. Rev. Met., 72(7-8), 

599–603 (1975) (Crys. Structure, Phase Diagram, Phase Relations, Experimental, Magn. Prop., *, 12) 

[1975Kol] Kolster, B.H., “Mechanism of Fe and Cr Transport by Liquid Sodium in Non-Isothermal Loop 

Systems”, J. Nucl. Mater., 55(2), 155–168 (1975) (Crys. Structure, Morphology, Experimental, Transport 


[1976Bal1] El Balkhi, A.M., Zanne, M., Gleitzer, C., “Preparation and Properties of the Sodium-Ferrite (II, III) 

Oxide. NaFe 2O 3” (in French), J. Solid State Chem., 18, 293–297 (1976) (Crys. Structure, Experimental) 

as quoted by [2003Lyk] 

[1976Bal2] El Balkhi, A.M., Zanne, M., Gleitzer, C., Aubry, J., “The Fe-FeO-NaFeO 2 System. II. Equilibrium Limits 

and Properties of Wustite Containing Na” (in French), Mem. Sci. Rev. Metall., 73(2), 761–768 (1976) 

(Crys. Structure, Phase Diagram, Phase Relations, Experimental, Magn. Prop., *, 5) 

[1977Bra] Brachtel, G., Hoppe, R., “The First Oxoferrate (III) with Single Layer Structure: Na 4Fe 2O 5” 

(in German), Naturwissenschaften, 64(5), 271–272 (1977) (Crys. Structure, Experimental, 8) 

[1977Kni] Knights, C.F., Phillips, B.A., “Phase Diagrams and Thermodynamic Studies of the Cs-Cr-O, Na-Cr-O 

and Na-Fe-O Systems and their Relationships to the Corrosion of Steels by Caesium and Sodium”, 

Special Publ. Chem. Soc., 30, 134–145 (1977) (Crys. Structure, Phase Diagram, Phase Relations, 

Thermodyn., Experimental, *, 43) 

[1977Sha] Shaiu, B.J., Wu, P.C.S., Chiotti, P., “Thermodynamic Properties of Double Oxides of Sodium Oxide 

with Oxides of Chromium, Nickel and Iron”, J. Nucl. Mater., 67, 13–23 (1977) (Thermodyn., Experimental) 

as quoted by [1981Lin] and [1999Kal] 

[1978Bra1] Brachtel, G., Hoppe, R., “On Oxoferrate with "Isolated" Anions: Na 8Fe 2O 7” (in German), Z. Anorg. 

Allg. Chem., 438, 15–24 (1978) (Crys. Structure, Experimental, 36) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_4 


23

24 4 

Fe–Na–O 

[1978Bra2] Brachtel, G., Hoppe, R., “New Oxoferrates (III). On the Knowledge of Na 5FeO 4” (in German), 

Z. Anorg. Allg. Chem., 446, 77–86 (1978) (Crys. Structure, Experimental, 18) 

[1978Bra3] Brachtel, G., Hoppe, R., “New Oxoferrates (III). On the Knowledge of Na 14{Fe 6O 16}” (in German), 

Z. Anorg. Allg. Chem., 446, 87–96 (1978) (Crys. Structure, Experimental, 18) 

[1978Zve] Zvezdinskaya, L.V., Smirnova, N.L., Belov, N.V., “System of Polymorphic Transition Between 

Structural Types of Ternary ABX 2 Compounds”, Sov. Phys.-Crystallogr. (Engl. Transl.), 23(3), 293–296 

(1978) (Crys. Structure, Review, 22) 

[1980Kes] Kessler, H., Son, L., “Study of the Magnetic Interactions between Na 5FeO 4 and {FeO 4} 5– Discrete 

Anions” (in French), Rev. Chimie Miner., 17(6), 541–547 (1980) (Crys. Structure, Experimental, Magn. 

Prop., 13) 

[1981Kes] Kessler, H., Ly, S., “Magnetic Interactions of {Fe 2O 7} 8– Groups in Na 8Fe 2O 7” (in French), J. Solid State 

Chem., 39, 22–28 (1981) (Crys. Structure, Experimental, Magn. Prop., 20) 

[1981Lin] Lindemer, T.B., Besmann, T.M., Johnson, C.E., “Thermodynamic Review and Calculations - Alkali- 

Metal Oxide Systems with Nuclear Fuels, Fission, Products and Structural Materials”, J. Nucl. Mater., 

100(1-3), 178–226 (1981) (Phase Diagram, Phase Relations, Thermodyn., Calculation, Review, 280) 

[1981Oka] Okamoto, S., “Crystallization and Phase Transformation Sodium Orthoferrites”, J. Solid State Chem., 

39, 240–245 (1981) (Crys. Structure, Phase Relations, Experimental, 10) 

[1982Bau] Baur, W.H., McLarnan, T.J., “Observed Wurtzite Derivatives and Related Dipolar Tetrahedral 

Structures”, J. Solid State Chem., 42, 300–321 (1982) (Crys. Structure, Review, 93) 

[1984Ban] Ban-ya, S., Hino, M., Takezoe, H., “Thermodynamics of Fe tO-Na 2O, Fe tO-SiO 2-Na 2O, Fe tO-P 2O 5- 

Na 2O and Fe tO-P 2O 5-SiO 2-Na 2O Slags in Equilibrium with Solid Iron”, Second Int. Symp. Metal. Slags 

and Fluxes (Proc. Conf.), Lake Tahoe, Nevada, U.S.A., 1984, The Metall. Soc. AIME, Warrendale, 

Pennsylvania, 395–416 (1984) (Phase Relations, Thermodyn., Experimental, 42) 

[1984Dai1] Dai, W., Seetharaman, S., Staffansson, L.-J., “A Thermodynamic Study of the System Fe-Na-O”, Scand. 

J. Metall., 13(1), 32–38 (1984) (Phase Diagram, Phase Relations, Thermodyn., Experimental, #, 20) 

[1984Dai2] Dai, W., Seetharaman, S., Staffanson, L.-J., “Phase Relationships in the System Fe-Na-O”, Metall. Trans. 

B, 15B, 319–327 (1984) (Morphology, Phase Diagram, Thermodyn., Experimental, #, 24) 

[1985Ban1] Ban-Ya, S., Hino, M., Takezoe, H., “Activities of the Constituents and Fe 3+ /Fe 2+ Equilibrium in Fe tO- 

Na 2O and Fe tO-SiO 2-Na 2O Slags” (in Japanese), Tetsu To Hagane, 15, 1765–1772 (1985) (Phase 

Diagram, Phase Relations, Thermodyn., Calculation, Experimental, 42) 

[1985Ban2] Ban-Ya, S., Hino, M., Takezoe, H., “Thermodynamic Properties of Fe tO-Na 2O, Fe tO-SiO 2-Na 2O, Fe tO- 

P 2O 5-Na 2O and Fe tO-P 2O 5-SiO 2-Na 2O Slags”, Trans. Iron Steel Inst. Jpn., 25(11), 1122–1131 (1985) 

(Phase Diagram, Phase Relations, Thermodyn., Experimental, 42) 

[1985Fru] Fruchart, D., Soubeyroux, J., Kessler, H., Lassalle, J.-M., “Magnetic Structure of Na 5FeO 4” (in French), 

J. Solid State Chem., 57, 191–196 (1985) (Crys. Structure, Experimental, Magn. Prop., 8) 

[1986Igu] Iguchi, Y., Amahiro, Y., Hirao, J., “Equilibrium Between FeO-M 2O (M = Na, Li) Solid Solution and 

Oxygen in Gas Phase at 1273 K” (in Japanese), J. Jpn. Inst. Met., 50(3), 282–287 (1986) (Crys. Structure, 

Phase Relations, Thermodyn., Experimental, #, 27) 

[1987Wri] Wriedt, H.A., “The Na-O (Sodium-Oxygen) System”, Bull. Alloy Phase Diagrams, 8(3), 234–246 (1987) 

(Assessment, Review, Phase Diagram, Phase Relations, Crys. Structure, 100) 

[1987Yam] Yamaguchi, S., Kaneko, Y., Iguchi, Y., “Activity Measurements of Na 2OinNa 2O-Fe 2O 3 System by EMF 

Method Using Sodium β Alumina as a Solid Electrolyte”, Trans. Jpn. Inst. Met., 28(12), 986–993 (1987) 

(Thermodyn., Experimental, 10) 

[1988Bha] Bhat, N.P., Borgstedt, H.U., “Thermodynamic Stability of Na 4FeO 3 and Threshold Oxygen Levels in 

Sodium for the Formation of this Compound on AISI 316 Steel Surfaces”, J. Nucl. Mater., 158, 7–11 

(1988) (Thermodyn., Calculation, Experimental, 20) 

[1989Rag] Raghavan, V., “The Fe-Na-O (Iron-Sodium-Oxygen) System” in “Phase Diagrams of Ternary Iron 

Alloys”, Indian Inst. Met., Calcutta, 5, 206–212 (1989) (Crys. Structure, Phase Diagram, Review, 17) 

[1993Sri] Sridharan, R., Gnanasekaran, T., Mathews, C.K., “Phase Equilibrium Studies in the Na-Fe-O System”, 

J. Alloys Compd., 191, 9–13 (1993) (Phase Relations, Phase Diagram, Experimental, *, 14) 

[1996Kal] Kale, G.M., Davidson, A.J., Fray, D.J., “Solid State Sensor for Measuring Antimony in Non-Ferrous 

Metals”, Solid State Ionics, 86-88, 1101–1105 (1996) (Phase Relations, Thermodyn., Experimental) as 

quoted by [1999Kal] 

[1996Zha] Zhang, L., Fray, D.J., Dekeyser, J.C., De Schutter, F., “Reference Electrode of Simple Galvanic Cells for 

Developing Sodium Sensors for Use in Molten Aluminium”, Metall. Mater. Trans. B., 27B, 794–800 

(1996) (Phase Relations, Thermodyn., Experimental) as quoted by [1999Kal] 



MSIT 1

Fe–Na–O 4 

[1997Ded] Dedushenko, S.K., Kholodkovskaya, L.N., Perfiliev, Yu.D., Kiselev, Yu.M., Saprykin, A.A., Kamozin, 

P.N., Lemesheva, D.G., “On the Possible Existence of Unusual Higher Oxidation States of Iron in 

the Na-Fe-O System”, J. Alloys Compd., 262-263, 78–80 (1997) (Crys. Structure, Experimental, Magn. 

Prop., 6) 

[1998Wu] Wu, E.J., Tepesch, P.D., Ceder, G., “Size and Charge Effects on the Structural Stability of LiMO 2 (M = 

Transition Metal) Compounds”, Philos. Mag. B, 77(4), 1039–1047 (1998) (Crys. Structure, Review, 22) 

[1999Kal] Kale, G.M., Srikanth, S., “Electrochemical Determination of the Gibbs Energy of Formation of 

Na 2Fe 2O 4 and Na 3Fe 5O 9 Employing Na-β-Al 2O 3 Solid Electrolyte”, J. Am. Ceram. Soc., 83(1), 175–180 

(1999) (Phase Relations, Thermodyn., Experimental, 24) 

[2000Mat] Mather, G.C., Dussarrat, C., Etourneau, J., West, A.R., “A Review of Cation-Ordered Rock Salt 

Superstructure Oxides”, J. Mater. Chem., 10, 2219–2230 (2000) (Crys. Structure, Review, 55) 

[2002Ama] Amann, P., Moeller, A., “Na 9{FeO 3}{FeO 4} a Mixed Valent Oxoferrat (II, III) with Isolated {FeO 3} 4– and 

{FeO 4} 5– Anions”, Z. Anorg. Allg. Chem., 628, 917–919 (2002) (Crys. Structure, Experimental, 12) 

[2003Hua1] Huang, J., Furukawa, T., Aoto, K., “Thermodynamic Study of Sodium-Iron Oxides. Part I. Mass 

Spectrometric Study of Na-Fe Oxides”, Thermochim. Acta, 405(1), 61–66 (2003) (Thermodyn., Experimental, 

20) 

[2003Hua2] Huang, J., Furukawa, T., Aoto, K., “Thermodynamic Study of Sodium-Iron Oxides. Part II. Ternary 

Phase Diagram of the Na-Fe-O System”, Thermochim. Acta, 405(1), 67–72 (2003) (Phase Diagram, 

Thermodyn., Assessment, Calculation, *, 15) 

[2003Lyk] Lykasov, A.A., Pavlovskaya, M.S., “Phase Equilibria in the Fe-Na-O System Between 1100 and 1300 K”, 

Inorg. Mater., 39(10), 1088–1091 (2003) translated from Neorg. Mater., 39(10), 1260-1263, (2003) 

(Phase Diagram, Phase Relations, Thermodyn., Calculation, Experimental, *, 6) 

[2003Mue] Mueller-Buschbaum, H., “The Crystal Chemistry of AM 2O 4 Oxometallates”, J. Alloys Compd., 349, 

49–104 (2003) (Crys. Structure, Review, 476) 

[2003Sob1] Sobotka, B.M., Moeller, A., “Crystal Structure of Na 3FeO 3” (in German), Anorg. Kristallstr. Kristallchem., 

20, 153 (2003) (Crys. Structure, Experimental, 2) 

[2003Sob2] Sobotka, B.M., Moeller, A., “Synthesis of Na 3FeO 3, a Ternary Oxoferrate (III) with a Chain Structure” 

(in German), Z. Anorg. Allg. Chem., 629, 2063–2065 (2003) (Crys. Structure, Experimental, 21) 



(1990) 






MSIT 1 

DOI: 10.1007/978-3-540-70890-2_4 


25

Iron – Niobium – Nickel 


Volodymyr Ivanchenko, Tetyana Pryadko 

Introduction 

Nickel steels and superalloys have found an increasing use in applications that required a 

combination of high strength, ductility and corrosion resistance at high temperatures. These 

applications have led to interest in the precipitation hardening characteristics of nickel base 

alloys. It has been established that in Nb bearing austenitic steels the Laves phase NbFe 2 can 

produce considerable precipitation hardening. 

[1975Pan] investigated alloys on the Nb 2Fe-NbNi 3 section and found it to be a quasibinary 

one of the simple eutectic type. Crystal structures of phases formed in the ternary alloys at 950˚ 

C along NbFe-NbNi and NbFe2-NbNi2 joins have been studied by [1981Var]. Growth crystallography 

of directionally solidified (αFe)+(Nb,Ni)Fe 2 eutectic alloy was investigated by 

[1980Tew]. 

The phase relations in alloys obtained by quenching directly from the melt were studied by 

[1982Osi, 1984Ska, 1989Sav]. [1989Sav] gives the phase distribution on the composition 

triangle for cast alloys quenched from liquid state at different cooling rates, up to 10 6 ˚C·s –1 . 

When the alloys were quenched directly from the melt at cooling rates up to 10 4 -10 6 ˚C·s –1 , all 

the three Laves forms C14 (λ 1), C15 (λ 2), and C36 (λ 3) appeared. Using the electron concentration 

considerations and comparisons with the isothermal sections in the related Co-Fe-Nb 

and Co-Nb-Ni systems, [1989Sav] comes to the unusual conclusion that the phase distribution 

obtained by quenching directly from the melt is closer to the equilibrium conditions and 

proposed the isothermal section at 1200˚C. This section was reproduced by [1992Rag1], but 

with a comment, that it clearly required confirmation and should be considered purely 

tentative. [2001Tak] and [2005Tak] studied phase equilibria among γ, NbNi 3 and NbFe 2 

phases. Isothermal section at 1200˚C was presented. It was redrawn by [2004Rag] from 

[2001Tak]. An attempt to estimate the concentration stability of topologically closed-packed 

phases was performed by [1992Mes] by calculation of the change in the factor of the electron 

concentration. 

The works on the phase relations, structures and thermodynamics are summarized in 

Table 1. 


Fe–Nb–Ni 5 

The Fe-Nb system is accepted from [1993Bej]. The Fe-Ni system is taken from the recent 

assessment of [2008Kuz]. The Nb-Ni system is accepted according to [1998Oka]. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_5 


1

2 5 

Fe–Nb–Ni 


The isostructural phases Nb 6Fe 7 and Nb 7Fe 6 form a continuous solid solution μ [1981Var, 

1989Sav, 2001Tak, 2005Tak]. The composition dependences of cell parameters obey the 

Vegard’s law [1981Var]. 

The effects of Ni content on the lattice parameters of the stoichiometric λ1 (NbFe2) phase 

and the Fe rich λ1 phase in equilibrium with γ phase are shown in Fig. 1, together with their 

calculated values (thin lines) based on Vegard’s law according to [2005Tak]. 

A new ternary intermetallic phase was found at the composition around Ni-22Nb-20Fe 

(at.%) by [2001Tak]. It’s crystal structure has been identified as ordered hexagonal (hP24 with 

stacking sequence of abcbcb). 

The amorphous state can be formed in alloys located along line parallel to the Fe-Ni side of 

the composition triangle with 25-50 at.% Nb under quenching from the liquid state with a 

cooling rate of ~10 6 K·s –1 [1984Ska]. 

Under ordering of (NbxFe1–x)Ni3 compound atoms of Nb are distributed in the both 

sublattice of Fe and Ni [1985Val]. Nb atoms try to set places to form a maximal number of Nb- 

Nb pairs [1987Val]. [1993Zhi] reported, that under annealing of quenched by spinning Ni-16 

Fe-6Nb (at.%) and Ni-16Fe-4Nb (at.%), ordering of the γ phase occurs. Nucleation and 

growth of the ordered γ’’- and γ’ phases proceed in an accelerated manner, although the 

mechanisms of nucleation are different. The fact that the density of quench-induced defects is 

relatively low is probably due to their relaxation and migration to sinks such as Nb rich areas. 

This can promote an accelerated phase transformation and ordering processes in the γ-matrix. 

The formation of tetrahedral stacking faults in the matrix during annealing also points to the 

relaxation of quench-induced defects. Thus the main factor accelerating phase transformations 

from the γ- into the γ’ phase is an excessive vacancy density. In the transformation from 

the γ- into the γ" phase, two more factors are operative: (1) dendritic segregation, that is, a 

higher Nb and Fe content in the interbranch spaces of dendritic cells; and (2) stresses, resulting 

from melt quenching, which promote the development of a sub-grain structure. 

[1989Sav] reported about the formation under rapid crystallization of C15 (λ 2) and C36 

(λ3) Laves phases in the Fe-Nb-Ni system and based on the electron concentration consideration 

contended that they are equilibrium phases. These results are in contradiction with the 

results of [2001Tak] and [2005Tak]. Therefore the C15 (λ 2) and C36 (λ 3) Laves phases 

discovered by [1989Sav] must be regarded as metastable. Crystal structures of solid phases 

formed in the Fe-Nb-Ni system are presented in Table 2. 


According to [1975Pan] the NbFe2-NbNi3 section is quasibinary of the eutectic type. The 

eutectic reaction is at 1290˚C and 70 mol% NbNi 3 (16.2Fe-27Nb-56.8Ni (at.%) [1975Pan]. No 

phase diagram was presented by [1975Pan]. Presented values are in good accordance with 

[2001Tak, 2005Tak]. 



MSIT 1


Only one three-phase invariant equilibrium was experimentally recorded in the Fe-Nb-Ni 

system by [1975Pan]. It is presented in Table 3. 


The solubility of Nb in Fe-30 mass% Ni (29.6 at.%) austenite at 1250˚C is about 3.4 mass% 

(2.1 at.%) and at 800˚C is about 1 mass% (0.6 at.%) [1971Lei]. 


The isothermal section at 1200˚C presented in Fig. 2 is taken from [2005Tak]. In the Fe rich 

corner a three-phase domain (λ1+(δFe)+γ) is drawn tentatively to account for the (δFe) phase 

which exists at this temperature. The section at the same temperature constructed by 

[1989Sav] is omitted here since it obviously presents metastable state, see above section 

“Introduction”. 



On aging at 800˚C of the Fe-30Ni-5Nb (mass%) alloy quenched from 1250˚C the hardness 

increases from 150 to 220 H V (1.471 to 2.158GPa).The precipitation of NbFe 2 is a heterogeneous 

process occurring mainly on dislocations on (111) γ planes and on grain boundaries. The 

rate of growth of NbFe 2 precipitate beyond the peak hardness is very slow and as a result no 

overaging was observed after aging at 800˚C for 250 h and at 700˚C for 1000 h [1971Lei]. The 

rate of solid solution hardening per 1 at.% Nb in Ni-Fe matrix alloys is larger than in Ni matrix 

alloys [1990Cho]. 

Magnetically soft alloys of the Fe-Ni system are used extensively in instrument building. 

This is connected with a favorable combination of a number of properties: single phase alloys 

in a stable condition over a wide concentration range, absence of allotropic transformations 

which cause development of internal stresses, existence of ordering and the possible effect of 

alloying on the degree of ordering, and passage of the constants for magnetic crystallographic 

anisotropy K I and magnetostriction i s through a zero value in the range 70-80% Ni. However, 

alloys of the Fe-Ni system have low strength and wear resistance which limit their use for 

example as magnetic recording heads. 

One of the most widespread methods for improving the mechanical properties of these 

alloys is alloying with elements which form solid solutions. Nb is one from such elements. His 

solid solution strengthening is observed which causes a specific increase in mechanical 

properties. 

The origin of high magnetic permeability in “Hardperm” of the Fe-Nb-Ni system was 

studied by [1976Hin]. The effect of structure on the hardness and permeability of Fe-Nb-Ni 

alloys was presented by [1979Wen]. Magnetic properties of intermetallic phases have been 

studied by [1982Osi]. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_5 


3

4 5 

Fe–Nb–Ni 

Magnetic properties, electrical resistivity and hardness of Ni-based alloys were studied by 

[1974Mas, 1978Mas]. Alloys with a very high permeability were proposed. 

An investigation of the structures of Fe-Nb-Ni alloys has been carried out by means of 

TEM supplemented by electron diffraction and X-ray diffraction analysis [1979Wen]. As the 

proportion of modulated structures increases, the hardness of the alloy also increases, but vice 

versa in the case of its magnetic permeability. The introduction of solute atoms of Nb would 

lower the degree of ordering in Ni3Fe alloy, but fortunately only certain degree of ordering was 

sufficient to yield conditions for high permeability. A preprecipitating phase possessing the fcc 

(ordered) Ni 3Nb (γ’) structure and being coherent with the matrix, was observed in the Fe- 

Nb-Ni alloy. This phase appears to promote the formation of modulated structures and exert a 

strengthening effect on matrix. 

Examination of the temperature dependence of the magnetic susceptibility of the Laves 

phase NbFe 2 has shown it to be a temperature-independent paramagnetic (χ = 9.6 · 10 –6 

m 3 ·kg –1 ). Substitution of the iron atoms by nickel ones along the section NbFe2-NbNi3 causes 

a smooth increase in magnetic susceptibility which reaches 1.82 · 10 –5 m 3 ·kg –1 for an alloy with 

46.67 at.% Fe + 22.5 at.% Ni + 30.83 at.% Nb (70 mol% NbFe 2, 30 mol% NbNi 3). The Nb 6Fe 7 

and Nb 7Ni 6 compounds are temperature-independent paramagnetics with magnetic susceptibilities 

of 1.85 · 10 –5 and 0.6 · 10 –5 m 3 ·kg –1 , respectively, i.e. the 3d band for these compounds 

is completely filled and the magnetic properties are determined by the S conductivity electrons 

which have temperature-independent susceptibility [1982Osi]. 

A strengthening effect is observed for microcrystalline alloys of the system Fe-Nb-Ni 

prepared by quenching from the melt with low-temperature heat treatment. Strengthening 

of these alloys is due to the effect of crystallite refinement in the initial stages of primary 

recrystallization and precipitation of the NbNi 3 phase. Low-temperature heat treatment 

provides preparation of the most effective magnetic permeability in the frequency range 

0.5-1 MHz for alloys Ni-16Fe-4Nb (at.%); Ni-16Fe-6Nb (at.%). Use of the rapid quenching 

method makes it possible to achieve a marked increase in mechanical properties of alloys of 

the system Fe-Nb-Ni compared with the properties of alloys prepared by traditional technology 

with retention of a high level of magnetic characteristics at frequencies of 0.5-1 MHz 

[1992Sos]. 

Phase hardening during martensite transformation as well as the hard particles of NbNi3 

and NbFe 2-type have the effect of increasing the degree of recovery of shape and partially 

constrict transformation hysteresis in Fe-Nb-Ni alloys due to effective prevent dislocation 

movement [1985Kov1, 1985Kov2, 1989Kov]. In Fe-30.5Ni-(2.9-4.3)Nb (at.%) alloys, the 

γ 00 -particles having a mean dimension more than 10 nm do not transform to another 

structure. However, the particle deformation takes place, providing an effect equivalent to 

inhomogeneous deformation of the martensite. The stored strain level causes a small tetragonal 

distortion of the martensite. The tetragonality is not a consequence of the ordered 

structure of the precipitates (D022) but rather is due to the tetragonal symmetry of the Bain 

strain. The particles can be considered as memory elements which are responsible for the 

shape memory effect in the steels, despite the relatively small tetragonality of α phase and the 

relatively wide thermal hysteresis [1993Kov]. 

Investigations of the Fe-Nb-Ni materials properties are summarized in Table 4. 



MSIT 1

Miscellaneous 

[1980Rus] studied martensite aging in Fe-13.4Ni-2.6Fe (at.%) alloy. It proceeds in two stages. 

At the preisolation stage (300-450˚C) there occure the formation of Ni and Nb enriched 

submicroregions and Fe atomic ordering. The second stage heating temperature 450˚C results 

in isolation of disperse particles of Ni- and Nb-based intermetallic phases. The first stage 

produces the main strengthening. Aligned lamellar microstructure was obtained on alloy with 

a nominal composition of Fe-12Nb-17.7Ni (at.%) directionally solidified at a growth rate of 

0.5 cm·h –1 with the temperature gradient in the liquid-solid interface of about 200˚C·cm –1 . 

The orientation relationship between (αFe) matrix phase and lamellas of ε(Nb,Ni)Fe 2 intermetallic 

phase has been expressed as {111} α //{001} ε growth direction and (112) α//(010) ε at 

the α-ε interface. 

It was shown by [1993Zhi] that upon heat treatment of rapidly quenched alloys, 

γ 00 (superstructure of the D0 22 type)- and γ’ (superstructure of the L1 2 type)- phase precipitation 

precedes the formation of the stable NbNi3 phase. Fine precipitates of the Ll2 type ordered 

phase observed upon annealing in the alloys with 6 and 8 at.% Nb result from ordering 

processes in the Ni base γ solid solution. The processes develop actively upon annealing at 

900 - 1100˚C in the alloy where the long-range order in the initial state has been suppressed by 

rapid quenching. 

. Table 1 

Investigations of the Fe-Nb-Ni Phase Relations, Structures and Thermodynamics 


[1975Pan] Optical metallography, X-ray 

diffraction, DTA 

[1980Rus] NGR, DSC, dilatometry, resistivity, 

Vickers hardness 


Studied 

NbFe 2 - NbNi 3 join, quasibinary section 

Fe-2.6 at.% Nb 13.4 at.% Ni, water quenching 

from 1200˚C, annealed for 1 h at 250-750˚C 

[1980Tew] SEM, TEM, electron diffraction Directionally solidified Fe-12 at.% Nb-17.7 at.% Ni 

alloy, (αFe)+NbFe 2 

[1981Var] Optical metallography, X-ray 

diffraction, EDAX 

950˚C, then quenched. NbFe-NbNi and NbFe 2- 

NbNi 2 joins 

[1984Ska] XRD 35 to 50 at.% Nb, < 85 at.% Ni, quenched with 

rates from 10 2 to 10 6 K·s –1 

[1985Val] XRD, Neutron diffraction, resistivity 

measurements 

[1987Val] Neutron diffraction on alloy with 

different Ni isotopic composition 

Ni 3Fe 1–xNb x, water quenched from 1100˚C with 

tempering at 900˚C 

Nb 0.3Fe 0.7Ni 3 annealed at 850˚C and slow cooled 

to room temperature 

[1989Sav] X-ray diffraction Ni-Nb and Fe-Nb quenched from the melt at 

cooling rates up to 10 4 -10 6 ˚C·s –1 

[1992Sos] Optical microscopy, TEM, XRD, 

microhardness, crystallographic 

texture 




16 at.% Fe, < 8 at.% Nb, rapid quenching by 

spinning, heat treatment in the temperature 

range 300-1000˚C for 1 h 

MSIT 1 

DOI: 10.1007/978-3-540-70890-2_5 


5

6 5 

Fe–Nb–Ni 



[1993Zhi] SEM, XRD, electron microdifraction, 

phase ordering investigation 

[1993Kov] X-ray diffraction, TEM, shape 

memory effect investigation 

[2001Tak] SEM, TEM, XRD, EPMA (Electron 

Probe Microanalysis) 


Studied 

Ni 85–xFe 15Nb x (x = 4, 6, 8); rapid quenching by 

spinning, annealed 200-1200˚C 

100 h at 1200˚C then water quenched, aged at 

650˚C for 6 to 100 h., 31 mass % Ni, 4.6 to 6.8 

mass% Nb. Shape memory effect 

1200-1250˚C, 15 to 25 at.% Nb, 5 to 25 at.% Fe, 

phase diagram 

[2005Tak] SEM, TEM, XRD, EPMA 1200˚C, 15 to 40 at.% Ni, 15 to 35 at.% Nb, phase 

diagram 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 



(δFe) cI2 a = 293.15 pure Fe at 1394˚C [V-C2, Mas2] 

1538 - 1190 Im3m 

W 

0-3.27 at.% Nb at 1370˚C [1993Bej] 

0-3.8 at.% Ni at 1514˚C [2008Kuz] 

(αFe) cI2 a = 286.65 pure Fe at 25˚C [Mas2] 

< 912 Im3m 0-0.73 at.% Nb at 960˚C [1993Bej] 

W 0-4.7 at.% Ni at 347˚C [2008Kuz] 

γ, (γFe,Ni) cF4 a = 354 Ni-10 at.% Fe 

Fm3m 

Cu 

a = 355.2 Ni-10 at.% Fe-2 at.% Nb [1990Cho] 

(γFe) a = 364.67 pure Fe at 915˚C [Mas2] 

1394 - 912 0-1.0 at.% Nb at 1190˚C [1993Bej] 

(Ni) a = 352.40 pure Ni at 25˚C [Mas2] 

< 1455 0-12.4 at.% Nb at 1282˚C [1998Oka] 

(Nb) cI2 a = 330.04 pure Nb at 25˚C [Mas2] 

< 2469 Im3m 0-4.2 at.% Ni at 1295˚C [1998Oka] 

W 0-7.0 at.% Fe at 1500˚C [1993Bej] 


P63/mmc Mg 

c = 396.0 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 




λ1,Nb1–y(Fe1–xNix) 2 hP12 Laves Phase 

P63/mmc x < 0.45, - 0.23 < y < 0.26 

MgZn2 [2005Tak] 

NbFe2 32-37 at.% Nb [1993Bej] 

< 1630 a = 483.8 

c = 788.9 

33.3 at.% Nb [2005Tak] 

a = 481.0 

c = 785.2 

27.1 at.% Nb [2005Tak] 

μ, (Fe,Nb,Ni) hP13 

Nb6Fe7 R3m a = 492.8 48-52 at.% Nb [1993Bej] 

< 1520 Fe7W6 c = 2683 

Nb7Ni6 a = 489.6 Nb49.6Ni50.4 [2002Jou] 

< 1295 c = 2661.4 

a = 495.9 

c = 2699.8 

Nb56..9Ni43.1 [2002Jou] 

FeNi3 cP4 a = 355.23 63 to 85 at.% Ni [2008Kuz] 

< 517 Pm3m 

AuCu3 FeNi (metastable) tP2 a = 357.9 [2008Kuz] 

P4/mmm 

AuCu 

c = 357.9 

NbNi3 oP8 22.7-27.5 at.% Nb [1998Oka] 

< 1402 Pmmm a = 511.6 [1991Gup] 

βCu3Ti b = 425.9 

c = 456.5 

NbNi8 tI* a = 1080 11.1 at.% Nb [1991Gup] 

< 535 - c = 360 

* τ, (Fe,Nb,Ni) hP24 - Fe-22Nb-58Ni [2001Tak] 

λ2,Nb1–y(FexNi1–x) 2 cF24 - Laves phase. Probably metastable 

Fd3m 

[1989Sav] 

MgCu2 0.35 < x < 0.67; y < 0.25 

λ3, Nb(FeNi) 2 hP24 - Laves phase. Probably metastable 

P63/mmc [1989Sav] 

MgNi2 ~ 40 at.% Fe and 40 at.% Ni 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_5 


7

8 5 

Fe–Nb–Ni 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

γ ’ cP4 Nearly the same 

Pm3m 

AuCu 3 



parameters as those of 

the mother γ phase 

Metastable phase formed by aging a 

rapid quenched melt Ni-16at.% 

Fe-(6, 8) at.% Nb [1993Zhi] 

γ ’’ tI8 a = 361.4 Metastable [1993Kov, 1993Zhi] 

I4/mmm c = 757.6 

TiAl 3 ? 

. Table 3 


Reaction T [˚C] Type Phase 

Fe 

Composition (at.%) 

Nb Ni 

L Ð NbFe2 + NbNi3 1290 e L 16.2 27 56.8 

NbFe2 38.8 29.9 31.3 

NbNi3 5.1 25.6 69.3 

. Table 4 

Investigations of the Fe-Nb-Ni Materials Properties 


[1971Lei] XRD, electron diffraction technique, 

TEM, hardness measurements 

[1972Mas, 

1974Mas] 

Electrical resistivity, initial 

permeability, coercive force, 

hardness 

[1976Hin] Electrical resistivity, crystal 

anisotropy, magnetostriction, 

[1978Mas] Magnetric permeability, coercive 

force 

Fe 67.3Ni 29.6Nb 3.1 (in at.%), quenched from 

1250˚C, aged at 700-800˚C, hardening 

950-1350˚C, 73-85 mass% Ni, 6-25 mass% Fe, 

high permeability alloys 

80 mass% Ni, 10 to 20 mass % Fe, alloys with 

high magnetic permeability 

Initial and maximum permeability 



MSIT 1



[1979Wen] TEM, X-ray diffraction, magnetic 

properties, Vickers hardness 

[1981Tai] X-ray diffraction, Vickers hardness, 

rolling texture 

Effect of modulated structure on hardness 

and magnetic permeability 

79Ni-8Nb-13Fe (mass%) alloy; after cold 

rolling with reduction of 50 and 94% 

[1982Osi] Magnetic susceptibility, Curie points 20-800˚C, NbFe 2 - NbNi 3 join. 

Magnetic properties of the Laves 

phase λ 1 

[1985Kov1] 

[1985Kov2] 

Optical microscopy, XRD, resistivity, 

tensile test, bending deflection 

[1989Kov] Optical microscopy, resistivity, 

bending deflection measurements 

Mechanical properties and the degree of 

recovery of shape (shape memory alloys) 

The degree of recovery of shape 

[1990Cho] Instron type testing machine 10 to 20 mass % Ni, < 4 mass% Nb, 

compressive flow stress at 77 K. 

[1992Sos] Coercive force, magnetic 

permeability, microhardness 



MSIT 1 


16 mass% Fe, < 4 mass% Nb, mechanical 

properties after rapid quenching 

DOI: 10.1007/978-3-540-70890-2_5 


9

10 5 

Fe–Nb–Ni 

. Fig. 1 

Fe-Nb-Ni. Change in lattice parameters of the λ 1-NbFe 2 Laves phase with Ni content (line - 

calculation; empty circles - stoichiometric composition, filled circles - Fe-rich compositions 



MSIT 1

. Fig. 2 

Fe-Nb-Ni. Isothermal section at 1200˚C 



MSIT 1 


DOI: 10.1007/978-3-540-70890-2_5 


11

12 5 

Fe–Nb–Ni 

References 

[1971Lei] Leitch, K., Chaturvedi, M., “Aging Behavior of Fe-30Ni Alloys Containing Niobium”, Metall. Trans., 

2(5), 1407-1413 (Crys. Structure, Morphology, Phase Relations, Experimental, Kinetics, Mechan. 

Prop., 25) 

[1972Mas] Masumoto, H., Murakami, Y., Hinai, M., “Magnetic Characteristics of Ni-Fe-Nb Alloys”, Trans. Jpn. 

Inst. Met., 13(3), 182-185 (1972), translated from J. Jpn. Ins. Met., 35(10), 985-988 (1971) (Experimental, 

Electr. Prop., Magn. Prop., 23) 

[1974Mas] Masumoto, H., Murakami, Y., Hinai, M., “Magnetic Properties of High Permeability Alloys Hardperm 

in the Ni-Fe-Nb System”, J. Jpn. Inst. Met., 38(3), 238-241 (1974) (Phase Relations, Electr. Prop., Magn. 

Prop., Experimental, 4) 

[1975Pan] Panteleimonov, L.A., Aleshina, L.V., “Alloys of the Fe 2Nb-Ni 3Nb System” (in Russian), Vestn. Moskov. 

Univ., (Khim), 16(5), 630-634 (1975) (Crys. Structure, Morphology, Phase Diagram, Experimental, #, 3) 

[1976Hin] Hinai, M., “The Origin of High Magnetic Permeability in Hardperm of the Ni-Fe-Nb System”, Trans. 

Jpn. Inst. Met., 17(11), 693-698 (1976), translated from J. Jpn. Ins. Met., 40(7), 682-686 (1976) (Phase 

Relations, Experimental, Magn. Prop., 21) 

[1978Mas] Masumoto, H., Hinai, M., Murakami, Y., “The Influence of Sheet Thickness and Heat Treatment on the 

Magnetic Properties of Hardperm Alloys in the Ni-Fe-Nb System”, Trans. Jpn. Inst. Met., 19(7), 385-389 

(1978) (Phase Relations, Experimental, Magn. Prop., 8) cited from abstract 

[1979Wen] Wenchong, X., Junjian, W., Xiujin, S., Zhihua, L., “An Investigation of Magnetic Ni-Fe-Mo and Ni-Fe- 

Nb Alloys” (in Chinese), Acta Metall. Sin., 15(2), 252-258 (1979) (Phase Relations, Experimental, 

Magn. Prop., 8) cited from abstract 

[1980Rus] Rusanenko, V.V., Perkas, M.D., Shaposhnikov, N.G., Edneral, A.F. “Ageing of Fe-Ni-Nb and Fe-Ni-Nb-Co 

Alloys Martensite” (in Russian), Metallofizika, 2(6), 56-62 (1980) (Phase Relations, Experimental, Electr. 

Prop., Mechan. Prop., 12) 

[1980Tew] Tewari, S.N., “Growth Crystallography of Directionally Solidified Fe-Nb-Ni Eutectic Alloy”, Metallography, 

13(4), 379-381 (1980) (Crys. Structure, Morphology, Phase Relations, Experimental, 2) 

[1981Tai] Tai, L.C., Tan, Z.J., “A Note on the Rolling Texture of Nickel-Iron-Niobium Alloy”, Texture of 

Crystalline Solids, 4(3), 153-157 (1981) (Morphology, Experimental, Mechan. Prop., 7) 

[1981Var] Varli, K.K., Druzhinia, T.I., D’yakonova, N.P., Pirogova, S.E., Rutman, A.M., “The Influence of Alloying 

with Cobalt and Nickel on the Phase Stability of the Fe-Nb System” (in Russian), Izv. Vys. Ucheb. Zaved. 

Chern. Metall., (9), 116-118 (1981) (Crys. Structure, Phase Relations, Experimental, 3) 

[1982Osi] Osipova, L.V., Panteleymonov, L.A., “Magnetic Properties of Fe-Ni-Zr and Fe-Ni-Nb Alloys”, Russ. 

Metall., (3), 183-185 (1982), translated from Izv. Akad. Nauk, Met., (3), 205-207 (1982) (Experimental, 


[1984Ska] Skakov, Y.A., Dyakonova, N.P., Savin, V.V., Semina, V.K., Sharshatkina, A.V., “Influence of Cooling 

Rate of Melt on Structure of Phases in Fe-Co-Nb and Fe-Ni-Nb Systems” (in Russian), Izv. Vys. Ucheb. 

Zaved. Chern. Metall., (5), 85-90 (1984) (Crys. Structure, Phase Relations, Experimental, 6) 

[1985Kov1] Koval’, Yu.N., Kozlov, A.P., Monastyrskii, G.E., “Martensitic Transformation and Memory Shape Effect 

in Fe-Nb-Ni Alloys”, Akad. Nauk Ukr. SSR, Metallofizika, 7(4), 53-59 (1985) (Crys. Structure, Morphology, 

Phase Relations, Experimental, Mechan. Prop., 15) 

[1985Kov2] Koval’, Yu.N., Kozlov, A.P., Monastyrskii, G.E., “The Effect of Phase Hardening on the Shape-Memory 

Effect in Fe-Ni-Nb Alloys” (in Russian), Akad. Nauk Ukr. SSR Metallofizika, 7(5), 95-99 (1985) 

(Morphology, Phase Relations, Experimental, Mechan. Prop., 5) 

[1985Val] Valiyev, E.Z., Men’shikov, A.Z., Panakhov, T.M., “The Structural State of Alloys Ni 3(Fe 1–xTi x) and 

Ni 3(Fe 1–xNb x) During Atomic Ordering”, Phys. Met. Metallogr., 59(1), 123-129 (1985) (Crys. Structure, 

Phase Relations, Experimental, Electr. Prop., 14) 

[1987Val] Valiev, E.Z., Menshikov, A.Z., “Nature of K State in Alloyed Permalloys” (in Russian), Fiz. Met. 

Metolloved., 63(5), 1030-1032 (1987) (Experimental, Crys. Structure, Phase Relations, 6) 

[1989Kov] Koval, Yu.N., Kozlov, A.P., Monastyrskii, G.E., “Influence of Work Hardening Caused by Martensitic 

Transformation on the Shape Memory Effect in Fe-Ni-Nb Alloys”, Scr. Metall., 23(10), 1731-1734 

(1989) (Morphology, Phase Relations, Experimental, Mechan. Prop., 3) 

[1989Sav] Savin, V.V., “Formation and Stability of Laves Phases in the System Ni-Fe-Nb”, Phys. Met. Metallogr., 

68, 140-146 (1989), translated from Fiz. Met. Metalloved., 68(1), 143-149 (1989) (Crys. Structure, Phase 

Diagram, Phase Relations, Experimental, 16) 



MSIT 1


[1990Cho] Choi, G., Shinoda, T., Mishima, Y., Suzuki, T., “Solid Solution Hardening in Ternary Ni-Y(Y:Co, Pd, 

Fe)-Nb Alloys”, ISIJ Int., 30(9), 780-785 (1990) (Thermodyn., Experimental, Kinetics, 20) 

[1991Gup] Gupta, K.L., “The Nb-Ni (Niobium-Nickel) System” in “Phase Diagrams of Ternary Nickel Alloys”, 

Indian Inst. Met., Calcutta, Part 2, 151 (1991) (Phase Diagram, Review, 1) 

[1992Mes] Meshkov, L.L., Nesterenko, S.N., Uskova, E.N., “The Laws of Phase Equilibria in Ternary Systems of 

Refractory Transition Metals with Group VIIIB Metals”, Russ. Metall., (6), 140-144 (1992), translated 

from Izv. Ross. Akad. Nauk. Met., (6), 153-157 (1992) (Phase Relations, Calculation, 10) 

[1992Rag1] Raghavan, V., “The Fe-Nb-Ni (Iron-Niobium-Nickel) System” in “Phase Diagrams of Ternary Iron 

Alloys”, Indian Inst. Met., Calcutta, 6B, 1025-1027 (1992) (Crys. Structure, Phase Diagram, Review, 11) 

[1992Rag2] Raghavan, V., “The Fe-Nb (Iron-Niobium) System” in “Phase Diagrams of Ternary Iron Alloys”, Indian 

Inst. Met., Calcutta, 6A, 38 (1992) (Crys. Structure, Phase Diagram, Review, 2) 

[1992Sos] Sosnin, V.V., Glezer, A.M., Zhigalina, O.M., “Structure and Properties of Microcrystalline Alloys of the 

System Ni-Fe-Nb(Mo)”, Met. Sci. Heat Treat., 34(3-4), 195-202 (1992) (Crys. Structure, Morphology, 

Experimental, Magn. Prop., Mechan. Prop., 12) 

[1993Bej] Bejarano, J.M.Z., Gama, S., Ribeiro, C.A., Effenberg, G., “The Iron-Niobiun Phase Diagram”, Z. 

Metallkd., 84(3), 160-164 (1993) (Crys. Structure, Morphology, Phase Diagram, Experimental, #, 6) 

[1993Kov] Koval, Yu.N., Monastyrsky, G.E., “Reversible Martensite Transformation and Shape Memory Effect in 

Fe-Ni-Nb”, Scr. Metall. Mater., 28(1), 41-46 (1993) (Morphology, Experimental, Kinetics, 15) 

[1993Zhi] Zhigalina, O.M., Sosnin, V.V., Glezer, A.M., “The Effects of Heat Treatment on Phase Transformations 

in Rapidly Quenched Ni-Fe-Nb Alloys”, Phys. Met. Metallogr., 75(2), 205-209 (1993), translated 

from Fiz. Met. Metallov., 75(2), 132-139 (1993) (Crys. Structure, Morphology, Phase Relations, Experimental, 

12) 

[1998Oka] Okamoto, H., “Nb-Ni (Niobium-Nickel)”, J. Phase Equilib., 19(3), 289 (1998) (Phase Diagram, 

Review, #, 7) 

[2001Tak] Takeyama, M., Morita, S., Yamauchi, A., Yamanaka, M., Matsuo, T., “Phase Equilibria Among γ, 

Ni 3Nb-δ and Fe 2Nb-ε Phases in Ni-Nb-Fe and Ni-Nb-Fe-Cr Systems at Elevated Temperatures”, Proc. 

Int. Sympos., TMS-Miner. Metals & Mater. Soc., 333-344 (2001) (Crys. Structure, Morphology, Phase 

Diagram, Phase Relations, Experimental, #, 17) 

[2002Jou] Joubert, J.-M., Feutelais, Y., “Contribution of the Rietveld Method to Non-Stoichiometric Phase 

Modeling. Part II: γ -Tl 5Te 3 and μ - Nb-Ni as Experimental Examples”, Calphad, 26(3), 427-438 (2002) 

(Crys. Structure, Calculation, Experimental, 15) 

[2004Rag] Raghavan, V., “Fe-Nb-Ni (Iron-Niobium-Nickel)”, J. Phase Equilib. Diffus., 25(6), 552 (2004) (Phase 


[2005Tak] Takeyama, M., Gomi, N., Morita, S., Matsuo, T., “Phase Equilibria and Lattice Parameters of Fe 2Nb 

Laves Phase in Fe-Ni-Nb Ternary System at Elevated Temperatures”, Mater. Res. Soc. Symp. Proc., 842, 

461-466 (2005) (Experimental, Morphology, Phase Diagram, Phase Relations, #, 11) 

[2008Kuz] Kuznetsov, V., “Fe-Ni (Iron-Nickel)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg, 

G. (Ed.), MSI, Materials Science International Services, GmbH, Stuttgart; to be published (2008) (Crys. 

Structure, Phase Diagram, Phase Relations, Assessment, 41) 


(1990) 





MSIT 1 

DOI: 10.1007/978-3-540-70890-2_5 


13

Iron – Niobium – Phosphorus 


Gabriele Cacciamani, Lesley Cornish, Damian M. Cupid, Jozefien De Keyzer 

Introduction 

The Fe-Nb-P system is only partially known. The main work on this system was done in the 

sixties by [1962Vog] who investigated the Fe rich corner. [1962Vog] prepared 250 alloy 

compositions in the Fe-FeP-Nb region from pure iron, red phosphorus and sheet niobium 

(purities not stated). The phase equilibria were studied by thermal analysis (cooling rate of 0.5 

to 2˚C·s –1 ), metallography, ray diffraction, hardness and magnetic measurements. Even though 

[1962Vog] presented a liquidus surface covering the Fe-FeP-NbP 2-Nb region of the system, 

their experimental measurements were limited to the Fe-FeP-Nb region. This is also the most 

important corner since niobium is used as a strengthening element in steels and phosphorus is 

a common impurity in steels [1987Gra]. The system was reviewed by [1988Rag]. 


The accepted binary Fe-Nb phase diagram is that from [1993Bej]. A thermodynamic calculation 

of the Fe-Nb system is from [2000Tof]. It incorporates many data points and is preferred 

to the earlier calculation of [1994Sri]. Both of these show the peritectic formation of the μ 

phase, rather than the earlier reported congruent formation [1986Pau]. 

The Fe-P system is accepted from the critical assessment of [2002Per]. 

The Nb-P phase diagram is not known, except for the partial diagram postulated by 

[1962Vog] to accommodate the NbP and NbP 2 phases [1931Hei]. 


Crystal structure data on unary, binary and ternary phase are summarized in Table 1. 

Since the Nb-P phase diagram not known, all binary Nb-P structures found in literature 

have been reported here, but it is not clear which are stable phases in the system. 

Three ternary compounds were identified by [1962Vog] in the Fe-FeP-Nb region. FeNbP 

(τ 1) is a well-established, congruently melting phase with the Co 2Si type structure [1962Vog, 

1966Run, 1965Kan1, 1973Mae]. The other two compounds melt incongruently and correspond 

to the formulae FeNb 2P(τ 2) and FeNb 4P(τ 3). The crystal structure of FeNb 4P has been 

determined by [1977Pal]. 


Fe–Nb–P 6 

In the Fe-FeP-Nb region, [1962Vog] found three quasibinary systems of the simple eutectic 

type: Fe-τ 1 (Fig. 1), Fe 2Nb-τ 1 (Fig. 2), and FeP-τ 1, together with two quasibinaries of the 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_6 


1

2 6 

Fe–Nb–P 

simple peritectic type: Fe 2P-τ 1 (Fig. 3), and τ 1-τ 2, which they drew schematically. Three of these 

quasibinary sections are included in the FeP-Nb section. However, the quasibinary character of 

the FeP-Nb section does not extend to pure FeP because, at higher temperatures, this phase is 

in equilibrium with liquid and gas and tie lines are presumably not in the plane of the section. 

Additionally, [1965Kan1] reported a wider solubility range in τ 1 at 800˚C. These data are given 

in Table 2. 


The reaction scheme shown in Fig. 4 is based on the work of [1962Vog]. The temperature and 

composition of the U 2 reaction (see Table 2), which was added by [1988Rag], were changed to 

be consistent with the currently accepted Fe-Nb binary system [1993Bej]. In the solid state, the 

three-phase univariant line arising from the eutectoid reaction in the Fe-Nb system at 1190˚C 

passes through the ternary region to return to the Fe-Nb side and culminate in the peritectoid 

reaction at 960˚C. This situation arises, as the γ phase (γFe) in the Fe-P system is fully enclosed by 

aloop. 

Liquidus Surface 

Even though [1962Vog] presented a liquidus surface covering the Fe-FeP-NbP2-Nb region of 

the system, their experimental measurements were limited to the Fe-FeP-Nb region. The rest 

of the system was inferred from the known binary and ternary compounds, and using 

compatibility triangles. The surface for the Fe-FeP-Nb region has been redrawn in Fig. 5 

using the currently accepted binary data. Reaction U 2 was introduced by [1988Rag] to account 

for the presence of the μ phase in the Fe-Nb system (not included by [1962Vog]), and altered 

here to be consistent with the currently accepted Fe-Nb binary of [1993Bej]. 

[1997Vav] studied the metastable (rapidly-cooled) liquidus around Fe 3P in order to obtain 

amorphous phases. 


[1988Rag] has drawn isothermal sections (at.% and mass%) at 25˚C using the data of 

[1962Vog] and adding μ, and this is redrawn here to be consistent with the currently accepted 

Fe-Nb binary system (Fig. 6). [1965Kan1] determined an isothermal section for the iron rich 

region at 800˚C. Their results indicated a wider homogeneity range for FeNbP (τ1) extending 

towards Fe3P, rather than the line compound of [1962Vog] at room temperature. Niobium 

drastically lowers the solubility of phosphorus in (αδFe) at 1000˚C [1965Kan2]. 

For non-equilibrium alloys (annealed rapidly-cooled specimens), [1997Vav] showed that 

Fe 2P extends further into the ternary than Fe 3P, and there was a (αδFe) + Fe 3P+Fe 2P threephase 

field at 1.1 at.% Nb. 



MSIT 1


[1962Vog] has drawn a number of vertical sections, including those between Fe 3P-NbFeP (Fig. 

7) (with some apparently unresolved data points at about 1050˚C); Fe 3Nb-Nb 4FeP, at 2 mass% 

Nb (Fig. 8) and at 2 mass% P. The latter is inconsistent with the currently accepted Fe-Nb 

binary diagram because of μ in the latter, but [1962Vog] only had one alloy in that region. 

A small region of amorphous phases was found in the Fe3P region and a metastable Fe2P 

phase was identified [1989Bab, 1997Vav]. 


The vapor pressure of phosphorus on liquid Fe-Nb-P alloys has been measured by the 

transportation method at 1400˚C by [1984Ban] (Table 3) and by Knudsen effusion method 

by [1979Yam, 1983Yam] at 1600˚C. 

The two authors calculated an interaction coefficient eNb P defined as: 

e Nb 

P 

@IngNb P ¼ 

@xNb Xp!0 

on the basis of the Chipman interstitial solution model. 

According to [1984Ban] eNb P = –16.1±1.6 while according to [1979Yam, 1983Yam] itis 

eNb P = –5.4±1.2. A calculation performed by [1993Din] at 1600˚C produced a value of 

= –6.92. 

e Nb 

P 


Fe–Nb–P 6 

Phosphorous is a glass-forming element and is used in the manufacture of iron-based 

amorphous magnetically soft materials [1997Vav]. Unfortunately, phosphorus is also one of 

the most harmful elements for steel products so that efforts have been made to remove 

phosphorus from molten iron in the steelmaking process, or employ alloying additions 

(e.g. Nb) that react to form precipitates and thus tie up P [1987Gra]. Iron phosphides may 

improve resistance to scale formation, but, unless rectified, phosphorous segregates to the 

grain boundaries, and also forms low melting point eutectics. These result in the impairment 

of mechanical properties from reduced grain boundary cohesion and temper embrittlement 

[1984Moe]. High Fe content alloys were studied [1984Moe], and P was consistently enriched 

at the grain boundaries, usually with Nb, but not in equilibrium conditions. Increased Nb 

decreased the grain boundary P segregation, as did increasing tempering temperature. The 

influence of various elements on the segregation of phosphorus atoms in iron was examined 

by Mössbauer spectroscopy [1999Vav], and ranked in decreasing influence as: Mn > Si > V > 

Nb > Mo. 

Experimental studies of properties are summarized in Table 4. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_6 


3

4 6 

Fe–Nb–P 

Miscellaneous 

Crystallization kinetics were derived by [1990Bab1] using DTA and electrical resistance under 

isothermal conditions. Mössbauer measurements undertaken by [1973Mae] indicated that Fe 

atoms only occupied the smaller lattice positions. Similar work by [1990Bab2, 1999Vav, 

2000Vav] on rapidly-quenched alloys, showed that metastable Fe2P made the stable formation 

of amorphous Fe3P difficult. Metastable Fe2P was anti-ferromagnetic [1999Vav]. [1962Vog] 

found that alloys containing (αδFe) were ferromagnetic; their other compositions were 

paramagnetic. 

. Table 1 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


αδ, (αδFe) cI2 up to 4.9 at.% P at 1048˚C [1997Hin] 

Im3m up to 3.2 at.% Nb at 1373˚C [1986Pau] 

W up to 0.7 at.% Nb at 961˚C [1986Pau] 

(δFe) 

1538 - 1394 

a = 293.15 pure Fe at 1390˚C [V-C2, Mas2] 

(αFe) 

< 912 

a = 286.65 pure Fe at 25˚C [Mas2] 

(γFe) cF4 a = 364.67 pure Fe at 915˚C [V-C2, Mas2] 

< 1394 - 912 Fm3m up to 0.6 at.% P at 1150˚C [1997Hin] 

Cu up to 0.9 at.% Nb at 1210˚C [1986Pau] 


P63/mmc Mg 

c = 396.0 

(Nb) cI2 a = 330.04 at 25˚C [Mas2] 

< 2469 Im3m 

W 

(P) (I) cP1 

Pm3m 

αPo 

a = 220 to 227 10 to 32 GPa [V-C2] 

(P) (II) hR6 a = 337.7 high pressure phase, 

R3m 

As 

c = 880.6 5 to 11.1 GPa [V-C2] 

(P) (red) c*66 a = 1131 sublimation at 1 bar triple point at 576˚C, > 36.3 

< 417 

bar; triple point at 589.6˚C at 1 atm [Mas2, V-C2] 

(P) (white) c** a = 718 at 25˚C [Mas2] 

< 44.14 ? common form of elemental P, probably less stable 

P (white) 

than P (red) at 25˚C [Mas2] 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


(P) (black) oC8 a = 331.36 at 25˚C [Mas2, V-C2] 

Cmca b = 1047.8 

P (black) c = 437.63 

ε, NbFe2 hP12 a = 483.8 32 to 37 at.% Nb [1993Bej] 

< 1630 P63/mmc MgZn2 c = 788.9 

μ, Nb6Fe7 hR39 a = 492.8 48.0-52.0 at.% Nb [1993Bej] 

≲ 1520 R3m 

Fe7W6 c = 268.3 “FeNb” [1986Pau] 

Nb3Fe2 1490 - 1460 

- - metastable [1991Bej] 

Fe3P tI32 a = 910.8 25 at.% P [Mas2, V-C2] 

< 1166 I4 c = 445.5 

Ni3P a = 917.4 

c = 452.99 

at 678˚C [2002Per] 

Fe2P hP9 a = 586.4 33.3 at.% P 

< 1370 P62m 

Fe2P c = 346.0 [Mas2, V-C2] 

Fe2P (I) oP12 a = 577.5 at 800˚C and 80 kbar [Mas2, V-C2] 

Pnma b = 357.1 

Co2Si c = 664.1 

FeP oP8 a = 520.8 [V-C2] 

< 1370 Pnma b = 316 

MnP c = 581.2 

FeP2 oP6 a = 497.29 [1934Mei] 

Pnnm b = 565.68 


c = 272.3 

FeP4 mP30 a = 461.9 [1978Jei] 

P21/c b = 1367.0 

FeP4 c = 700.2 

β =101.48˚ 

FeP4 (I) oC20 a = 500.5 at 1100˚C and 60 kbar [1978Sug] 

C2221 b = 1021.3 

FeP4 c = 553.0 

Nb3P tP32 a = 1012.8 [V-C2] 

P42/n Ti3P c = 508.9 



MSIT 1 

Fe–Nb–P 6 

DOI: 10.1007/978-3-540-70890-2_6 


5

6 6 

Fe–Nb–P 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


Nb2P oP54 a = 1807.9 [V-C2] 

Pmma b = 342.5 

Nb2P c = 1385.8 

Nb7P4 mC44 a = 1495.0 [V-C2] 

C2/m b = 344.0 

Nb7P4 c = 1384.8 

β = 104.74˚ 

Nb5P3 oP64 a = 2538.4 [V-C2] 

Pnma b = 343.3 

Nb5As3 c=1148.3 

Nb8P5 oP54 a = 2620.0 [V-C2] 

Pbam b = 946.5 

Nb8P5 c = 346.4 

NbP tI8 a = 333.4 [V-C2] 

I41md NbAs 

c = 1137.6 

Nb4P7 tP29 a = 746.8 [V-C2] 

P4m2 

V4P7 c=764.9 

NbP2 mC12 a = 887.15 [V-C2] 

C2 b=326.63 

NbSb2 c = 751.94 

β = 119.10˚ 

Nb2P5 oP28 a = 1674.2 prepared at 5 GPa [V-C2] 

Pnma b = 335.0 

Nb2P5 c=791.2 

* τ1, NbFeP oP12 a = 613.9 [1966Run, V-C2] 

< 1820 Pnma b = 358.5 Congruent melting point [1962Vog] 

Co2Si c=700.6 

* τ2, Nb2FeP 

≲ 1585 

- - Incongruent melting point [1962Vog] 

* τ3,Nb4FeP tP12 a = 613.0 [V-C2] 

≲ 1545 P4/mcc 

CoNb4Si c = 500.6 Incongruent melting point [1962Vog] 



MSIT 1

. Table 2 



Fe 


Nb P 

L+τ1 Ð τ2 ~1750 p1 L 21.3 57.8 20.9 

L+τ2 Ð τ3 1660 p2 L 10.1 80.0 9.9 

L Ð τ3 + (Nb) ~1600 e1 L 9.2 82.4 8.4 

L Ð ε + τ1 1555 e2 L 52.6 33.3 14.1 

L+τ1 Ð ε + τ2 1537 U1 L 38.9 48.6 12.5 

L+ε Ð μ + τ2 ~1510 U2 L ~41 ~51.5 ~7.5 

L+τ2 Ð μ + τ3 1503 U3 L 39.5 56.8 3.7 

L Ð μ + τ3 + (Nb) 1489 E1 L 36.3 61.2 2.5 

L+τ1 Ð Fe2P 1405 p4 L 64.7 2.0 33.3 

L Ð τ1 + FeP ~1400 e4 L 46.5 7.7 45.8 

L Ð τ1 +(αδFe) ~1303 e6 L 83.5 8.2 8.3 

L Ð ε + τ1 +(αδFe) 1295 E2 L 84.0 9.3 6.7 

L+τ1 Ð FeP + Fe2P 1275 U4 L 58.9 1.8 39.3 

L+Fe2PÐ τ1 +Fe3P 1125 U5 L 76.0 0.5 23.5 

L Ð μ + τ3 + (Nb) 1045 E3 L 82.6 0.7 16.7 

. Table 3 

Vapor Pressure Measurements 

Phase(s) Temperature [˚C] Pressure [bar] Comments 

Liquid (x Nb = 0.032, 

xP = 0.164) 

Liquid (xNb = 0.049, 

xP = 0.196) 

Liquid (xNb = 0.057, 

xP = 0.200) 

Liquid (x Nb = 0.064, 

xP = 0.209) 



1400 p P = 4.9·10 –5 

1400 p P = 5.1·10 –5 

1400 pP = 6.0·10 –5 

1400 p P = 4.0·10 –5 

MSIT 1 

Fe–Nb–P 6 

[1984Ban] transportation 

method 


method 


method 


method 

DOI: 10.1007/978-3-540-70890-2_6 


7

8 6 

Fe–Nb–P 

. Table 4 

Investigations of the Fe-Nb-P Materials Properties 

Reference 

Method / Experimental 

Technique Type of Property 

[1973Mae] Mössbauer Site occupancy; ordering 

[1984Moe] Auger electrons P grain boundary enrichment 

[1990Bab1] DTA, electrical resistance, TEM Kinetics; time dependence of crystallization 

volume 

[1990Bab2] Mössbauer Site occupancy; ordering 

[1999Vav] Mössbauer Phase identification; magnetic studies 



MSIT 1

. Fig. 1 

Fe-Nb-P. The (αδFe) - τ 1 quasibinary system 



MSIT 1 

Fe–Nb–P 6 

DOI: 10.1007/978-3-540-70890-2_6 


9

10 6 

Fe–Nb–P 

. Fig. 2 

Fe-Nb-P. The NbFe 2 - τ 1 quasibinary system 



MSIT 1

. Fig. 3 

Fe-Nb-P. The Fe 2P-τ 1 quasibinary system 



MSIT 1 

Fe–Nb–P 6 

DOI: 10.1007/978-3-540-70890-2_6 


11

12 6 

Fe–Nb–P 

. Fig. 4 

Fe-Nb-P. Partial reaction scheme in the Fe-FeP-Nb region 



MSIT 1

. Fig. 5 

Fe-Nb-P. Partial liquidus projection in the Fe-FeP-Nb region 



MSIT 1 

Fe–Nb–P 6 

DOI: 10.1007/978-3-540-70890-2_6 


13

14 6 

Fe–Nb–P 

. Fig. 6 

Fe-Nb-P. Partial isothermal section at 25˚C 



MSIT 1

. Fig. 7 

Fe-Nb-P. Vertical section τ 1 -Fe 3P 



MSIT 1 

Fe–Nb–P 6 

DOI: 10.1007/978-3-540-70890-2_6 


15

16 6 

Fe–Nb–P 

. Fig. 8 

Fe-Nb-P. Section at 2 mass% Nb, plotted in at.% 



MSIT 1

References 

Fe–Nb–P 6 

[1931Hei] Heinerth, E., Biltz, W., (in German) Z. Anorg. Allg. Chem., 198, 168-177 (1931) (Phase Diagram, 

Experimental, 12) quoted in [1962Vog] 

[1934Mei] Meisel, K., “Crystal Structure of FeP 2” (in German), Z. Anorg. Chem., 218(4), 360-364 (1934) (Phase 

Diagram, Crys. Structure, Experimental, 5) 

[1962Vog] Vogel, R., Bleichroth W., “The Iron-Phosphorus-Niobium Ternary System” (in German), Arch. 

Eisenhuttenwesen., 33(1), 195-210 (1962) (Phase Diagram, Experimental, #, *, 27) 

[1965Kan1] Kaneko, H., Nishizawa, T., Tamaki, K., “Phosphide-Phases in Ternary Alloys of Fe, P and Other 

Elements” (in Japanese), Nippon Kinzoku Gakkai-shi, 29(2), 159-165 (1965) (Phase Diagram, Morphology, 


[1965Kan2] Kaneko, H., Nishizawa, T., Tamaki, K., Tanifuji, A., “Solubility of Phosphorus in α and γ Iron” (in 

Japanese), Nippon Kinzoku Gakkai-shi, 29(2), 166-170 (1965) (Experimental, 20) 

[1966Run] Rundqvist, S., Nawapong, P.C., “The Crystal Structure of ZrFeP and Related Compounds”, Acta Chem. 

Scand., 20(8), 2250-2254 (1966) (Crys. Structure, Experimental, 9) 

[1973Mae] Maeda, Y., Takashima, Y., “Mössbauer Studies of FeNiP and Related Compounds”, J. Inorg. Nucl. 

Chem., 35(6), 1963-1969 (1973) (Crys. Structure, Thermodyn., Experimental, Electronic Structure, 12) 

[1977Pal] Palfii, Ya.F., Kuzma, Yu.B., “New Ternary Phosphides with the Nb 4CoSi Type Structure”, Dopov. Akad. 

Nauk Ukrain. RSR, A(3), 262-265 (1977) (Experimental, 3) 

[1978Jei] Jeitschko, W., Baun, D.J., “Synthesis and Crystal Structure of the Iron Polyphosphide FeP4”, Acta 

Crystallogr., 34B, 3196-3201 (1978) (Phase Diagram, Crys. Structure, Experimental, 30) 

[1978Sug] Sugitani, M., Kinomura, N., Koizumi, M., “Preparation and Properties of a New Iron Phosphide FeP 4”, 

J. Solid State Chem., 26(2), 195-201 (1978) (Crys. Structure, Experimental, 14) 

[1979Yam] Yamada, K., Kato, E., “Mass Spectrometric Determination of Activities of Phosphorus in Liquid 

Fe-P-Si, Al, Ti, V, Cr, Co, Ni, Nb and Mo Alloys” (in Japanese), Tetsu to Hagane (J. Iron Steel Inst. Jpn.), 

65(2), 273-280 (1979) (Experimental, Thermodyn., 40) 

[1983Yam] Yamada, K., Kato, E., “Effect of Dilute Concentrations of Si, Al, Ti, V, Cr, Co, Ni, Nb and Mo on the 

Activity Coefficient of P in Liquid Fe”, Trans. Iron Steel Inst. Jpn., 23(1), 51-55 (1983) (Experimental, 

Thermodyn., 16) translated from [1979Yam] 

[1984Ban] Ban-Ya, S., Maruyama, N., Kawase, Y., “Effects of Ti, V, Cr, Mn, Co, Ni, Cu, Nb, Mo and W on the 

Activity of Phosphorus in Liquid Iron” (in Japanese), Tetsu to Hagane, 70(1), 65-72 (1984) (Thermodyn., 


[1984Moe] Moeller, R., Grabke, H.J., “Grain Boundary Segregation of Phosphorus in Fe-Nb-P and Fe-Nb-C-P 

Alloys”, Scr. Metall., 18, 527-530 (1984) (Experimental, Kinetics, 7) 

[1986Pau] Paul, E., Swartzendruber, L.J., “The Fe-Nb (Iron-Niobium) System”, Bull. Alloy Phase Diagrams, 7(3), 

248-254 (1986) (Assessment, Crys. Structure, Magn. Prop., Phase Diagram, Review, Thermodyn., 83) 

[1987Gra] Grabke, H.J., Moller, R., Erhart, H., Brenner, S.S., “Effects of the Alloying Elements Ti, Nb, Mo and V 

on the Grain Boundary Segregation of P in Iron and Steels”, Surf. Interface Anal., 10, 202-209 (1987) 

(Experimental, Phys. Prop., 20) 

[1988Rag] Raghavan, V., “The Fe-Nb-P (Iron-Niobium-Phosphorus) System” in “Phase Diagrams of Ternary Iron 

Alloys”, Indian Inst. Met., Calcutta, 3, 111-119 (1988) (Crys. Structure, Phase Diagram, Phase Relations, 

Review, 7) 

[1989Bab] Babaeva, R.M., Vavilova, V.V., Kovneristyi, Yu.K., “Metastable Phase Equilibria and Inclination to 

Amorphization of the Alloys in the Systems Fe-P-M (M: Mo, Nb, V)” (in Russian), Dokl. Akad. Nauk 

SSSR, 304(1), 139-142 (1989) (Experimental, Phase Diagram, Phase Relations, 5) 

[1990Bab1] Babaeva, R.M., Vavilova, V.V., Kovneristyi, Y.K., Musin, V.R., “Kinetics of Crystallization 

of Amorphous-Alloys of Fe-P-M (M = Mo, Nb, V) Systems”, Russ. J. Inorg. Chem. (Engl. Transl.), 

35(8), 1224-1226 (1990), translated from Zh. Neorg. Khim., 35, 2147-2150 (1990) (Experimental, 

Morphology, Thermodyn., 7) 

[1990Bab2] Babaeva, R.M., Baldokhin, Yu.V., Kolotyrkin, P.Ya., Vavilova, V.V., “Mössbauer Study of Rapidly 

Quenched Alloys of the Systems Fe-P-M (M: Mo, Nb, V)” (in Russian), Dokl. Akad. Nauk SSSR, 310(2), 

366-371 (1990) (Crys. Structure, Experimental, Phase Relations, 7) 

[1991Bej] Bejarano, J.M.Z., Gama, S., Ribeiro, C.A., Effenberg, G., Santos, C., “On the Existence of the Fe 2Nb 3 

Phase in the Fe-Nb System”, Z. Metallkd., 82(8), 615-620 (1991) (Assessment, Experimental, Phase 

Diagram, 8) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_6 


17

18 6 

Fe–Nb–P 

[1993Bej] Bejarano, J.M.Z., Gama, S., Ribeiro, C.A., Effenberg, G., “The Iron-Niobium Phase Diagram”, 

Z. Metallkd., 84(3), 160-164 (1993) (Experimental, Phase Diagram, 6) 

[1993Din] Ding, X., Wang, W., Han, Q., “Thermodynamic Calculation of Fe-P-j System Melt”, Acta Metall. Sin. 

(China), 29(12), B527-B532 (1993) (Calculation, Theory, Thermodyn., 7) 

[1994Sri] Srikanth, S., Petric, A., “A Thermodynamic Evaluation of the Fe-Nb System”, Z. Metallkd., 85, 164-170 

(1994) (Calculation, Thermodyn., 49) 

[1997Hin] Hino, M., Nagasaka, T., Ban-Ya, S., “Activity of Phosphorus in α-Fe and Phase Diagram of Fe-Fe 2P 

System Above 1273 K”, Z. Metallkd., 88(12), 938-944 (1997) (Thermodyn., Phase Diagram, Experimental, 

34) 

[1997Vav] Vavilova, V.V., Kovneristyi, Y.K., “Preparation and Thermal Stability of Fe-P-M (M = Mo, V, Nb, Mn, 

Si) Amorphous Alloys”, Inorg. Mater. (Engl. Trans.), 33(3), 275-281 (1997), translated from Neorgan. 

Mater., 33(3), 333-339 (1997) (Experimental, Phase Relations, Thermodyn., 15) 

[1999Vav] Vavilova, V.V., Baldokhin, Yu.V., “Mössbauer Study of Rapidly Quenched Fe-P-E Alloys (E = V, Nb, 

Mo, Mn, Si)”, Russ. Metall., (1), 132-139, (1999), translated from Russ. Akad. Nauk, Met., (1), 103-112 

(1999) (Experimental, Phase Relations, 20) 


Si) Amorphous Alloys”, Inorg. Mater., 33(3), 275-281 (1997) (Experimental, Phase Relations, 13) 

[2000Tof] Toffolon, C., Servant, C., “Thermodynamic Assessment of the Fe-Nb System”, Calphad, 24(2), 97-112 

(2000) (Assessment, Calculation, Phase Relations, Thermodyn., #, *, 40) 

[2002Per] Perrot, P., Batista, S., Xing X., “Fe-P (Iron-Phosphorus)”, MSIT Binary Evaluation Program, in MSIT 

Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services, GmbH, Stuttgart; Document 

ID: 20.16107.1.20, (2002) (Phase Diagram, Assessment, Crys. Structure, Phase Relations, #, 23) 


(1990) 





MSIT 1

Iron – Niobium – Silicon 


Ludmila Tretyachenko 

Introduction 

Only a few experimental works were performed to determine phase equilibria in the Fe-Nb-Si 

system. [1956Gol] noted an extreme complexity of the phase diagram of this system and an 

existence of numerous ternary compounds. The isothermal section at 1000˚C was published 

by [1960Gol]. At least six compounds were found to exist in this system. Their exact 

compositions and crystal structures were not determined. A possibility of three more compounds 

was suggested. The compositions and crystal structure of six ternary compounds were 

established as a result of further investigations [1963Spi, 1965Gla, 1967Mar, 1969Yar, 1969Jei, 

1975Ste, 1980Ste, 1982Mal, 1983Mal]. 

The homogeneity range boundary of the Laves phase at 1300˚C was determined by 

[1967Den]. The regions of the Laves and μ phases at 1100˚C were studied by [1972Sin]. 

[1982Mal] investigated the phase equilibria in the range of 30 to 50 at.% Si at the temperature 

interval from 1000 to 1200˚C. 

Solid solutions based on the binary Laves phase NbFe 2 were studied by [1963Bar, 1967Den, 

1972Sin, 1985Tro, 1986Bla]. 

Literature data on the phase equilibria and the ternary compounds were used by [1984Rag, 

1987Rag] to construct a tentative liquidus surface projection and the isothermal section at 

1150˚C. 

Investigations performed during last years concerned the structure and properties, such as 

magnetic, amorphous and nanocrystalline niobium alloys [1993Gao, 1994Gao, 2001Rix, 

2001Tur, 2005Bar, 2005Pen, 2005Tur, 2006Tur1, 2006Tur2]. 

The only investigation of thermodynamic properties of the Fe-Nb-Si alloys was carried out 

by [1989Sud]. 

The experimental investigations of the structure of alloys and the phase equilibria in the 

Fe-Nb-Si system are listed in Table 1. 


The binary phase diagrams are accepted from [1993Bej] (Fe-Nb), [1982Kub] (Fe-Si) and 

[Mas2] (Nb-Si). 


Fe–Nb–Si 7 

Data on solid phases pertinent to the Fe-Nb-Si system are listed in Table 2. 

Significant solubility of the third element in the binary compounds was found only for the 

NbFe 2 (λ) and Nb 19Fe 21 (μ) phases. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_7 


1

2 7 

Fe–Nb–Si 

The λ phase homogeneity range reaches 25 at.% Si at 1300˚C [1967Den] and at 1100˚C 

[1972Sin]. [1960Gol] reported the silicon solubility in NbFe 2 at 1000˚C to be 25 at.% Si at 38 

at.% Nb. However, in the isothermal section at 1000˚C presented by [1960Gol] the homogeneity 

range of the λ phases is extended up to ~ 34 at.% Si. 

Silicon additions to the λ phase replace iron atoms rather than niobium and decrease 

the c parameter whereas the a parameter remains nearly constant along the isopleth ~33 at.% 

Nb. [1972Sin] did not reveal the c parameter to change along the constant niobium line 

30 at.% Nb. 

The μ phase was considered to be σ phase by [1960Gol]. 

The solubility in other binary phases does not exceed 1 at.% Nb or Si. 

The homogeneity ranges of the ternary phases E, V, τ 1, τ 3 and τ 4 are insignificant, about 1 

at.%. The single phase τ 2 was found in the range of 38.4 to 40.4 at.% Nb at 40.4 at.% Si 

[1979Ste]. The Nb 4FeSi phase (τ 4) was detected by [1965Gla]. However, [1972Sin] did not 

reveal this phase. [1980Ste] reported an existence of two modifications of the τ3 compound. 

The high temperature βNb4Fe3Si5 phase (Nb4Fe3Si5 type crystal structure [1982Mal]) was 

found to transform at 1130 ± 10˚C into a low temperature modification αNb 4Fe 3Si 5, for which 

the MgZn 2 crystal structure type was detected. The relation of the αNb 4Fe 3Si 5 to the NbFe 2 

Laves phase, which has the same crystal structure, is not clear. 

The ternary phase Nb 6Fe 16Si 7 (Cu 6Mg 16Si 7 type, D8 a) was obtained after annealing of an 

amorphous material prepared by mechanical alloying [2001Rix]. For the first time Nb 6Fe 16Si 7 

was identified by [1992Rix] in an annealed melt spun Fe 73.5Cu 1Nb 3Si 13.5B 9 alloy and was 

supposed to be stabilized by a certain B content. It was considered to be metastable. The alloy 

of the stoichiometric composition Nb:Fe:Si = 6:16:7 analyzed by [2001Rix] after a heat 

treatment at 900˚C for 1 h contained mainly the Nb 6Fe 16Si 7 phase. The Nb 6Fe 16Si 7 phase 

persisted after the heat treatment at 1050˚C for 90 h. The crystalline Nb 6Fe 16Si 7 also could be 

synthesized by melting pressed tablets of the elemental powders [2001Rix]. 

It should be noted that [1960Gol] reported a phase with unknown structure in the region 

near the composition of Nb 6Fe 16Si 7 in the section at 1000˚C. 


Melting temperatures of investigated alloys have been determined in argon arc furnace using 

an optical pyrometer [1960Gol]. The results are shown in the concentration triangle but fields 

of primary crystallization of phases were not delimited. 

[1978Hao] found a eutectic, which had the composition 2.16Nb-74.61Fe-22.23Si (in at.%, 

4.5Nb-83.5Fe-12Si mass%) and melted at 1360˚C. The compositions of phases in the eutectic 

were not determined but [1978Hao] proposed the phase composition of the eutectic to be 

NbSi2 + Fe(Si), what is impossible. The eutectic may be composed from NbFe2 + (Fe). 

A tentative liquidus surface projection was constructed by [1984Rag] using the data of 

[1960Gol] and [1978Hao] as well as an assumption that none of the ternary compounds has a 

primary solidification field. The phase diagram of the Fe-Nb accepted by [1984Rag] does not 

correspond to the last version of this system [1993Bej]. Moreover, the eutectic reported by 

[1978Hao] is a three-phase eutectic, but not a four-phase, as assumed by [1984Rag]. So, the 

liquidus surface is not given here. 



MSIT 1


The isothermal section at 1000˚C was reported by [1960Gol]. Phase equilibria involving six 

ternary phases were shown in this section. However, the compositions of the ternary phases 

were not determined exactly. Additionally three possible ternary phases not included in the 

presented equilibria were shown tentatively. The binary phase diagrams accepted by [1960Gol] 

do not correspond to the up to date versions [1993Bej, Mas2]. The λ phase field was found to 

be very wide (~ 15 - 40 at.% Nb) and to extend up to ~ 34 at.% Si. 

The isothermal section at 1000˚C reported by [1960Gol] was redrawn in the review by 

[1961Eng]. 

[1967Den] determined the boundaries of the λ phase field at 1300˚C. It was shown that 

this field is smaller than that by [1960Gol] at 1000˚C. [1967Den] reported also that the size of 

the λ field was smaller by up to 2 at.% Nb at 1000˚C than at 1300˚C. 

A partial isothermal section in the region of the λ and μ phases at 1100˚C was published by 

[1972Sin]. The size of the λ phase field was found to be close to that determined by [1967Den], 

from ~ 25 to ~ 35 at.% Nb and up to 25 at.% Si. 

Both the λ and μ phase fields extend along constant niobium lines [1960Gol, 1963Bar, 

1967Den, 1972Sin]. Bewilderment arises from the statement of [1986Bla] that the homogeneity 

range of the phase with the MgZn 2 type crystal structure (Friauf - Laves phase) extends 

from NbFe 2 up to Nb 0.2Si 0.8Fe 2, that is along the line of constant Fe content of 66.7 at.% at Si 

content from 0 up to 26.7 at.%. 

[1982Mal] published the partial section in the region of silicon content above 30 at.%, 

which shows the phase equilibria in the temperature range of 1000 - 1200˚C. The phase 

equilibria in this region involve NbFeSi2, Nb4Fe4Si7, NbFe3Si5, NbFeSi2 and NbFeSi ternary 

phases. 

The data by [1967Den, 1972Sin, 1982Mal] as well as those by [1965Gla, 1975Ste, 1979Ste, 

1980Ste, 1985Gle1, 2001Ito, 2005Tur, 2006Tur1] were used to construct the isothermal section 

at ~ 1150˚C (Fig. 1). 

Calculations of the α - γ (bcc - fcc) phase equilibria were performed by [1989Kum]. The 

calculated partial isothermal sections are shown in Figs. 2 to 5. 


Partial and integral enthalpies of dissolution (ΔH d) and mixing (ΔH mix, ΔH i) were determined 

by calorimetry [1989Sud] and are given in Table 3. A thermodynamic model used for 

calculation of the bcc - fcc equilibrium in the ternary system Fe-Nb-Si is presented by 

[1989Kum]. 

Notes on Materials Properties and Application 


Mechanical properties of Fe-Si alloys with additions of niobium were investigated by 

[1985Gle1, 1985Gle2]. It was found that alloying of the high-silicon iron containing 11 at.% 

Si with niobium (up to 3 at.%) decreased the transition temperature from ductile to brittle 

fracture and extended a temperature range of plasticity. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_7 


3

4 7 

Fe–Nb–Si 

Investigations of magnetic and electric properties of these alloys were carried out by 

[1985Gle2]. It was revealed that niobium does not cause practically any change in magnetostriction, 

specific magnetic losses, magnetic induction and coercive force of high-silicon iron. 

A number of works concerned magnetic properties of Fe-Si alloys with addition of 

niobium rapidly quenched by melt spinning [2001Tur, 2005Bar, 2005Tur, 2006Tur1, 

2006Tur2] (amorphous or nanocrystalline materials). [2001Tur] revealed Nb to enhance the 

coercivity (about 10 times) in the alloys Fe100–(x+y)SixNby. However, the coercive force is nearly 

temperature independent up to about 400˚C in Fe 76Si 20Nb 2. An increase in the local magnetic 

stiffness with increasing Nb content was found by [2005Bar]. An increase of the coercive field, 

H c, and the Curie temperature, T C, for Fe 80–xSi 20Nb x (0 ≤ x ≤ 10) were reported [2005Tur]. 

The temperature dependence of the coercive field in the melt-spun alloys was reported by 

[2006Tur1]. Magnetic transitions in the nanocrystalline alloy were investigated by [2006Tur2]. 

Magnetic properties of the Laves phases were examined by [1960Gol]. He reported that a 

boundary exists, which divides the Laves phase field into two parts in accordance with 

magnetic properties of the alloys. However, the ferromagnetism of the alloys in the region of 

the Laves phase shown by [1960Gol] seems more probable to be explained by the presence of 

Fe based phases in these alloys. 

Microhardness of the alloys Nb 1–xSi xFe 2 was measured by [1986Bla] (for Nb 0.8Si 0.2Fe 2 also 

by [1985Tro]). Microhardness values were found to decrease from 10418 N·mm –2 to 7853 

N·mm –2 for Nb 0.2Si 0.8Fe 2. However, it should be reminded that all the alloys from NbFe 2 up to 

Nb 0.2Si 0.8Fe 2 were considered to be continuous solid solutions of the MgZn 2 type that contradicts 

to other available data. 

The influence of Nb doping on thermoelectric properties of βFeSi2 has been studied by 

[2001Ito]. The electrical resistivity, thermoelectric power and thermal conductivity were 

measured in the range from room temperature to 900˚C. 

Resistance to oxidation of some Fe-Nb-Si alloys has been studied by [1960Gol] at 1000˚C 

in still air. Only negligible oxidation was observed for the 55Fe-20Nb-25Si (at.%) alloy. That is 

the composition where [2001Rix] has found the new compound Nb 6Fe 16Si 7. 

An oxidation study in slowly flowing oxygen was carried out at 1150˚C by [1978Hao]. The 

85Fe-8.5Nb-6.5Si (mass%) (80.3Fe-3.7Nb-16Si (at.%)) was found to be oxidized at a catastrophic 

rate. Resistance to oxidation of the eutectic found by [1978Hao] at the composition 

of 83.5Fe-4.5Nb-12Si (mass%) (75.9Fe-2.4Nb-21.7Si (at.%)) was poor. The specific gravity of 

this eutectic was detected to be 8000 kg·m –3 . 

Miscellaneous 

Alloys Fe-(1 to 3)Nb-11Si (at.%) have been studied after a stepped heat treatment from 

1000˚C, 1 h down to 500˚C, 100 h and further cooling to room temperature [1985Gle1, 

1985Gle2]. It was revealed that niobium changed neither an ordering temperature nor an 

equilibrium degree of atomic order. Precipitations of NbFe 2 phase were observed, their 

quantity increased with Nb content. 

Thermal stability of a nanocrystalline alloy (Fe 3Si) 0.95Nb 0.05 was studied by [1993Gao]. 

The alloy prepared using high energy ball milling consisted of disordered bcc solid solution 

and had grain size of 7-9 nm. During annealing at 450˚C the alloy containing Nb was 

considerably more stable against grain growth than the binary Fe3Si alloy. It was somewhat 



MSIT 1

more stable against ordering. Niobium segregation away from the D0 3 (α 1) ordered domains 

was observed. 

A structural study [2005Pen] ofFe 80–xNb xSi 20 (0 ≤ x ≤ 20) ribbons prepared by melt 

spinning has revealed that these alloys were composed of amorphous, cubic bcc (Fe) and 

hexagonal NbFe 2–xSi x (λ) phases. The ordered α 2 (D0 3) and α 1 (B2 CsCl type) also were 

formed in the alloys with low Nb content and disappeared in the alloys with higher 

(10-12 at.%) Nb content. During annealing at 850˚C the λ phase decomposes into two 

hexagonal phases with similar structures. Nb atoms hindered growth of grains in the alloys. 

The grain size in as cast and annealed alloys at x = 0.5 was large, about 1 μm. However, 

the addition of 3 at.% Nb caused a decrease in grain size, which abruptly diminished to about 

100 nm and reached 37 nm for Fe 68Nb 12Si 20. There was no evidence that Nb atoms enter the 

cubic bcc (Fe) lattice, as it was supposed earlier [2001Tur]. 

Similar results were obtained by [2005Bar, 2005Tur, 2006Tur1, 2006Tur2] in structural 

studies of melt-spun Fe-Nb-Si alloys. The grain size of 18 nm was obtained for Fe 60Nb 20Si 20 

[2006Tur2]. 

Crystallization of mechanically alloyed 55Fe-21Nb-24Si (at.%) was studied by [2001Rix]. 

As-milled material was found to be amorphous. A crystallization peak was determined at 

750˚C. An isothermal heat treatment at 900˚C resulted in the formation of a D8 a phase with a 

small amount of the hexagonal λ phase (NbFe 2). The Mössbauer spectroscopy did not reveal 

magnetic ordering down to 77 K. 

. Table 1 

Investigations of the Fe-Nb-Si Phase Relations, Structures and Thermodynamics 

Reference Method / Experimental Technique 

[1960Gol] Arc melting, XRD, melting point 

determination, magnetic properties, 

oxidation resistance 


Temperature / Composition / Phase 

Range Studied 

1000˚C, 250 alloys, 15 binary and six (or 

nine) ternary phases 

[1963Bar] Arc melting, optical microscopy (OM), XRD 1100˚C, Nb(Fe1–xSix) 2 (x = 0, 0.165, 0.330) 

(λ) 

[1963Spi] Arc melting, OM, XRD 1100˚C, NbFeSi (E) 

[1965Gla] XRD 1100˚C, Nb4FeSi (66.7 at.% Nb 

isoconcentrate) 

[1967Den] Arc melting, OM, XRD 800, 1000, 1300˚C, Laves phase 

[1967Mar] Arc melting, XRD 800˚C, ~ NbFeSi2 [1969Jei] Arc melting, XRD, OM 1200˚C, NbFeSi (E), Nb4Fe4Si7 (V) 

[1969Yar] Arc melting, XRD NbFeSi 

[1972Sin] Arc melting, OM, XRD 1100˚C, 30 alloys, λ, μ 

[1975Ste] OM, Electron microprobe analysis (EMPA), 

electron microdiffraction (EMD) 

1200˚C, NbFeSi2 Landolt‐Börnstein 


MSIT 1 

DOI: 10.1007/978-3-540-70890-2_7 


5

6 7 

Fe–Nb–Si 



[1978Hao] Induction melting; DTA, scanning electron 

microscopy (SEM), oxidation studies at 

1150˚C, specific gravity measurement 

[1979Ste] Chemical vapor transport reaction, XRD, 

EMPA 


Range Studied 

3 alloys, 73Fe-15.5Nb-11.5Si, 80Fe-10Nb- 

10Si, 85Fe-8.5Nb-6.5Si (mass%), eutectic 

composition 

1100˚C, Nb ~2Fe ~1Si ~2 

[1980Ste] EMPA, XRD 1200˚C, Nb 32.7±1Fe 26±1Si 41.3±1 

(αNb 4Fe 3Si 5, βNb 4Fe 3Si 5) 

[1982Mal] Chemical vapor transport reaction, XRD 

(single crystal), EMPA 

[1983Mal] Chemical vapor transport reaction, XRD 

(single crystal) 

[1985Gle1] Induction melting, XRD, SEM, 

photoelectron spectroscopy, mechanical, 

magnetic, electrical properties 

[1985Gle2] Transmission electron microscopy (TEM), 

XRD, high temperature XRD, mechanical 

properties 

[1985Tro] Arc melting, XRD, microhardness 

measurements, OM 

[1986Bla] Arc melting, XRD, OM, microhardness 

measurements 

1200˚C, 40Nb-20Fe-40Si (at.%), 

isothermal section for the temperature 

range 1000-1200˚C, 30-50 at.% Si, 

βNb 4Fe 3Si 5 

Nb 4Fe ~3Si ~5 

Fe-11Si-1(2; 3)Nb (at.%) 

Fe-11(12)Si-(0 to 12)Nb (at.%), 500-800˚C 

900-1200˚C, Nb 0.8Si 0.2Fe 2 

(66.6Fe-26.7Nb-6.7Si (at.%)) 

800-1200˚C, NbFe 2-Nb 0.2Si 0.8Fe 2 

[1989Kum] Calculation 950, 1050, 1150, 1250˚C, isothermal 

sections of the Fe corner 

[1989Sud] Calorimetry 1614˚C, FeSi-Nb (0 ≤ xNb ≤ 0.4), enthalpy 

of dissolution and mixing 

[1993Gao] Mechanical alloying, XRD, Mössbauer 

spectroscopy, TEM, energy dispersive 

X-ray spectrometry (EDS) 

[1994Gao] Mechanical alloying, Mössbauer 

spectroscopy, XRD, TEM, EDX 

[2001Rix] Mechanical alloying and inductive 

melting; XRD, Mössbauer spectroscopy, 

DTA 

[2001Ito] XRD, SEM, EDX, electrical resistivity, 

thermoelectric power, thermal 

conductivity 

450˚C, nanocrystalline powder 

(Fe 3Si) 0.95Nb 0.05 

450˚C, (Fe 3Si) 0.95Nb 0.05 

up to 1050˚C, Fe 16Nb 6Si 7 (D8 a) 

from room temperature to 900˚C, 

Fe 1–xNb xSi 2 (0 ≤ x ≤ 0.04) 

[2005Bar] Melt spinning, NMR, magnetic properties Rapidly quenched ribbons, 

Fe 100–x–ySi xNb y (9.5 ≤ x ≤ 20, 0.5 ≤ y ≤ 12) 



MSIT 1




Range Studied 

[2005Pen] Melt spinning, high-resolution XRD as cast and annealed at 850˚C, 

Fe 80–xSi 20Nb x (0 ≤ x ≤ 12) 

[2005Tur] Melt spinning, high-resolution XRD, SEM, 

NMR, magnetic properties 

[2006Tur1] Melt spinning, magnetic properties (2- 

1123 K), Mössbauer spectroscopy, XRD 

as cast and annealed at 850˚C, 

Fe 80–xSi 20Nb x (x = 0.5, 1.5, 2.0, 3.0, 10) 

ribbons 

Fe 77.9Nb 10Si 12.1, Fe 70Nb 10Si 20 

[2006Tur2] Melt spinning, XRD, magnetic properties 2-413 K, Fe 80–xSi 20Nb x (x = 12, 20) 

. Table 2 


Phase / 

Temperature 

Range [˚C] 

Pearson 

Symbol / 

Space 

Group / 

Prototype 


Lattice 

Parameters 


α, (αFe,δFe) cI2 

(δFe) Im3m a = 293.15 pure Fe at 1390˚C [Mas2, V-C2] 

1538 - 1190 W Fe-Nb system, dissolves up to 3.2 at.% Nb 

[1993Bej] 

Fe-Si system, dissolves up to 19.5 at.% Si 

[1982Kub] 

(αFe) a = 286.65 pure Fe at 25˚C [Mas2] 

< 912 [1993Bej], dissolves 0.73 at.% Nb 

< 960 δα (Fe-Si) solid solutions [1982Kub] 

γ, (γFe) cF4 a = 364.67 pure Fe at 915˚C [Mas2, V-C2] 

1394 - 912 Fm3m 

Cu 

dissolves 1 at.% Nb [1993Bej], 

3.19 at.% Si [1982Kub] 

(Nb) cI2 a = 330.04 [Mas2] 

< 2469 Im3m 

W 

dissolves 7 at.% Fe [1993Bej], 3.5 at.% Si 

[Mas2] 

a = 330.4 ~1.9 at.% Fe, 1000˚C [1960Gol] 

a = 329.1 ~3.4 at.% Fe, 1200˚C [1960Gol] 

(Si) cF8 a = 543.06 [Mas2] 

< 1414 Fd3m 

C (diamond) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_7 


7

8 7 

Fe–Nb–Si 



Temperature 

Range [˚C] 

Pearson 

Symbol / 

Space 

Group / 

Prototype 

Lattice 

Parameters 


λ, 

hP12 [1960Gol, 1963Bar, 1967Den, 1972Sin, 

Nb1±y(Fe1–xSix) 2 P63/mmc 1985Tro, 1986Bla] 

MgZn2 0 ≤ x ≤ 0.375, ~ 0.79 ≤ 1±y ≲; 1.06 

1100˚C [1972Sin] 

1300˚C [1967Den] 

(25 at.% Si); 

at 1000˚C 0 to ~34 at.% Si [1960Gol] 

a = 483.7 [1993Bej, V-C2] 

c = 788.4 32 to 37 at.% Nb [1993Bej] 

NbFe2 a = 481.1 to 483.2 from 20 to 40 at.% Nb, annealed at 1000˚C 

< 1630 c = 785.7 to 787.1 

a = 483.5 to 483.9 

[1960Gol] 

c = 788.5 to 786.8 Nb(Fe1–xSix) 2,0≤ x ≤ 0.33, homogenized at 

a = 484.14 to 483.6 1100˚C [1963Bar] 

c = 789.33 to 785.9 at ~33 at.% Nb, 0 to 25 at.% Si (annealed at 

1300˚C) [1967Den] 

a = 482.1 70Fe-30Nb (at.%), annealed at 1100˚C 

c = 786.4 [1972Sin] 

a = 482.2 65Fe-30Nb-5Si (at.%) (annealed at 1100˚C 

c = 786.1 [1972Sin] 

a = 482.2 55Fe-30Nb-15Si (at.%) (annealed at 

c = 785.7 1100˚C) [1972Sin] 

a = 481.0 55Fe-25Nb-20Si (at.%) (1100˚C, three- 

c = 780.0 phase alloy) [1972Sin] 

a = 481.4 Nb0.8Si0.2Fe2 (annealed at 900-1200˚C) 

c = 785.5 [1985Tro] 

μ, Nb19Fe21 hR39 a = 492.6 [1993Bej, V-C2] 

< 1520 R3m c = 268.0 48 to 52 at.% Nb, < 1400˚C, ~50 to 54 at.% 

W6Fe7 Nb at 1520 to 1500˚C [1993Bej] 

dissolves up to 15 at.% Si at 1000˚C 

[1960Gol], 10 at.% Si at 1100˚C [1972Sin] 

Nb3Fe2 metastable [1993Bej] 

1490 - 1460 cF96 [Mas2] 

Fd3m 

Ti2Ni a = 1126.1 [1960Gol] 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol / 

Space 

Group / 

Prototype 


Lattice 

Parameters 


α2, Fe-Si cP2 ordered B2 modification of Fe with 10 to 22 

≲ 1280 Pm3m 

at.% Si [1982Kub, Mas2] 

CsCl a = 281 [V-C2] 

α1,Fe3Si cF16 ordered D03 modification of Fe with 11 to 

≲ 1235 Fm3m 

30 at.% Si [1982Kub, Mas2] 

BiF3 a = 565.0 [V-C2] 

β, Fe2Si hP6 ~33.0 to ~34.3 at.% Si [1982Kub] 

1212 - 1040 P3m1 a = 405.2 ± 0.2 [V-C2] 

Fe2Si c = 508.55 ± 0.03 

η, Fe5Si3 hP16 37.5 at.% Si [1982Kub] 

1060 - 825 P63/mcm a = 675.9 ± 0.5 [V-C2] 

Mn5Si3 c = 472.0 ± 0.5 

ε, FeSi cP8 49.6 to 50.8 at.% Si [1982Kub] 

< 1410 P213 FeSi 

a = 451.7 ± 0.5 [V-C2] 

ζl, αFeSi2(r) oC48 66.7 at.% Si [1982Kub] 

< 982 Cmca a = 986.3 ± 0.7 [V-C2] 

αFeSi2 b = 779.1 ± 0.6 

c = 783.3 ± 0.6 

ζh, βFeSi2(h) tP3 69.5 to 73.5 at.% Si [1982Kub] 

1220 - 937 P4/mmm a = 269.01 [V-C2] 

βFeSi2 c = 513.4 

Nb3Si tP32 a = 1022.4 ± 0.3 [Mas2, V-C2] 

1980 - 1770 P42/n Ti3P 

c = 518.9 ± 0.1 

βNb5Si3 tI32 a = 1002.6 37.5 to 40.5 at.% Si [Mas2, V-C2] 

2520 - 1650 I4/mcm 

W5Si3 

c = 507.17 

αNb5Si3 tI32 a = 657.1 37.5 to 38.5 at.% Si [Mas2, V-C2] 

< 1940 I4/mcm 

Cr5B3 

c = 1188.9 

NbSi2 hP9 a = 481.9 ± 0.2 [Mas2, V-C2] 

< 1940 P6422 CrSi2 

c = 659.2 ± 0.2 

*V,Nb4Fe4Si7 tI60 a = 1265.2 ± 0.2 [1969Jei] 

I4/mmm 

Zr4Co4Ge7 

c = 498.1 ± 0.1 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_7 


9

10 7 

Fe–Nb–Si 



Temperature 

Range [˚C] 

Pearson 

Symbol / 

Space 

Group / 

Prototype 

Lattice 

Parameters 


* E, NbFeSi oP12 a = 623.1 ± 0.2 [1969Jei] 

Pnma b = 367.7 ± 0.2 

TiNiSi c = 719.0 ± 0.4 

or a = 711 [1963Spi] 

Co2Si b = 529 

c = 1125 

a = 624 

b = 722 

c = 369 

[1969Yar] 

* τ1, NbFeSi2 tI56 a = 1258 ~NbFeSi2 [1967Mar] 

I4/mmm, 

I4m2, I42m, 

I4mm or I422 

TiNiSi2 or 

c = 497 

Co3Nb4Si7 [V-C2] 

orthorhombic a = 868.9 ± 0.5 [1975Ste] 

Pmmm, 

Pmm2 or 

P222 

b = 973.3 ± 0.5 

c = 757.6 ± 0.5 

or 

oP48 

Pbam 

TiMnSi2 [V-C2] 

* τ2, Nb2FeSi2 tP198 

P42/mcm Nb2FeSi2 [1979Ste, V-C2] 

a = 2372 ± 3 

c = 495.5 ± 0.7 

for Nb76Fe42Si80 [1979Ste] 

a = 2376 ± 1 

c = 495.9 ± 0.1 


a = 2378 ± 3 

c = 496.0 ± 0.7 


* τ3, βNb4Fe3Si5 oP72 a = 1282.1 ± 0.6 [1980Ste, 1982Mal, 1983Mal] (1200˚C) 

> 1130 ± 10 Pmn21 b = 491.2 ± 0.1 exact formula Nb24Fe19Si29 [1983Mal] 

Nb4Fe3Si5 c = 1552.1 ± 0.2 

* τ3´, αNb4Fe3Si5 hP12 a = 486.8 ± 0.1 annealed at 1100˚C [1980Ste] 

< 1130 ± 10 P63/mmc MgZn2 

c = 775.8 ± 0.1 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol / 

Space 

Group / 

Prototype 

Lattice 

Parameters 


* τ4,Nb4FeSi tP12 a = 619.3 ± 0.2 annealed at 1100˚C [1965Gla, V-C2] 

P4/mmc 

Nb4CoSi c = 505.6 ± 0.1 

*Nb6Fe16Si7 cF116 a = 1133.5 ± 0.1 [1992Rix, 2001Rix], in mechanically alloyed 

Fm3m 

Th6Mn23 or 

Mg6Cu16Si7 

alloy annealed at 900˚C; presumably 

metastable 

. Table 3 

Enthalpies of Dissolution and Mixing of the FeSi-Nb Alloys at 1164˚C [1989Sud] 


x Nb, at. fraction –ΔH d [kJ·mol –1 ] –ΔH mix [kJ·mol –1 ] –ΔH Nb [kJ·mol –1 ] –ΔH FeSi [kJ·mol –1 ] 

0 0 0 125 ± 15 0 

0.1 8.2 ± 0.1 11.1 ± 0.1 80 ± 10 3.3 ±0.5 

0.2 10.9 ±0.1 16.5 ± 0.2 43 ±10 10.5 ± 0.8 

0.3 10.4 ± 0.2 18.7 ± 0.3 23 ± 3 17.2 ± 1.0 

0.4 10.2 ± 0.2 18.5 ± 0.3 15 ± 2 21.6 ± 1.5 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_7 


11

12 7 

Fe–Nb–Si 

. Fig. 1 

Fe-Nb-Si. Isothermal section at ~1150˚C 



MSIT 1

. Fig. 2 

Fe-Nb-Si. Partial calculated isothermal section at 950˚C 



MSIT 1 


DOI: 10.1007/978-3-540-70890-2_7 


13

14 7 

Fe–Nb–Si 

. Fig. 3 




MSIT 1

. Fig. 4 




MSIT 1 


DOI: 10.1007/978-3-540-70890-2_7 


15

16 7 

Fe–Nb–Si 

. Fig. 5 




MSIT 1

References 


[1956Gol] Goldschmidt, H.J., “The Metallurgy of Niobium”, J. Inst. Met., 85, 547-558 (1956) (Phase Diagram, 

Phase Relations, Review, 2) 

[1960Gol] Goldschmidt, H.J., “The Constitution of the Fe-Nb-Si System”, J. Iron Steel Inst., 169-180 (1960) (Crys. 

Structure, Experimental, Magn. Prop., Phase Diagram, Phase Relations, Phys. Prop., 51) 

[1961Eng] English, J.J., “Binary and Ternary Phase Diagrams of Columbium, Molybdenum, Tantalum and Tungsten”, 

Defense Metals Information Center, Batelle Memorial Institute, Columbus, Ohio, 152, 101-102 (1961) 

(Phase Diagram, Phase Relations, Review, 1) 

[1963Bar] Bardos, A.M., Bardos, D.I., Beck, P.A., “The Effective Atomic Radius of Si in Ternary Laves Phase 

Alloys”, Trans. Metall. Soc. AIME, 227, 991-993 (1963) (Crys. Structure, Experimental, 12) 

[1963Spi] Spiegel, F.X., Bardos, D., Beck, P.A., “Ternary G and E Silicides and Germanides of Transition 

Elements”, Trans. Metall. Soc. AIME, 227, 575-579 (1963) (Crys. Structure, Experimental, 13) 

[1965Gla] Gladyshevsky, E.I., Kuzma, Yu.B., “The Nb 4FeSi, Nb 4CoSi, and Nb 4NiSi Compounds and Their Crystal 

Structures”, J. Struct. Chem., 6, 60-63 (1965), translated from Zh. Strukt. Khim., 6, 70-74 (1965) (Crys. 

Structure, Experimental, 5) 

[1967Den] Denham, A.W., “Extent and Lattice Parameters of the Laves Phase Field in the Fe-Nb-Si System”, J. Iron 

Steel Inst., 205, 435-436 (1967) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 5) 

[1967Mar] Markiv, V.Ya., Gladyshevsky, E.I., Skolozdra, R.V., Kripyakevich, P.I., “Ternary Compounds of the 

RX´X´´2 Type in the Ti-V(Fe, Co, Ni)-Si and Similar Systems” (in Ukrainian), Dopov. Akad. Nauk 

Ukrain. RSR (A), (3), 266-269 (1967) (Crys. Structure, Experimental, 12) 

[1969Yar] Yarmolyuk, Y.P., Markiv, V.Y., Gladyshevsky, E.I., “Compounds with the TiNiSi Structure in the 

Systems of Two Transition Metals and Either Si or Ge” (in Ukrainian), Vestn. L’vov. Univ. Khim., 11, 14- 

17 (1969) (Crys. Structure, Experimental, 5) 

[1969Jei] Jeitschko, W., Jordan, A,G., Beck, P.A., “V and E Phases in Ternary Systems with Transition Metals and 

Si or Ge”, Trans. Met. Soc. AIME, 245, 335-339 (1969) (Crys. Structure, Experimental, 27) 

[1972Sin] Singh, B.N., Gupta, K.P., “Laves and μ Phases in the Nb-Fe-Si and Nb-Co-Si Systems”, Metall. Trans., 3, 

1427-1431 (1972) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 17) 

[1975Ste] Steinmetz, J., Albrecht, J.-M., Zanne, M., Roques, B., “A New Ternary Silicide of Nb and Fe, NbFeSi 2” 

(in French), Compt. Rend. Acad. Sci. Paris, 281(C), 831-833 (1975) (Experimental, Crys. Structure, 6) 

[1978Hao] Haour, G., Mollard, F., Lux, B., Wright, G., “New Eutectics Based on Fe, Co or Ni”, Z. Metallkd., 69, 26- 

32 (1978) (Experimental, Morphology, Phase Diagram, Phase Relations, Phys. Prop., 24) 

[1979Ste] Steinmetz, P.J., Roques, B., Courtois, A., Protas, J., “Crystal Structure of Nb 78Fe 40Si 80” (in French), Acta 

Crystallogr., Sect. B: Struct. Crystallogr. Crys. Chem., 35, 2509-2514 (1979) (Crys. Structure, Experimental, 

9) 

[1980Ste] Steinmetz, J., Steinmetz, P., “Structure of NbFe 2–xSi x Alloys” (in French), J. Less-Common Met., 69, 379- 


[1982Kub] Kubaschewski, O., “Iron - Silicon” in “Iron Binary Phase Diagrams”, Springer Verlag, Berlin, 136-139 

(1982) (Phase Diagram, Phase Relations, Review, #, 23) 

[1982Mal] Malaman, B., Steinmetz, J., Venturini, G., Roques, B., “Crystal Structure of the Phase Nb 4Fe ~3Si ~5-β 

and a Diagram of the Nb-Fe-Si System” (in French), J. Less-Common Met., 87, 31-43 (1982) (Crys. 

Structure, Experimental, Phase Diagram, Phase Relations, 11) 

[1983Mal] Malaman, B., Steinmetz, J., Venturini, G., Roques, B., “β-Nb 4Fe 3Si 5 with New Orthorhombic Structure 

Type; Its Relationships to Other Ternary Silicides of Niobium-Iron” in “VII International Conference on 

Solid Compounds of Transition Elements”, Proc. CNRS, 11A8 (1983) (Crys. Structure, Experimental, 


[1984Rag] Raghavan, V., Ghosh, G., “The Fe-Nb-Si System”, Trans. Ind. Inst. Met., 37, 421-425 (1984) (Experimental, 

Phase Diagram, Phase Relations, 18) 

[1985Gle1] Glezer, A.M., Maleeva, I.V., Zakharov, A.I., “Atomic Ordering and Mechanical Properties of Alloyed 

High-Silicon Iron” (in Russian), Izv. Acad. Nauk SSSR, Ser. Fiz., 49, 1633-1644 (1985) (Crys. Structure, 

Experimental, Mechan. Prop., Phase Relations, 12) 

[1985Gle2] Glezer, A.M., Maleeva, I.V., Zakharov, A.I., “Influence of Alloy Elements on the Plasticity of High- 

Silicon Iron”, Met. Sci. Heat Treat., 27, 908-912 (1985), translated from Metallov. Term. Obrab. Met., 27, 

27-30 (1985) (Crys. Structure, Experimental, Morphology, Thermodyn., 7) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_7 


17

18 7 

Fe–Nb–Si 

[1985Tro] Trojko, R., Blazina, Z., “Metal-Metalloid Exchange in Some Friauf-Laves Phases Containing Two 

Transition Metals”, J. Less-Common Met., 106, 293-300 (1985) (Crys. Structure, Experimental, 13) 

[1986Bla] Blazina, Z., Trojko, R., “Structural Investigations of the Nb 1–xSi xT 2 and Nb 1–xAl xT 2 (T = Cr, Mn, Fe, Co, 

Ni) Systems”, J. Less-Common Met., 119, 297-305 (1986) (Crys. Structure, Experimental, 6) 

[1987Rag] Raghavan, V., “The Fe-Nb-Si (Iron-Niobium-Silicon) System” in “Phase Diagrams of Ternary Iron 

Alloys”, Ind. Inst. Techn. Delhi, 1, 55-59 (1987) (Crys. Structure, Phase Diagram, Phase Relations, 

Review, 20) 

[1989Kum] Kumar, K.C.H., Raghavan, V., “BCC – FCC Equilibrium in Ternary Iron Alloys. – II”, J. Alloy Phase 

Diagr., 5, 77-96 (1989) (Calculation, Phase Diagram, Phase Relations, Thermodyn., #, 24) 

[1989Sud] Sudavtsova, V.S., Zelenina, L.N., Sharkina, N.O., “Reaction in the System FeSi-Nb(Zr)”, Inorg. Mater. 

(Engl. Trans.), 1330-1331 (1989), translated from Izv. Akad. Nauk SSSR, Neorg. Mater., 25, 1569-1570 

(1989) (Experimental, Thermodyn., 2) 

[1992Rix] Rixecker, G., Schaaf, P., Gonser, U., “Crystallization Behaviour of Amorphous Fe 73.5Cu 1Nb 3Si 13.5B 9”, 

J. Phys.: Condens. Matter, 4, 10295-10310 (1992) (Crys. Structure, Experimental, Morphology, Phase 


[1993Bej] Bejarano, J.M.Z., Gama, S., Ribeiro, C.A., Effenberg, G., “The Iron-Niobium Phase Diagram”, 

Z. Metallkd., 84, 160-164 (1993) (Experimental, Phase Diagram, Phase Relations, #, 6) 

[1993Gao] Gao, Z., Fultz, B., “The Thermal Stability of Nanocrystalline Fe-Si-Nb Prepared by Mechanical 

Alloying”, Nanostruct. Mater., 2, 231-240 (1993) (Electronic Structure, Experimental, Kinetics, Magn. 

Prop., Morphology, Nano, 35) 

[1994Gao] Gao, Z.Q., Fultz, B., “Inter-Dependence of Grain Growth, Nb Segregation, and Chemical Ordering in 

Fe-Si-Nb Nanocrystals”, Nanostruct. Mater., 4, 939-947 (1994) (Experimental, Kinetics, Magn. Prop., 

19) 

[2001Ito] Ito, M., Nagai, H., Katsuyama, S., Majima, K., “Effects of Ti, Nb and Zr Doping on Thermoelectric 

Performance of β-FeSi 2”, J. Alloys Compd., 315, 251-258 (2001) (Crys. Structure, Experimental, Phase 


[2001Rix] Rixecker, G., Haberkorn, R., “Fe 16Nb 6Si 7 and Fe 16Ta 6Si 7:NewD8 a Phases Synthesized by the Crystallization 

of Mechanically Alloyed Amorphous Powders”, J. Alloys Compd., 316, 203-208 (2001) (Crys. 

Structure, Experimental, Phase Relations, 18) 

[2001Tur] Turtelli, R.S., Schonhart, M., Sassik, H., Grossinger, R., Kolbeck, C., Duong, V.H., Ferrara, E., 

“Enhancement of the Coercive Force with Addition of Nb in α-FeSi as-Quenched Ribbons”, J. Magn. 

Magn. Mater., 226(2), 1498-1500 (2001) (Experimental, Magn. Prop., 5) 

[2005Bar] Barbatti, C.F., Turtelli, R.S., Schoenhart, M., Sassik, H., Sinnecker, J.P., Sinnecker, E.H.C.P., Sarthour, R. 

S., Guimaraes, A.P., Groessinger, R., “NMR, Magnetic and Structural Study of Fe-Si-X (X = Nb, Ta) 

Alloys”, J. Magn. Magn. Mater., 290-291, 612-614 (2005) (Crys. Structure, Experimental, Magn. Prop., 


[2005Pen] Penton-Madrigal, A., Turtelli, R.S., Estevez-Rams, E., Grossinger, R., “Structural Evolution with Nb 

Content in Melt-Spun Fe 80–xSi 20Nb x Ribbons”, J. Alloys Compd., 395, 63-67 (2005) (Crys. Structure, 


[2005Tur] Turtelli, R.S., Penton-Madrigal, A., Barbatti, C.F., Groessinger, R., Sassik, H., Estevez-Rams, E., 

Sarthour, R.S., Sinnecker, E.H.C.P., Guimaraes, A.P., “Effect of the Addition of Cr, Ta and Nb on 

Structural and Magnetic Properties of Fe-Si Alloys”, J. Magn. Magn. Mater., 294, e151-e154 (2005) 

(Crys. Structure, Experimental, Magn. Prop., Phase Relations, 6) 

[2006Tur1] Turtelli, R.S., Sinnecker, J.P., Grossinger, R., Wiesinger, G., de Morais, E., Penton-Madrigal, A., Estevez- 

Rams, E., “Magnetic Transitions in Melt-Spun Nanocrystalline Fe-Si-Nb Alloys”, Phys. B: Condens. 

Mater., 384, 303-305 (2006) (Experimental, Magn. Prop., Phase Relations, 7) 

[2006Tur2] Turtelli, R.S., Sinnecker, J.P., Penton-Madrigal, A., Groessinger, R., Skorvanek, I., Krenicky, T., Estevez- 

Rams, E., “An Unusual Temperature Dependence of the Coercive Field in the Melt-Spun Fe 80–xSi 20Nb x 

(x = 12, 20)”, J. Magn. Magn. Mater., 304, e690-e692 (2006) (Experimental, Magn. Prop., Phase 

Relations, 4) 


(1990) 





MSIT 1

Iron – Niobium – Zirconium 


Jean-Claude Tedenac, Pierre Perrot 

Introduction 

The Fe-Nb-Zr system is a base for nuclear materials. Due to their corrosion resistance some of 

zirconium alloys are used as cladding and structural materials. One other field of nuclear 

applications concerns their use in active zone of nuclear reactors [2002Gra, 2002Ram, 

2002Tof]. Two problems were evidenced in this ternary system. The first one is related to 

the existence of intermetallic compounds in the phase diagram, greatly influencing the 

mechanical properties, of the alloys. The situation was clarified recently in [2002Ram, 

2002Tof], where the phase relationship have been redetermined. The second problem concerns 

the oxygen acting as an impurity but taking part to phase equilibria [2004Bar]. 

Investigations of the system related to phase relations, structures and thermodynamic are 

presented in Table 1. Crystal structures of phases are summarized in Table 2. 

Reviews of early works on phase equilibria in the Fe-Nb-Zr system have been presented by 

[1973Sve, 1992Rag] and some isothermal sections were presented, but contradictory information 

on phase relationships in this system exists [1968Gru, 1973Sve, 1979Ale, 1989Ale, 

1989Kor1, 1997Per, 2002Gra]. Finally, the last review of Fe-Nb-Zr presented by [2003Rag] is 

mainly based on the work of [2002Gra], but it does not reproduce the stability domain of the 

ternary compound τ2. 


The Nb-Zr binary system is accepted from the thermodynamic assessment of [1991Fer]. The 

miscibility gap of the solid solution (βZr,Nb) is at 977˚C and 59.2 mass% Nb; the minimum of 

the liquidus is at 1742˚C and 22 mass% Nb. The Fe-Nb binary system is accepted from the 

thermodynamic assessment carried out by [2000Tof]. The μ phase presents an incongruent 

melting at 1520˚C, which is 70˚C lower than that given in [Mas2]. The eutectic invariant 

reaction L Ð μ + (Nb) is at 1500˚C, which is 100˚C higher than given in [Mas2]. The Fe-Zr 

binary system is accepted from experimental study of [2002Ste]. In this study it was pointed 

out that the phase of Zr 6Fe 23 shown by [Mas2] is oxygen stabilized and is not an equilibrium 

phase. According to [2002Ste] the Zr 2Fe phase is stable in quite narrow temperature range of 

780-951˚C, while according to [Mas2] it is stable below 974˚C. Beside cubic ZrFe 2 (C15 

structure, stable below 1673˚C, λ 2) exists a hexagonal ZrFe 2 (C36 structure, stable between 

1240 and 1345˚C, λ 3). 


Fe–Nb–Zr 8 

Since the first published experimental work in this system, three Laves phases and one μ phase 

have been evidenced. The existence of ternary intermetallic compounds is more or less 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_8 


1

2 8 

Fe–Nb–Zr 

controversial. For example the ternary compound Zr 54Nb 9Fe 37 cited by [1989Ale, 1989Kor1, 

1989Kor2] was not shown in the recent experimental work [2002Gra, 2003Ram, 2007Ram2] 

and its crystal structure is unknown. On the other hand, its composition lies very near by that 

of the τ 1 compound. It is the reason why this new compound was not introduced in Table 2. 

Depending on the niobium content, the intermetallic phase Zr 1–xNb xFe 2 presents three 

different Laves-type structures (see Table 2) [1968Kan, 1969Kan, 1972Fuj]. The crystal structure 

changes from C15 (MgCu2 up to x = 0.3) to C14 (MgZn2 from x = 0.5). In the middle 

composition range (0.35 < x < 0.5) this phase adopts a superstructure C36 (MgNi 2 type) with 

six atom layers leading to a c axis value approximately equal to 2c (C14) [1969Kan]. The crystal 

parameters of the C15 and C14 solid solutions from [1968Kan] are shown in Fig. 1. 

The phase transformation from C15 to C14 in the solid solutions was studied as a function 

of temperature of heat treatment and the Nb content by X-ray and magnetization experiments 

[1972Fuj]. It shows that the Nb content where the phase transformation appears depends on 

the temperature of heat treatment. 

[2002Gra] in an experimental investigation on the zirconium rich corner found two new 

intermetallic phases in this system: τ 1,aTi 2Ni type phase (labeled λ 1 in the original work) 

ranging from 2.4 to 13 at.% Nb and 31 to 33 at.% Zr, and τ 2,aC14 Laves phase (labeled λ 2 

in the original work) with a homogeneity range of 32-53 at.% Fe, 12-31 at.% Nb and 

35-37 at.% Zr. As this work does not concern the niobium rich part, he did not report on 

the μ phase which was evidenced in the former researches. 


[1972Pet] presents a quasibinary diagram of the ZrFe 2-NbFe 2 section showing, towards 

1200˚C, a solubility of 30 mol% NbFe 2 in λ 2 (ZrFe 2, C15), a solubility of 50 mol% ZrFe 2 in 

λ 1 (NbFe 2, C14), and between 30 and 50 mol% NbFe 2, a two-phase domain. Now, it is 

recognized that this two-phase domain is actually a solid solution of the C36 structure. 

It is not clear if the transitions C15-C36 and C36-C14 are of the first or second order. From 

the shape of the solidus and liquidus lines proposed by [1972Pet], it is probable that the 

liquidus of the ZrFe2-NbFe2 system presents a minimum towards 1600˚C and 40 mol% NbFe2. 


A partial reaction scheme in the Fe-ZrFe 2-NbFe 2 region is presented in Fig. 2 [1989Kor1]. The 

τ 1 phase is formed by a peritectic reaction P at the temperature of 950˚C. Two solid state 

transformations appear at 864˚C for the eutectoid reaction of formation of the mixture 

{ZrFe2+NbFe2+(γFe)} and at 928˚C for the last reaction {ZrFe2+NbFe2+(αFe)}. 


The liquidus projection has been investigated in the whole composition range by [1989Ale] 

and in the iron-rich corner by [1989Kor1] and mainly reproduced by [1992Rag]. Figure 3 

represents the liquidus projection and the primary crystallization field, mainly from [1989Ale, 

1992Rag], and slightly modified to take into account the phase equilibria in the accepted 



MSIT 1

inary systems. The primary crystallization field labeled τ by [1989Kor1] has been labeled τ 1 in 

Fig. 3 because we have identified above the ternary compound τ with the Laves phase τ 1.It 

must be pointed out that the ternary compound τ 2 does not seems to have a primary 

crystallization domain. Actually, it is probable that the domain labelled NbFe 2 (C14) must 

be split in two: one domain “NbFe 2” and one domain “τ 2”, both phases NbFe 2 and τ 2 having 

the same C14 structure. 


The sub-ternary system Fe-ZrFe 2-NbFe 2 was first investigated by [1989Kor1] at the temperatures 

1337˚C and 1315˚C. The samples were prepared by melting in arc furnace, remelted four 

times, annealed at 900˚C. The alloys were treated at the temperatures of the sections and then 

quenched. [1989Ale] and [1989Kor2] studied seven isothermal sections at the temperatures 

500, 650, 700, 800, 900, 945 and 1200˚C. This study was taken into account by [1992Rag] in its 

evaluation. But new experimental determinations, [2002Gra], are in disagreement because 

[1989Kor2] does not take into account the τ 1 and τ 2 phases whose existence and crystal 

structure are well established [2003Ram, 2007Ram2] and according to those results a tentative 

isothermal section at the temperature of 800˚C is given by [2003Rag]. It is presented in Fig. 4 

and differs from the section presented by [2003Rag] mainly by the shape of the τ 2 domain, 

which presents, in [2003Rag], an extension which has never been reported by [2002Gra, 

2002Tof]. Due to the lack of more experimental informations the solubilities in the (Nb) 

solid solution and the triangulation for the compositions are presented only as an indication. 

[2007Ram2] made some complementary X-ray determinations and presented, also as an 

indication, phase equilibria at 900˚C which are very similar to the diagram given in Fig. 4. 

In [2004Bar] the zirconium rich part of the ternary system has been studied at the 

temperature of 580˚C. The authors precise this part of the isothermal section and the solubility 

of Nb in (αZr). They used for that study specially elaborated alloys with 600-1200 ppm of 

oxygen. The phase repartition in the Zr rich corner is presented in Fig. 5. The influence of Fe 

and Nb ((Fe+Nb) < 3 mass %) on the αZr/βZr transition and the reversibility of the 

precipitation/dissolution of the secondary phase has been investigated by [2008Tof]. 



The main experimental works are reported in Table 3. Several investigations have been made 

on magnetic properties of intermetallic phases. [1994Cro] studied magnetic order resulting 

from 10 at.% substitution of Zr for Nb in the weak itinerant antiferromagnet NbFe 2. The Curie 

temperature for Zr1–xNbxFe2 as a function of the niobium content has been studied by 

[1968Kan, 1969Kan]. It was shown that the magnetic moment is strongly dependent on the 

crystal structure, decreasing dramatically during the transition from C15 to C14. 

In [1978Zak] the decomposition of the (βZr,Nb) solid solution in Nb-Zr alloys with added 

Fe was studied by electron microscopy and X-ray diffraction on single crystals. 

The Mössbauer effect, X-ray diffraction, and electron microscopy were used to study 

structural-phase transformations in an alloy rolled at room temperature of the Zr-0.5Nb- 

0.31Fe composition after annealing in the range 300-700˚C [1985Kir]. The main effect 

observed is the strengthening of Zr by precipitation of (Zr,Nb)2Fe (C16) and (Zr,Nb)Fe2 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_8 


3

4 8 

Fe–Nb–Zr 

(C15) compounds. The segregation of Fe and Nb near the Zr surface with precipitation of the 

C15 and C16 phases was also observed by [1988Igr, 1999Ram] in Zr rich alloys. Samples with 

the following compositions: Zr 62Nb 14Fe 24, Zr 65Nb 10Fe 25 and Zr 52Nb 10Fe 38 were analyzed by 

[2002Ram]. All of them showed the precipitation of τ 1, a ternary cubic Ti 2Ni type phase and 

traces of C16 (tetragonal Zr 2Fe) phase. [2007Ram1] prepared Zr-Nb-Fe alloys with Nb 

contents between 5 and 50 at.% and Fe contents between 10 and 60 at.%. After a heat 

treatment at 900˚C for 4 month, analysis of the phases showed the presence of C15 and C16 

phases. The kinetics of the phase precipitation during annealing of (αZr) alloyed with Fe and 

Nb was carried out by [1985Kir, 1988Igr]. The presence of Fe as impurities in a Zr+2.5 at.% 

Nb induces the precipitation of the C16-Zr 2Fe phase [1990Woo]. The partition coefficient of 

Fe between (αZr) and (βZr) has been evaluated at {Fe} β / {Fe} α = 1.5 to 2, which agrees with the 

β stabilizer characteristics of Fe. The presence of Fe in a (βZr,Nb) alloy lowers the solvus line 

(α+β)/β [1993Per]. 

Miscellaneous 

Amorphous state and glassy materials were evidenced by [1987Tre, 2004Yao]. The ternary Fe- 

Nb-Zr takes part in glass forming quaternary systems. The composition Fe 91–x Nb 4Zr 5B x was 

studied as glassy material by [2004Yao] as a function of the boron content as well as the 

magnetic properties. In [1993Per], an analytical transmission electron microscopy study of 

two-phase (α-β) structures in a Zr-2.5 mass% Nb pressure tube alloy was used to follow the 

distribution of Nb and Fe as a function of alloy heat treatment and tube processing. The 

presence of Fe (~0.1 mass%) modifies the (α-β) phase equilibria as Fe is a beta-stabilizing 

element, [1993Per]. Significant segregation of Fe to βZr and Nb structures was measured. 

The effects of different Nb and Fe addition ratios on the microstructure, corrosion and 

oxide characteristics of Zr based alloys were investigated by [1995Per, 2005Kim]. The Nb/Fe 

ratio was controlled to with the same amount of Nb + Fe in each alloy. The microstructural 

analysis and precipitate characterization were performed to obtain the correlation between the 

corrosion and the microstructures. 

. Table 1 

Investigations of the Co-Fe-Si Phase Relations, Structures and Thermodynamics 


[1968Gru] Thermal analysis, metallography, 

hardness 

[1972Pet] XRD ZrFe 2-NbFe 2 join 

[1989Ale] Thermal analysis, XRD, 

metallography 

[1989Kor1] Thermal analysis, XRD, 

metallography 

[1989Kor2] Thermal analysis, XRD, 

metallography 

Temperature / Composition / Phase Range 

Studied 

700-1000˚C, > 84 mass% Zr, Fe/Nb = 1/3, 1/1 

and 3/1 

850-1600˚C, Zr-Nb-NbFe2-ZrFe2, isothermal 

sections, reaction scheme 

850-1600˚C, Fe-ZrFe 2-NbFe 2, isothermal 

section, reaction scheme 

500-800˚C, the whole diagram, isothermal 

section 



MSIT 1




Studied 

[1997Per] SEM, EDX, XRD 600-800˚C, < 20 at.% Nb, < 0.1 at.% Fe, 

equilibrium (α+β)/β 

[2002Gra] XRD, SEM, metallography, EMPA 800-900˚C, > 40 at.% Zr, < 40 at.% Nb, < 40 at.% 

Fe 

[2002Tof] XRD, TEM, EDX, analysis of 

secondary phase particles 

700-1100˚C, < 2 mass% Nb, < 0.75 mass% Fe 

[2003Ram] XRD, SEM, EPMA, Mössbauer 800˚C, 35 at.% Fe, < 15 at.% Nb 

[2007Ram2] XRD, SEM, metallography 900˚C, phase equilibrium in the whole diagram 

[2008Tof] DTA, TEM, calorimetry 750-1050˚C, < 2 mass% Nb, < 1 mass% Fe, αZr/ 

βZr transition 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Lattice 

Parameters 



P63/mmc Mg 

c = 396.0 

(δFe) cI2 a = 293.15 [Mas2] 

1538 - 1394 Im3m 

W 

Dissolves up to 3.2 at.% Nb at 1373˚C and 4.5 

at.% Zr at 1357˚C 

(γFe) cF4 a = 364.67 at 915˚C [Mas2] 

1394 - 912 Fm3m 

Cu 

Dissolves up to 0.9 at.% Nb at 1210˚C and 0.7 

at.% Zr at 1337˚C 

(αFe) cI2 a = 286.65 at 25˚C [Mas2] 

< 912 Im3m 

W 

Dissolves up to 0.7 at.% Nb at 961˚C 

(ωZr) hP3 a = 503.6 at 25˚C, HP > 1 atm [Mas2] 

P6/mmm 

ωTi 

c = 310.9 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_8 


5

6 8 

Fe–Nb–Zr 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


β, (βZr,Nb) cI2 

Im3m 

(βZr) W a = 360.90 pure βZr [Mas2, V-C2] 

1855 - 863 Dissolves up to 6 at.% Fe at 928˚C 

Zr0.5Nb0.5 a = 344.5 

(Nb) a = 330.04 

< 2469 pure Nb at 25˚C [Mas2] 

Dissolves up to 7.6 at.% Fe at 1500˚C 

(αZr) hP2 a = 323.16 at 25˚C [Mas2] 

< 863 P63/mmc Mg 

c = 514.75 Dissolves up to 0.03 at.% Fe at 730˚C and 0.6 

at.% Nb at 620˚C 

μ, Nb6Fe7 hR39 a = 492.8 ± 4 [2000Tof] 

< 1520 R3m 

W6Fe7 c = 2683 ± 2 47 to 49 at.% Nb 

Zr3Fe oC16 a = 332 74.8 to 75.4 at.% Zr 

< 851 Cmcm b = 1100 [2002Ste] 

BRe3 c = 882 Dissolves up to 1.7 at.% Nb [2002Gra] 

Zr2Fe tI12 a = 638 66.7 to 67.2 at.% Zr [2002Ste] 

951 - 780 

(Zr1–xNbx)Fe2 I4/mcm 

Al2Cu c = 560 C16 structure. Dissolves up to 0.5 at.% Nb 

[2003Ram] 

hP12 0.5 < x



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


Zr6Fe23 cF116 a =1169 Sometimes labelled ZrFe3 [1997Oka]. 

1482 - 1175 Fm3m 

Th6Mn23 Metastable, stabilized by oxygen [2002Ste] 

*τ1, (Zr1–xNbx) 2Fe1–y cF96 0.035 < x < 0.25 [2003Ram] 

Fd3m 0

8 8 

Fe–Nb–Zr 


Reference 


Technique 

[1990Woo] Microstructural analysis, neutron 

and electron diffraction, 

Mössbauer 

[1993Per] SEM, energy dispersive X-Ray 

analysis (EDX) 

[1994Cro] Magnetic moments, spontaneous 

magnetization 

[1995Per] SEM, EDX, XRD, neutron 

irradiation 


Studied 

Zr-2.5 at.% Nb + Fe impurities, Fe partition 

between (αZr) and (βZr) 

500-800˚C, 2.5 mass% Nb, 0.1 mass% Fe, 

C14 Nb 1–xZr xFe 2 (x < 0.5), magnetic diagram 

Zr-2.5 Nb-0.1 Fe (in mass%), Fe and Nb 

distribution between α and β 

[1999Ram] SEM, XRD, Mössbauer, EMPA 800˚C, 0.9 to 2.4 mass% Nb, 0.6 to 10.0 mass% Fe 

[2002Kim] Thermoelectric power 540-940˚C, < 0.8 at.% Nb 

[2002Ram] XRD, Mössbauer, optical Zr62Nb14Fe24, Zr65Nb10Fe25, Zr52Nb10Fe38, 

metallography, SEM, EPMA 1200 h at 800˚C 

[2003Ram] XRD, Mössbauer, optical 

metallography, SEM, EPMA 

Zr64.5Nb0.5Fe35, Zr61Nb4Fe35, Zr55Nb10Fe35, [2004Bar] Microstructures by TEM, corrosion 

in autoclaves 

[2004Yao] XRD, DTA, DSC, TEM magnetic 

properties by VSM. 

Zr50Nb15Fe35 

Nb < 1.2 mass%, Fe < 0.1 mass% 

Fe91–x Nb4Zr5Bx with 5 < x < 30 prepared by arc 

melting solidification 

[2005Kim] EDS, TEM, XRD Nb/Fe = 0.6 to 7.0. Corrosion by H2O at 360˚C 

under 18.9 MPa 

[2006Fil] Mössbauer spectroscopy Dependence of Mössbauer absorption line area 

from effective thickness of sample 

[2007Ram1] Mössbauer, XRD, DTA, DSC, TEM, 

magnetic properties 

Zr-Nb-Fe alloys with Nb contents between 5 and 

50 at.% and Fe contents between 10 and 60 at.% 



MSIT 1


. Fig. 1 

Fe-Nb-Zr. Crystal parameters of the C15 and C14 solid solutions in the ZrFe 2-NbFe 2 system 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_8 


9

10 8 

Fe–Nb–Zr 

. Fig. 2 

Fe-Nb-Zr. Reaction scheme 



MSIT 1

. Fig. 3 

Fe-Nb-Zr. Liquidus surface projection 



MSIT 1 


DOI: 10.1007/978-3-540-70890-2_8 


11

12 8 

Fe–Nb–Zr 

. Fig. 4 

Fe-Nb-Zr. Isothermal section at 800˚C 



MSIT 1

. Fig. 5 

Fe-Nb-Zr. The Zr-rich part of the diagram at 580˚C 



MSIT 1 


DOI: 10.1007/978-3-540-70890-2_8 


13

14 8 

Fe–Nb–Zr 

References 

[1968Gru] Gruzdeva, N.M., Zagorskaya, T.N., Raevsky, I.I., “The Zr corner of the Zr-Fe-Nb Phase Diagram”, Fiz. 

Khim. Splavov Tsirkoniya, 117–121 (1968) (Phase Diagram, Experimental, 5) 

[1968Kan] Kanematsu, K., “Magnetism and Crystal Structures of Zirconium Compounds with Laves Structure”, 

J. Appl. Phys., 39, 465–466 (1968) (Calculation, Crys. Structure, Experimental, Magn. Prop., 2) 

[1969Kan] Kanematsu, K., “Structural and Magnetic Properties of Pseudobinary System (Zr 1–xNb x)Fe 2”, J. Phys. 

Soc. Jpn., 27, 849–856 (1969) (Crys. Structure, Experimental, Magn. Prop., 17) 

[1972Fuj] Fujita, Y., “The Effect of Heat Treatment on Crystallographic and Magnetic Properties of 

Zr 0.80MO 0.20Fe 2 and Zr 0.60Nb 0.40Fe 2”, J. Phys. Soc. Jpn., 33, 1720 (1972) (Crys. Structure, Experimental, 


[1972Pet] Petkov, V.V., Cherkashin, E.E., “Interaction of Laves Phases in the Quasibinary Sections ZrFe 2-(NbFe 2, 

TaFe 2)” (in Ukrainian), Dop. Akad. Nauk Ukr. RSR, (A) (3), 276–279 (1972) (Crys. Structure, Phase 

Diagram, Phase Relations, Experimental, 11) 

[1973Sve] Svechnikov, V.N., Kocherzhinsky, Yu.A., Markiv, V.Ya., Pet’kov, V.V., “Laves Phases in Transition Metal 

Systems of the IV-VII Groups of Periodic Systems” (in Russian), Akad. Nauk Ukr. SSR, Metallofizika, 

46, 35–45 (1973) (Experimental, Phase Diagram, Phase Relations, Review, 74) 

[1978Zak] Zakharova, M.I., Kirov, S.A., Khundzhua, A.G., “Formation of Metastable and Equilibrium Phases in 

the Decomposition of the β Solid Solution in Zr Alloys”, Phys. Status Solidi A, 49A(2), 803–10 (1978) 

(Crys. Structure, Phase Relations, Kinetics, Experimental, 11) 

[1979Ale] Alekseenko, G.K., “Influence of U and Fe on the Distribution of the Metastable Phases in the Zr-Nb 

System” (in Russian), in “Alloys for Atomic Energy”, Ivanov, O.S., Alekseeva, Z.M. (Eds.), Nauka, 

Moscow, 144–148 (1979) (Experimental, Mechan. Prop., Morphology, Phase Relations, 5). 

[1983Bus] Buschow, K.H.J., van Engen, P.G., Jongebreur, R., “Magneto-Optical Properties of Metallic 

Ferromagnetic Materials”, J. Magn. Magn. Mater., 38, 1–22 (1983) (Magn. Prop., Optical Prop., 


[1985Kir] Kirichenko, V.G., Snurnikova, A.I., Chekin, V.V., “Structural and Phase Transformations during 

Thermomechanical Treatment of α-Zr Alloys with Nb and Fe”, Phys. Met. Metallogr., 59(5), 100–103 

(1985), translated from Fiz. Met. Metallov., 59(5), 943–946 (1985) (Electronic Structure, Experimental, 

Phase Relations, Kinetics, 9) 

[1987Tre] Tregubov, I.A., Evseeva, L.N., Maslenkov, S.B., “Production and Examination of Zirconium Alloys in 

the Amorphous State”, Phys. Chem. Mater. Treatment, 21(1), 85–87 (1987), translated from Fiz. Khim. 

Obrab. Mater., USSR, 21(1), 124–127 (1987) (Experimental, Phase Relations, 9) 

[1988Igr] Igrushin, V.V., Kirichenko, V.G., Petel’guzov, I.A., Chekin, V.V., “Kinetics of a Phase Transformation of 

Iron Intermetallics during Annealing of α-Zr Alloyed with Nb and Fe”, Phys. Met. Metallogr., 65(1), 

126–129 (1988), translated from Fiz. Met. Metallov., 65(1), 137–140 (1988) (Experimental, Electronic 

Structure, Kinetics, 6) 

[1989Ale] Alekseeva, Z.M., Korotkova, N.V., “Isothermal Sections of State Diagram of Zr-Nb-Fe in the 

Temperature Range 1600–850˚C”, Russ. Metall., (1), 199–205 (1989), translated from Izv. Akad. Nauk 

SSSR, Met., (1), 199–205 (1989) (Experimental, Phase Diagram, Phase Relations, 17) 

[1989Kor1] Korotkova, N.V., “The Fe-ZrFe 2-NbFe 2 Phase Diagram”, Russ. Metall., (6), 185–188 (1989), 

translated from Izv. Akad. Nauk SSSR, Met., (6), 194–197 (1989) (Experimental, Phase Diagram, 


[1989Kor2] Korotkova, N.V., Alekseeva, Z.M., “Topology of the Zr-Nb-Fe Phase Diagram in the Range 500-800˚C”, 

Russ. Metall., (3), 198–204 (1989), translated from Izv. Akad. Nauk SSSR, Met., (3), 207–214 (1989) 

(Experimental, Phase Diagram, Phase Relations, 19) 

[1990Woo] Woo, O.T., Carpenter, G.J.C., Sawicki, J.A., MacEwen, S.R., “Zr-Fe Intermetallic Precipitates and Fe 

Partitioning in Zr-2.5 at.% Nb”, J. Nucl. Mater, 172, 71–76 (1990) (Electronic Structure, Experimental, 


[1991Fer] Fernandez-Guillermet, A., “Thermodynamic Analysis of the Stable Phases in the Zr-Nb System and 

Calculation of the Phase Diagram”, Z. Metallkd., 82(6), 478–487 (1991) (Phase Diagram, Phase 

Relations, Thermodyn., Assessment, 38) 

[1992Rag] Raghavan, V., “The Fe-Nb-Zr (Iron-Niobium-Zirconium) System” in “Phase Diagrams of Ternary Iron 

Alloys”, Indian Institute of Metals, Calcutta, 6B, 1031–1041 (1992) (Crys. Structure, Phase Diagram, 




MSIT 1


[1993Per] Perovic, A., Perovic, V., Weatherly, G.C., Purdy, G.R., Fleck, R.G., “A Study of the Distribution of Nb 

and Fe in Two-Phase Zr-2.5 wt.% Nb Alloys”, J. Nucl. Mater, 199, 102–111 (1993), (Experimental, 


[1994Cro] Crook, M.R., Cywinski, R., “Spin Fluctuations and Magnetic Order in Nb 1–xZr xFe 2”, Hyperfine 

Interact., 85, 203–208 1994 (Crys. Structure, Electronic Structure, Experimental, Magn. Prop., 8) 

[1995Per] Perovic, V., Perovic, A., Weatherly, G.C., Purdy, G.R., “The Distribution of Nb and Fe in a Zr-2.5 wt% 

Nb Alloy, before and after Irradiation”, J. Nuclr. Mater, 224, 93–102 (1995) (Experimental, Kinetics, 


[1997Oka] Okamoto, H., “Fe-Zr (Iron-Zirconium)”, J. Phase Equilib., 18(3), 316 (1997) (Phase Diagram, Phase 

Relations, Review, 5) 

[1997Per] Perovic, A., Weatherly, G.C., “The Promonotectoid Region of the Nb-Zr System”, J. Phase Equilib., 18 

(3), 245–248 (1997) (Experimental, Phase Relations, Review, 10) 

[1999Ram] Ramos, C., Saragovi, C., Granovsky, M., Arias, D., “Mössbauer Spectroscopy of the Zr-Rich Region in 

Zr-Nb-Fe Alloys with Low Nb Content”, Hyperfine Interact., 122, 201–207 (1999) (Electronic Structure, 

Experimental, Phase Relations, 9) 

[2000Tof] Toffolon, C., Servant, C., “Thermodynamic Assessment of the Fe-Nb System”, Calphad, 24(2), 97–112 

(2000) (Phase Diagram, Phase Relations, Thermodyn., Assessment, 40) 

[2002Gra] Granovsky, M.S., Canay, M., Lena, E., Arias, D., “Experimental Investigation of the Zr Corner of the 

Ternary Zr-Nb-Fe Phase Diagram”, J. Nucl. Mater., 302, 1–8 (2002) (Crys. Structure, Experimental, 

Morphology, Phase Diagram, Phase Relations, 25) 

[2002Kim] Kim, S.J., Hong, H.S., Oh, Y.M., “Study of the Thermoelectric Power Evolution of Zr-based Alloys 

with Nb Additions”, J. Nucl. Mater, 306, 194–201 (2002) (Electronic Structure, Experimental, Morphology, 


[2002Ram] Ramos, C., Saragovi, C., Granovsky, M., Arias, D., “Mössbauer Spectroscopy Studies of some 

Intermetallics in the Zr-Nb-Fe System”, Hyperfine Interact., 139, 363–368, (2002) (Electronic Structure, 


[2002Ste] Stein, F., Sauthoff, G., Palm, M., “Experimental Determination of Intermetallic Phases, Phase 

Equilibria, and Invariant Reaction Temperatures in the Fe-Zr System”, J. Phase Equilib., 23(6), 480–494 

(2002) (Phase Diagram, Phase Relations, Crys. Structure, Experimental, #, 88) 

[2002Tof] Toffolon-Masclet, C., Brachet, J.-Ch., Jago, G., “Studies of Second Phase Particles in Different 

Zirconium Alloys Using Extractive Carbon Replica and an Electrolytic Anodic Dissolution Procedure”, 

J. Nucl. Mater., 305, 224–231 (2002) (Crys. Structure, Experimental, Morphology, Phase Relations, 19) 

[2003Rag] Raghavan, V., “Fe-Nb-Zr (Iron-Niobium-Zirconium)”, J. Phase Equilib., 24(4), 354–355 (2003) (Assessment, 

Crys. Structure, Phase Diagram, Phase Relations, 6) 

[2003Ram] Ramos, C., Saragov, C., Granovsky, M., Arias, D., “Effects of Nb Content on the Zr 2Fe Intermetallic 

Stability”, J. Nucl. Mater., 312, 266–269 (2003) (Crys. Structure, Experimental, Morphology, Phase 


[2004Bar] Barberis, P., Charquet, D., Rebeyrolle, V., “Ternary Zr-Nb-Fe(O) System: Phase Diagram at 853 K and 

Corrosion Behaviour in the Domain Nb < 0.8%”, J. Nucl. Mater., 326, 163–174 (2004) (Crys. Structure, 

Phase Diagram, Phase Relations, Experimental, Interface Phenomena, Morphology, 30) 

[2004Yao] Yao, B., Zhang, Y., Si, L., Tan, H., Li, Y., “Boron Content Dependence of Crystallization, Glass Forming 

Ability and Magnetic Properties in Amorphous Fe-Zr-B-Nb Alloys”, J. Alloys Compd., 370, 1–7 (2004) 

(Crys. Structure, Kinetics, Magn. Prop., Morphology, Phase Relations, 35) 

[2005Kim] Kim, H.G., Park, J.Y., Jeong, Y.H., “Ex-reactor Corrosion and Oxide Characteristics of Zr-Nb-Fe Alloys 

with the Nb/Fe Ratio”, J. Nucl. Mater., 345, 1–10 (2005) (Crys. Structure, Kinetics, Morphology, 


[2006Fil] Filippov, V.P., Petrov, V.I., Lauer, D.E., Shikanova, YuA., “Calculation of Absolute Concentrations and 

Probability of Resonant Absorption for Iron-bearing Precipitates in Zirconium Alloys”, Hyperfine 

Interact., 168, 965–971 (2006) (Electronic Structure, Experimental, Phase Relations, 7) 

[2007Ram1] Ramos, C.P., Granovsky, M.S., Saragovi, C., “Mössbauer Spectroscopy Characterization of Zr-Nb-Fe 

Phases”, Physica B: Condens. Matter., 389B, 67–72 (2007) (Electronic Structure, Experimental, Phase 

Relations, 9) 

[2007Ram2] Ramos, C., Saragovi, C., Granovsky, M.S, “Some New Experimental Results on the Zr-Nb-Fe 

System”, J. Nucl. Mater. 366, 198–205 (2007) (Crys. Structure, Phase Diagram, Phase Relations, 




MSIT 1 

DOI: 10.1007/978-3-540-70890-2_8 


15

16 8 

Fe–Nb–Zr 

[2008Tof] Toffolon-Masclet, C., Guilbert, T., Brachet, J.C., “Study of Secondary Intermetallic Phase 

Precipitation/Dissolution in Zr Alloys by High Temperature - High Sensitivity Calorimetry”, J. 

Nucl. Mater., 372, 367–378 (2008) (Phase Relations, Transport Phenomena, Thermodyn., Experimental, 

25) 


(1990) 





MSIT 1

Iron – Neodymium – Silicon 


Peter Rogl 

Introduction 

Various research groups have contributed to the phase relations in the ternary system. Phase 

equilibria along the section Fe - NdSi 2–x and for the section at 33.3 at.% Nd have been 

investigated by [1969May, 1970Bod, 1972May, 1973Bau, 1973May, 1973Pin, 1974Nar, 

1975Fel, 1978Kot, 1978Ros, 1983Noa, 1983Uma, 1990Mal, 1998Wel] with emphasis in many 

cases on the physical properties of solution phases and compounds and revealed five different 

structure types: AlB 2 [1969May, 1972May, 1973May, 1974Nar], ThSi 2, TiNiSi [1973May] or 

PbFCl [1970Bod, 1998Wel], and NdFeSi 2 [1990Mal]. Further ternary compounds were discovered: 

with ThCr2Si2 structure [1972May, 1973Bau, 1973Fel, 1973Pin, 1975Fel, 1978Ros, 

1983Noa, 1983Uma, 1987Lec]; Nd 6Fe 13Si [1990All, 1994Yan, 1996Lei, 1998Gro, 2002Taj, 

2002Isn], NdFe 10Si 2 [1991Bus, 2003Sor] and NdFeSi 3 [1996Sal]. Two independent investigations 

have supplied information on the phase equilibria within a partial isothermal section at 

500˚C [1995Zhu] and a full isothermal section at 600˚C [1996Sal]. Unfortunately information 

gathered is not without controversies on the phase regions and stabilities as a function of 

temperature and therefore only a tentative version of the phase equilibria can be provided 

throughout this assessment. New studies are encouraged to solve the puzzling situation. 

An early assessment of the formation of compounds in the Fe-Nd-Si system is due to 

[1984Rog]. Table 1 includes all experimental data on phase equilibria, crystal structure and 

thermodynamics. 


The Fe-Si phase diagram adopted for this assessment is based on [1982Kub] complimented by 

recent experimental data of [2005Mec] for the liquidus and solidus curves in the Fe rich part. 

A thermodynamic assessment is due to [1998Mie]. The Fe-Nd system is taken from a 

thermodynamic calculation by [1993Hen]. The Nd-Si system as presented by [2000Oka] 

needs to be revised in many aspects (i) with respect to the existence of two modifications 

for the Nd 5Si 4 compound [2006Rog], (ii) with respect to the correct position of the phase 

labelled as “Nd 3Si 4” at NdSi 1.4 [1992Sch, 2001Bou, 2006Rog], and (iii) with respect to the 

exact location of the phases with AlB 2 type, GdSi 2–x type and ThSi 2 type (see Table 1). It is 

unclear if Nd 5Si 3 with the Mn 5Si 3 structure type is part of the Nd-Si binary [2001Bou, 

2006Rog] or is impurity stabilized. 


Fe–Nd–Si 9 

Although at least nine ternary compounds have so far been reported in literature, ternary phase 

equilibria after [1996Sal] show only four ternary compounds NdFeSi ~3 (τ 1), NdFe 2Si 2 (τ 2), 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_9 


1

2 9 

Fe–Nd–Si 

NdFe 1+xSi 1–x (τ 3) and Nd 6Fe 13Si (τ 4), which except for τ 3 were reported to exist at fixed 

compositions without significant homogeneity regions. The crystal structures of these phases 

(except τ 1) have all been elucidated (see Table 2). 

Particularly the section at constant 33.3 at.% Nd {Nd(Fe 1–xSi x) 2} shows the formation of a 

series of compounds: Nd(Fe 0.125Si 0.875) 2 (τ 6), Nd(Fe 0.20Si 0.80) 2 (τ 9), and Nd(Fe 0.33Si 0.66) 2 (τ 5). 

According to early data by Mayer and Tassa [1969May] Nd(Fe0.125Si0.875)2 (τ6) crystallized 

with the ThSi2 structure type and Nd(Fe0.20Si0.80)2 (τ9) was single phase AlB2 type. The ThSi2 

type structure was reported to be stable for compositions x < 0.4 at 700 - 800˚C [1969May, 

1973May]. For a statistical distribution of Fe and Si atoms in the 2d sites of P6/mmm of Nd 

(Fe 0.20Si 0.80) 2 the calculated and observed X-ray powder intensity data were said to be in good 

agreement. Nd(Fe 0.33Si 0.66) 2 (τ 5) was said to transform above 950˚C: the d values of the new 

phase were reported as 2.61(90), 2.53(100), 2.06(70) and 1.62(50), with relative intensities in 

brackets [1972May]. It is interesting to note that both structure types ThSi 2 and AlB 2 are 

found with binary defect Nd-silicides NdSi2–y. 

Some controversies exist along the concentration line Fe - NdSi2 which contains two 

phases: NdFeSi 2 (τ 8) and NdFe 1+xSi 1–x (τ 3). NdFeSi was claimed to be single-phase with an 

orthorhombic “TiNiSi type” of structure [1973May]. The existence of a compound NdFeSi 

was confirmed by [1970Bod, 1995Zhu, 1998Wel], but at variance with [1973May] a tetragonal 

PbFCl type of structure (CeFeSi type) was obtained from arc-melted alloys heat treated at 

800˚C for 3 months (low-temperature phase?). Due to the high temperature of preparation 

and homogenization the “TiNiSi type” phase as reported by Mayer and Felner [1973May] is 

likely to represent a high-temperature modification. At variance to [1996Sal], the findings of 

[1995Zhu] revealed a significant homogeneity region NdFe1+xSi1–x extending at 500˚C from 

28 to 36 at.% Si. 

NdFeSi 2 (τ 8) with TbFeSi 2 structure type was prepared at 1000˚C (1273 K) and quenched. 

The material was consecutively investigated at temperatures below 300 K (27˚C) without any 

signs of decomposition [1990Mal]. Presently it is unclear if NdFeSi 2 is stable at high temperatures 

only. 

Many contributions are concerned with the physical and predominantly the magnetic 

properties of NdFe2Si2 (τ2) (see section Notes on Materials Properties and Applications). 

Although the compound ties to most neighboring phases (see phase relations in Fig. 1), 

heating of NdFe 2Si 2 above 700˚C was reported to result in a decomposition into a mixture of 

Nd 5Si 4 and Fe 3Si [1972May]. 

The crystal structure of Nd 6Fe 13Si (τ 4) (space group I4/mcm) was derived from single 

crystal X-ray data and was found to be an ordered version of the Nd 6Fe 11Ga 3 type [1990All]. 

At subsolidus temperatures solubility of Si in Nd 2Fe 17 was found to extend at least to 

NdFe 12.91Si 4.09 from a neutron diffraction experiment on samples Nd 2Fe 17–xSi x (x up to 4) 

reducing anisotropically the unit cell volume: silicon atoms avoid the 6c site but prefer the 18h 

site (the site with the highest Nd-coordination number) [1993Lon, 1995Yel, 1996Yel, 

1996Gir]. Samples at x = 5 annealed at 1000˚C for one month showed in the X-ray spectrum 

besides majority of Nd 2Fe 17–xSi x phase also NdFe 2Si 2, Fe-Si and small amounts of a bct Nd(Fe, 

Si) 11 phase [1997Hua]. 

The crystal structures of the ternary compounds are all summarized in Table 2. 



MSIT 1


A partial isothermal section at 500˚C for the region < 40 at.% Nd and < 40 at.% Si [1995Zhu] 

and a full isothermal section at 600˚C [1996Sal] have been derived. Although the two 

investigations were only apart in temperature by 100˚C, there are severe differences in (i) 

the extent of the homogeneity region of the NdFeSi phase (point compound in [1996Sal], but 

NdFe1+xSi1–x with –0.8 < x < 0.16 reported by [1995Zhu]); (ii) the phase equilibria NdFeSi + 

Nd6Fe13Si + Nd5Si3 [1996Sal] in contrast to NdFe1+xSi1–x + Nd2(Fe1–xSix)17 + Nd by 

[1995Zhu], and (iii) maximal solubility of Si in Nd 2Fe 17 given at about 4 at.% Si by 

[1996Sal] but 12 at.% Si by [1995Zhu]. Figure 1 shows the isothermal section at 600˚C, 

which was slightly modified to comply with the accepted binary systems. Furthermore, 

equilibria as given by [1996Sal] were used for the Fe-Nd rich side but a homogeneity region 

was inferred from [1995Zhu] for the NdFeSi phase and a higher solubility of 12 at.% Si was 

adopted for the Nd 2Fe 17 phase. It needs to be noted, however, that at 600˚C only few of the 

compounds discovered were reported and neither phases such as τ9 (AlB2 type) and τ6 (ThSi2 

type) nor solid solutions of Fe in these phases have been observed [1996Sal], although both 

structure types exist in the binary Nd-Si system. Furthermore phases τ 5, τ 7, τ 8 were not 

observed [1996Sal, 1995Zhu]. This may be either due to slow reaction kinetics and diffusion 

at low temperature or on the fact that these phases are all high temperature phases which are 

only stable at temperatures above 600˚C. 



In view of the various magnetic and electric properties of binary Nd-silicides basic interest in 

Nd-Fe-silicides essentially covered Si rich compounds τ 2, τ 6, τ 9, τ 8 among which the most 

studied phase is τ 2 (NdFe 2Si 2, tetragonal with the ordered ThCr 2Si 2 type of structure: I4/mmm, 

a = 399.2, c = 1007.0 pm, p x = 6.46 kg·dm –3 [1978Ros]; X-ray powder diffraction). After the 

discovery of the permanent magnet Nd 2Fe 14B with high magnetic anisotropy and high 

magnetic energy product due to the interaction of magnetic Nd and Fe sublattices, scientific 

interest in permanent magnet materials was concerned with Fe-Nd rich phases stabilized by 

silicon: Nd6Fe13Si (τ4), NdFe10Si2 (τ7) and the solid solution Nd2Fe17–xSix. 

τ 2-NdFe 2Si 2: In a neutron powder diffraction study of NdFe 2Si 2 by Pinto and Shaked 

[1973Pin] five superlattice reflections were observed at 4.2 K. These lines were found to be 

consistent with a doubling of the c-axis according to a new unit cell a’ = 398.0 and c’ = 1990 pm 

with the magnetic space group P 2c4/nm’m’. The Nd sublattice with Nd atoms in the “2a sites” 

{3.01(3) μ B per Nd atom} orders antiferromagnetically. A collinear magnetic structure with 

tetragonal symmetry of the Fe sublattice could be excluded. The Néel temperature at T N = 15.6 

K was determined from the intensity-temperature curve of the strongest superlattice reflections. 

The magnetic structure consists of ferromagnetic sheets perpendicular to the c-axis 

(magnetic axis along c) and with a stacking sequence ++ –. The neutron powder diffraction 

pattern at room temperature (I4/mmm, a = 398.3, c = 1003 pm) was refined to R = 0.083 and 

yielded a small statistical distribution of Fe/Si atoms according to: Nd in 2a sites, 0.902 Fe + 

0.098 Si in 4d, and 0.098 Fe + 0.902 Si in the 4e sites with z Si= 0.372. The structure type at 

room temperature was confirmed (a = 3.995 ± 0.05, c = 1007 ± 5 pm) by [1973Bau, 1975Fel], 

who also reported magnetic susceptibility data with a weak ferromagnetic ordering at 

713 ±⊊5 K; the rare earth sublattice orders antiferromagnetically at TN = 11 K, and from 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_9 


3

4 9 

Fe–Nd–Si 

magnetization measurements a spin-flop transition is observed for a field of 11 kOe below the 

Néel temperature. Mössbauer effect and magnetization measurements reveal most of the iron 

to be diamagnetic (94 %). More recent magnetization and Mössbauer data by [1983Noa, 

1983Uma]( 57 Fe, 297 K, 4.2 K) prove the absence of a magnetic moment at the Fe site and the 

spectra at 4.2 Kwere interpreted by the presence of an internal magnetic field at the Fe nucleus, 

due to the antiferromagnetic ordering of the R atom (conduction electron polarization caused 

by Nd ion). Thus two magnetic sites were concluded for the Fe atoms without and with an 

internal field of 22 ± 1 kG [1983Uma]. The thermal expansion coefficients of NdFe 2Si 2 have 

been determined by Mayer and Felner [1972May] by means of high temperature diffractometry 

(see also NdFe 0.4Si 1.6): α a = 5.5 · 10 –6 deg –1 ; α c = 11.1 · 10 –6 deg –1 ; a = 7.4 · 10 –6 deg –1 . The 

volume expansion coefficient was γ = 22.6 · 10 –6 deg –1 . The electrical resistivity of NdFe 2Si 2 

was 9.7 mΩ·cm at 300 K [1973Fel]. For a calculation of the electronic state of the Fe atoms in 

NdFe 2Si 2, see Koterlin and Lutsiv [1978Kot]. Magnetic data on NdFe 2Si 2 were discussed by 

[1987Lec] as part of a summary on isotypic rare earth and actinide compounds. Crystal 

growth and analysis of basic thermodynamic properties of NdFe2Si2 was reported by 

[2003Svo, 2003Vej]. 

Nd(Fe0.20Si0.80)2 (τ9): 

Mayer and Felner [1972May] determined the thermal expansion coefficient of NdFe 0.4Si 1.6 by 

means of high-temperature X-ray diffraction. Samples were held in Ta crucibles and the 

temperature was accurate within ± 10˚C: αa = 10.5 · 10 –6 deg –1 , αc = 15.00 · 10 –6 deg –1 and 

a = 12.0 · 10 –6 deg –1 ; the volume expansion coefficient was γ = 35.0 · 10 –6 deg –1 . NdFe 0.4Si 1.6 

was said to exhibit a complex magnetic spin structure [1974Nar]. 

NdFeSi2 (τ8): 

A detailed study of the magnetic structure of NdFeSi2 revealed a sine-modulated antiferromagnetic 

structure (Nd-moments = 2.52μB at 4.2 K) q = (0,0.591,0) below TN = 6.5 K 

[1990Mal]. 57 Fe Mössbauer data prove the absence of a magnetic moment at the Fe site but 

indicated a progressive squaring of the sine modulation of the Nd-moments with a pure 

square wave at 3 K suggesting orbital polarization of conduction electrons [1990Mal]. 

Nd6Fe13Si (τ4): 

Nd6Fe13Si was found to be an antiferromagnet below TN = 725 K (452˚C) [1990All] 

whereas [1998Gro] reported T N = 421 K (148˚C). Magnetization and Mössbauer measurements 

on Nd 6Fe 13Si show antiferromagnetism with a net moment of 0 - 1μ B/formula unit 

but on hydrogenation to Nd 6Fe 13SiH 14.6 there is ferromagnetic behavior with a moment of 

23 - 27 μ B/formula unit at room temperature [1996Lei]. The hydrogenation properties show a 

marked reduction of the maximum hydrogen uptake related directly to the Si substitution rate 

[1999Art]. 

[2002Taj] investigated magnetoelastic interactions in Nd6Fe13Si by magnetostriction and 

thermal expansion measurements (77 - 300 K). A reversal in sign of magnetostriction versus 



MSIT 1

temperature occurred at 115 K, accompanied by a spin re-orientation of iron ions from basal 

plane to c axis at higher temperatures. At the spin re-orientation temperature (T sr) of 115 K, 

magnetostriction remains around zero due to the compensation of the negative magnetostriction 

of the low-temperature phase by positive magnetostriction of the high temperature spin 

phase. The magnetostriction compensation effect appears as a peak in the thermal expansion 

coefficient curve. 

A reinvestigation of the magnetic structure Nd6Fe13Si by means of powder neutron 

diffraction and Mössbauer spectral studies between 2 - 295 K [2002Isn] confirmed earlier 

findings: a collinear antiferromagnetic structure with the wave vector q = (0, 0, 1) below the 

T N = 421 K. A spin reorientation is observed at T < 100 K in both the neutron diffraction 

patterns and the Mössbauer spectra. Above and below 100 K, the magnetic moments of the 

four iron and the two neodymium crystallographic sites are ferromagnetically coupled within 

one block along the c axis and the resulting magnetic moment of this block is antiferromagnetically 

coupled with that of the adjacent block along the c axis through a layer of silicon 

atoms. Above and below 100 K, the magnetic moments are found to be parallel or very close to 

the c axis and within or close to the (a, b) basal plane of the tetragonal unit cell, respectively. 

NdFe10Si2 (τ7): 

The substitutional effect on magnetic properties has been studied by X-ray powder diffraction 

and Mössbauer spectroscopy on Nd 2Fe 15Si 2, NdFe 10Si 2 [2003Sor]. A review on crystal structure, 

formation and magnetic properties of the hard magnetic phase NdFe 10Si 2 (T C = 574˚C) is 

presented in [1991Bus]. 

Solution Nd2Fe17–xSix: 


Substitution of Si for Fe in Nd 2Fe 17–xSi x was investigated by [1993Lon, 1995Yel, 1995Zha, 

1996Yel] by magnetization [1993Lon, 1997She, 1997Hua] and Mössbauer spectroscopy 

[1993Lon], by neutron diffraction [1995Yel, 1996Yel] and high temperature X-ray diffraction 

[1995Zha]. Fe/Si substitution was observed to raise the Curie temperature from TC = 325 K 

(52˚C) for x =0toT C = 492 K (219˚C) for x =3[1993Lon, 1996Gir, 1997She]; reaching a 

maximum at x =4[1995Yel]. The easy direction of magnetization was found to change from 

basal at low Si content (x < 3) to axial at high Si content [1996Yel, 1995Zha] consistent with 

Mössbauer spectra, magnetization and hyperfine field parallel to the c axis [1993Lon]. The 

iron moment decreases on Si substitution [1997She]. Due to the various substitution effects 

an Invar type of anomalies were reported for the temperature dependence of a, c parameters 

below T C [1995Zha]. The observed spontaneous magnetostriction is due to isotropic exchange 

contribution - no spin reorientation was observed for x

6 9 

Fe–Nd–Si 

. Table 1 

Investigations of the Fe-Nd-Si Phase Relations, Structures and Thermodynamics 


[1969May] HF melting under Ar from RE-ingots and 

Fe,Si powders on MgO or Al 2O 3 crucibles. 

Annealing in quartz at 700 to 800˚C for 24 

to 96 h. Microstructure analysis, XPD 

[1970Bod] Ar-arc melting from 50 g RE-ingots and Fe, 

Si powders. Annealing in quartz at 800˚C 

for 3 months. Single crystals isolated from 

center of alloy; X-ray single crystal study 

[1972May] HF melting under He from RE-ingots and 


Annealing in quartz at 700˚C for 48 h. 

In situ high temperature XPD 20 to 1200˚C 

in Ta-sample holder. 

[1973Bau] HF melting under Ar from RE-ingots and 


Annealing in HF at 1600˚C (reaction 

temperature) for 20 min. XPD, 57 Fe 

Mössbauer analysis (4.2 and 300 K), 

magnetic susceptibility (1.5 to 300 K) 

[1973Fel] HF melting under Ar from RE-ingots and 


Annealing in HF at 1600˚C (reaction 

temperature) for 30-60 min. XPD, electrical 

resistivity (100 to 280 K) 

[1973May] HF melting under Ar from ingots on Al 2O 3 

crucibles. Annealing in HF at 1600˚C 

(reaction temperature) for 30 min. XPD 


Studied 

Synthesis of Nd(Fe 0.2Si 0.8) 2 with AlB 2 type. 

Determination of the crystal structure of 

NdFeSi (PbFCl type); R F = 0.135. 


Synthesis of NdFe 2Si 2 with ThCr 2Si 2 type. 

Determination of thermal expansion 

coefficients. 

Synthesis of Nd(Fe 0.125Si 0.875) 2 with ThSi 2 

type. 


Synthesis of NdFeS with TiNiSi type. 

Synthesis of NdFe2Si2 with ThCr2Si2 type. 

Electrical resistivity (100 to 280 K) 


Electrical resistivity (100 to 280 K) 

[1973Pin] See [1973May]; XPD, NPD at 4.2, 300, 650 K Synthesis of NdFe 2Si 2 with ThCr 2Si 2 type. 

Determination of crystal and magnetic 

structure by neutron diffraction. 

[1974Nar] HF melting under Ar from ingots in Al 2O 3 

crucibles. Annealing in Vycor tubes at 

850˚C for 1 week. Microstructure analysis, 

XPD. Magnetic susceptibility and 

magnetization measurements (4.2 to 

630 K) 

[1975Fel] See [1973May]; magnetic susceptibility 

and magnetization measurements (1.5 to 

300 K) 


Elucidation of magnetic structure. 


Determination of magnetic behavior. 



MSIT 1



[1978Ros] HF melting under Ar from ingots. 

Annealing in Vycor tubes at 500˚C for 

1 week. Microstructure analysis, XPD. 

[1990All] Single crystals of Nd 6Fe 13Si were isolated 

from an alloy 90Nd10Fe + 2 mass% Si 

melted under vacuum and slowly cooled 

from 700 to 500˚C (3˚C/h). 

[1990Mal] Sintering of pellets from powders of Fe,Si 

and filings of Nd at 1000˚C in silica tubes 

with repeated crushing. 

X-ray (RT) and neutron (1.5 to 40 K) 

powder diffraction ; 57 Fe Mössbauer 

analysis (1.6 and 295 K) 

[1993Lon] HF melting (or arc casting) under Ar from 

ingots. X-ray and neutron powder 

diffraction; 57 Fe Mössbauer spectrometry 

at 295K. Susceptibility and magnetization 

(1.8 to 300 K) 

[1995Zhu] 88 alloys prepared by HF melting under Ar 

from ingots in alumina crucibles. 

Annealing for alloys < 20 at.% Nd: 800˚C 

30 d - cooled to 500˚C at 10 K/h. Other 

alloys were annealed at 650˚C for 40 d, 

cooled at 10 K/h to 500˚C kept for 7 d 

prior to quenching in ice water. XPD 

[1996Sal] Ar-arc melting of ingots annealed in 

quartz at 600˚C for 3 weeks. XPD 

[1995Yel] 

[1996Yel] 

[1996Gir] 

Ar-arc or HF melting of ingots annealed in 

vacuum at 980˚C for 1 to 3 weeks 

[1995Yel, 1996Yel] or at 1070˚C under Ar 

for several days [1996Gir]. X-ray and 

neutron powder diffraction 

[1998Wel] HF melting of ingots under Ar, annealed in 

quartz at 1000˚C for 10 d. Crystals for 

X-ray analyses isolated from ingot. 

[2003Sor] Ar arc-melting of ingots, annealed in 

quartz at 950 to 1050˚C for 10 d. XPD, 57 Fe 

Mössbauer spectrometry at 295 K. 



MSIT 1 



Studied 


Synthesis of Nd 6Fe 13Si. Determination of 

crystal structure from X-ray single crystal 

data. 

Synthesis of NdFeSi 2. Determination of 

crystal and magnetic structure from X-ray 

and neutron powder data. 

Samples Nd 2Fe 17–xSi x (x up to 4). 

Determination of crystal and magnetic 

structure from X-ray and neutron powder 

data. 

Constitution of a partial isothermal 

section at 500˚C for the region < 40 at.% 

Nd and < 40 at.% Si. 

Determination of isothermal section at 

600˚C. 

Samples Nd 2Fe 17–xSi x (x up to 4.2). X-ray 

and neutron powder diffraction to 

determine detailed atom site distribution 

as a function of x. 

X-ray single crystal structure 

determination of NdFeSi. 

Preparation of Nd 2Fe 15Si 2, NdFe 10Si 2 

DOI: 10.1007/978-3-540-70890-2_9 


7

8 9 

Fe–Nd–Si 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 

Lattice 

Parameters 


(βNd) cI2 a = 413 [Mas2] 

1021 - 863 Im3m 

W 

(αNd) hP4 a = 365.82 [Mas2] 

< 863 P63/mmc αLa 

c = 1179.66 


1538 - 1394 Im3m 

W 

(γFe) cF4 a = 364.67 pure Fe at 915˚C [Mas2] 

1394 - 912 Fm3m 

Cu 


< 912 Im3m 

W 

(αSi) cF8 a = 543.06 at 25˚C [Mas2] 

< 1414 Fd3m 

C (diamond) 

Nd5Si3 tI32 a = 776.8 at 25˚C [V-C2] 

< 1477 I4/mcm 

Cr5B3 c = 1369 

a = 778.7 

c = 1373 

at 280˚C [V-C2] 

Nd5Si3 hP16 a = 867.1 ± 2 [2006Rog] 

? P63/mmc Mn5Si3 c = 657.7 ± 2 

a = 778.7 

c = 1373 

may be impurity stabilized 

Nd5Si4 tP36 a = 787.30 ± 0.01 [2006Rog] 

< 1567 P41212 Zr5Si4 c = 1483.89 ± 0.01 

Nd5Si4 oP36 a = 786.7 [V-C2] 

Pnma b = 1474 

Sm5Ge4 c = 790.7 

a = 786.70 ± 0.03 

b = 1508.35 ± 0.05 

c = 789.20 ± 0.03 

[2006Rog] 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 


Lattice 

Parameters 


NdSi oP8 a = 818.74 ± 0.09 [2001Bou] 

< 1677 Pnma b = 392.35 ± 0.04 

FeB c = 588.40 ± 0.06 

Nd2Si3–x (NdSi1.33) oC20 Listed as “Nd3Si4”[2000Oka] < 1397 Cmcm 

Ho3Si4 a = 435.89 ± 0.01 at NdSi1.40 [2001Bou] 

or better V2B3 b = 2457.74 ± 0.04 [1992Sch] attributed V2B3 type 

c = 391.61 ± 0.01 

a = 436.2 x = 0.5 at 293 K [1992Sch] 

b = 2458.4 

c = 391.6 

Ferromagnetic TC =80K 

a = 434.75 

b = 2456.42 

c = 391.11 

x = 0.5 at 20 K [1992Sch] 

NdSi2–x hP3 x close to 0.4 [V-C2] 

(h1) P6/mmm a = 395.03 ± 0.03 x close to 0.34 [2001Bou] 

< 1507 AlB2 c = 425.73 ± 0.04 

a = 394.8 [1990Pie] 

c = 426.9 TN1 = 3.5 K, antiferromagnetic 

Tm = 1.5 K, metamagnetism 

NdSi2–x oI12 a = 417.6 NdSi1.8 [V-C2] 

(h2) Imma b = 414.5 

< 527 ? GdSi2–x c = 1359.9 

a = 413.5 NdSi1.73 b = 410.1 

c = 1374 

TC = 10 K, ferromagnetic [1990Pie] 

NdSi2–x(h3) tI12 a = 414.2 ± 0.6 x close to 0.2 [V-C2] 

< 1757 I41/amd c = 1365 ± 2 [1990Pie]: 

ThSi2 TN1 = 10 K, antiferromagnetic 

TN2 = 6 K, collinear antiferromagnet 

α1,Fe3Si cF16 D03, 11.0 to 30.0 at.% Si [1982Kub] 

≤ 1235 Fm3m 

BiF3 

a = 565 [V-C2] 

α2, Fe-Si cP2 B2, 10.0 to 22.0 at.% Si [1982Kub] 

≤ 1280 Pm3m 

CsCl 

a = 281 [V-C2] 

Fe2Si hP6 ~33.0 to ~34.3 at.% Si [1982Kub] 

1212 - 1040 P3m1 a = 405.2 ± 0.2 

Fe2Si c = 508.55 ± 0.03 [V-C2] 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_9 


9

10 9 

Fe–Nd–Si 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 

Lattice 

Parameters 


Fe5Si3 hP16 37.5 at.% Si [1982Kub] 

1060 - 825 P63/mmc a = 675.9 ± 0.5 [V-C2] 

Mn5Si3 c = 472.0 ± 0.5 

FeSi cP8 49.6 to 50.8 at.% Si [1982Kub] 

< 1410 P213 FeSi 

a = 451.7 ± 0.5 [V-C2] 

FeSi2(h) tP3 69.5 to 73.5 at.% Si [1982Kub] 

1220 - 937 P4/mmm a = 269.01 [V-C2] 

FeSi2 c = 513.4 

FeSi2(r) oC48 66.7 at.% Si [1982Kub] 

< 982 Cmca a = 986.3 ± 0.7 [V-C2] 

FeSi2 b = 779.1 ± 0.6 

c = 783.3 ± 0.6 

Nd2Fe17(r) hR57 a = 857 to 859 [V-C2] 

< 1208 R3m 

Th2Zn17 c = 1244 to 1248 

Nd2(Fe1–xSix) 17 

a = 859.0 

c = 1247.6 

a = 852.1 

c = 1249.7 

a = 856.1 

c = 1247.5 

0



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 


Lattice 

Parameters 


NdFe5 hP6 a = 494.6 [1986Sta] 

metastable? P6/mmm 

CaCu5 c = 417.0 from splat-cooled alloy 

* τ1, NdFeSi3 - [1996Sal] 

* τ2, NdFe2Si2 tI10 a = 398.1 ± 0.1 at 25˚C [1972May] 

< 700 I4/mmm 

ThCr2Si2 c = 1002 ± 0.2 at 400˚C [1972May] 

a = 399.2 ρexp = 6.46 Mg·m –3 [1978Ros] 

c = 1011 a supercell was found at 4.2 K 

a = 398.0, c = 1990 pm = 2c0 [1973Pin] 

TN = 15.6 K 

a = 400.7 at 1150˚C [1972May] 

c = 1026 linear dependency 25 to 1150˚C 

* τ3, NdFeSi (h) oP12 a = 689 [1973May] 

Pnma b = 532 

TiNiSi or Co2Si c = 1118 

* τ3, NdFe1+xSi1–x (r) tI12 –0.8 < x < 0.16 at 500˚C [1995Zhu] 

P4/nmm a = 405.7 x = 0, quenched from 800˚C; 

PbClF c = 689.3 ρexp= 6.54 Mg·m –3 [1970Bod] 

(CeFeSi type) [V-C2] lists Cu2Sb type 

a = 392.1 

c = 694.2 

[1995Zhu] noxgiven a = 405.7 ± 0,3 x = 0, SC data from alloy at 1000˚C 

c = 691.9 ± 0,5 [1998Wel]; R = 0.076 

* τ4,Nd6Fe13Si tI80 a = 803.4 [1990All] 

I4/mcm c = 2278 RF = 0.07 

Nd6Fe13Si derivative of Nd6Fe11Ga3 type 

* τ5, Nd(Fe0.33Si0.67) 2 

< 950 

- - [1972May] 

* τ6, Nd(Fe0.125,Si0.875)2 tI12 a = 411.5 [1973May] 

I41/amd ThSi2 c = 1390 

*τ7, NdFe10Si2 cF296 - [1991Bus, 2003Sor] 

Fm3m 

ThMn12 no lattice parameters given 

* τ8, NdFeSi2 oC16 a = 408.2 ± 0,3 [1990Mal] 

Cmcm b = 1698 ± 3 TbFeSi2 type 

variant of 

CeNiSi2 c = 400.4 ± 0,3 TN = 6.5 K sine modulated AF 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_9 


11

12 9 

Fe–Nd–Si 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 

Lattice 

Parameters 


* τ9, Nd(Fe0.2Si0.8) 2 tP3 a = 403.1 quenched from 700 to 800˚C 

< 950 P6/mmm 

AlB2 c = 419.2 [1969May] 

a = 404.6 

c = 421.7 

at 25˚C [1972May] 

a = 405.9 

c = 423.7 

at 500˚C [1972May] 

a = 406.5 

c = 425.3 

at 600˚C [1972May] 

a = 407.2 

c = 426.1 

at 820˚C [1972May] 



MSIT 1


. Fig. 1 

Fe-Nd-Si. Isothermal section at 600˚C. Location of ternary compounds, τ 5 to τ 9, not detected by 

[1996Sal], are shown as filled circles 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_9 


13

14 9 

Fe–Nd–Si 

References 

[1969May] Mayer, I., Tassa, M., “Rare-Earth-Iron (Cobalt, Nickel)-Silicon Compounds”, J. Less-Common Met., 

19, 173–177 (1969) (Crys. Structure, Experimental, 9) 

[1970Bod] Bodak, O.I., Gladyshevsky, E.I., Kripyakevich, P.I., “Crystal Structure of Ce-Fe Silicide and Similar 

Compounds.”, Zh. Strukt. Kim., 11, 305–310 (1970) (Experimental, Crys. Structure, 20) 

[1972May] Mayer, I., Felner, I., “High-Temperature X-Ray Study of Rare-Earth Silicides”, J. Less-Common Met., 


[1973Bau] Bauminger, E.R., Felner, I., Froindlich, D., Grill, A., Lebenbaum, D., Mayer, I., Nowik, I., Ofer, S., 

Schieber, M., “Magnetic Properties of RFe 2Si 2 and RFe 2Ge 2 Compounds” in “Proc. Intl. Conf. Magnetism”, 

Moscow, 5, 56–59 (1973) (Experimental, Crys. Structure, Magn. Prop., 5) 

[1973Fel] Felner, I., Mayer, I., “The Electrical Resistivity of RFe 2Si 2 Type Rare-Earth Silicides”, Mater. Res. Bull., 

8, 1317–1319 (1973) (Crys. Structure, Electr. Prop., Experimental, 5) 

[1973May] Mayer, I., Felner, I., “Structure Types of Ternary Rare Earth - Transition Metal Silicides of the LnM xSi 2–x 

Type”, J. Solid State Chem., 7, 292–296 (1973) (Crys. Structure, Experimental, 12) 

[1973Pin] Pinto, H., Shaked, H., “Neutron-Diffraction Study of NdFe 2Si 2”, Phys. Rev. B (Solid State), 7(7), 


[1974Nar] Narasimhan, K.S.V.L., Steinfink, H., “Magnetic Investigations on AlB 2 Type Structures”, J. Solid State 

Chem., 10, 137–141 (1974) (Crys. Structure, Experimental, Magn. Prop., 10) 

[1975Fel] Felner, I., Mayer, I., Grill, A., Schieber, M., “Magnetic Ordering in Rare-Earth Fe Silicides and 

Germanides of the RFe 2X 2 Type”, Solid State Commun., 16, 1005–1009 (1975) (Crys. Structure, Experimental, 


[1978Kot] Koterlin, M.D., Lutsiv, R.V. “Electron State of Iron Atoms in the Neodymium Iron Silicide (NdFe 2Si 2) 

Compound” (in Russian), Fiz. Elektronika, 17, 18–21 (1978) cited from Ref. Zh., Fiz., E, Abstr. No. 2E58 

(1979) (Experimental, Phys. Properties, 4) 

[1978Ros] Rossi, D., Marazza, R., Ferro, R., “Lattice Parameters of Some ThCr 2Si 2 Type Phases in Ternary Alloys of 

Rare Earths with Cobalt (or Iron) and Silicon (or Germanium)”, J. Less-Common Met., 58(2), 203–207 

(1978) (Crys. Structure, Experimental, 10) 

[1982Kub] Kubaschewski, O., “Iron-Silicon” in “Iron - Binary Phase Diagrams”, Springer Verlag, Berlin, 136–139 

(1982) (Phase Diagram, Review, #, *, 23) 

[1983Noa] Noakes, D.R., Umarji, A.M., Shenoy, G.K., “Mössbauer Studies of REFe2Si2 (RE = Gd-Lu) Compounds”, 

J. Magn. Magn. Mater., 39, 309–316 (1983) (Experimental, Crys. Structure, Magn. Prop., 22) 

[1983Uma] Umarji, A.M., Noakes, D.R., Vccaro, P.J., Shenoy, G.K., Aldred, A.T., “Magnetic Properties of REFe 2Si 2 

Compounds”, J. Magn. Magn. Mater., 36(1–2), 61–65 (1983) (Experimental, Crys. Structure, Magn. 

Prop., 19) 

[1984Rog] Rogl, P., “Phase Equilibria in Ternary and Higher Order Systems with Rare Earth Elements and Silicon” 

in “Handb. Phys. Chem. Rare Earths”, North-Holland Publ. Co, Amsterdam, vol. 7, 1–264 (1984) 

(Review, Crys. Structure, Phys. Properties, 10) 

[1986Sta] Stadelmaier, H.H., Schneider, G., Ellner, M., “A CaCu 5-type Iron-Neodymium Phase Stabilized by 

Rapid Solidification”, J. Less-Common Met., 115, L11–L14 (1986) (Crys. Structure, Experimental, 5) 

[1987Lec] Leciejewicz, J., Szytula, A., “The Systematics of Magnetic Structure Observed in MT 2X 2 Compounds”, 

Acta Phys. Pol., A72(1), 65–68 (1987) (Assessment, Electronic Structure, Magn. Prop., 8) 

[1990All] Allemand, J., Letant, A., Moreau, J.M., Nozieres, J.P., Perrier de la Bathie, R., “A New Phase in Nd 2Fe 14B 

Magnets. Crystal Structure and Magnetic Properties of Nd 6Fe 13Si”, J. Alloys Compd., 166, 73–79 (1990) 

(Experimental, Crys. Structure, Magn. Prop., 9) 

[1990Mal] Malaman, B., Venturini, G., Le Caer, G., Potonnier, L., Fruchart, D., Tomala, K., Sanchez, J.P., 

“Magnetic Structures of PrFeSi 2 and NdFeSi 2 from Neutron and Mössbauer Studies”, Phys. Rev. B, 41(7), 

4700–4712 (1990) (Experimental, Crys. Structure, Magn. Prop., 33) 

[1990Pie] Pierre, J., Auffret, S., Siaud, E., Madar, R., Houssay, E., Rouault, A., Senateur, J.P., “Magnetic Properties 

of Rare Earth Silicide Single Crystals RSi 2–x (R = Pr, Nd, Gd)”, J. Mag. Magn. Mater, 89(1-2), 86–96 

(1990) (Experimental, Crys. Structure, Magn. Prop., 10) 

[1991Bus] Buschow, K.H.J., “New Developments in Hard Magnetic Materials”, Rep. Prog. Physics, 54, 1123–1213 

(1991) (Review, Magn. Prop., 223) 



MSIT 1


[1991Lan] Landgraf, F.J.G., Missell, F.P., Rechenberg, H.R., Schneider, G., Villas-Boas, V., Moreau, J.M., Paccard, 

L., Nozieres, J.P., “Magnetic and Structural Characterization of Nd 5Fe 17”, J. Appl. Phys., 70(10), 

6125–6127 (1991) (Crys. Structure, Magn. Prop., Experimental, 16) 

[1992Sch] Schobinger-Papamantellos, P., DeMooij, D.B., Buschow, K.H.J., Fischer, P., “Magnetic Ordering in 

Silicon Defect Nd-Si Compounds Studied by Neutron Diffraction and Magnetic Measurements”, 

J. Alloys Compd., 178, 151–159 (1992) (Crys. Structure, Experimental, Magn. Prop., 13) 

[1993Hen] Hennemann, K., Lukas, H.L., Schaller, H.J., “Constitution and Thermodynamics of Fe-Nd Alloys”, Z. 

Metallkd., 84, 668–674 (1993) (Experimental, Calculation, Thermodyn., Phase Diagram, 34) 

[1993Lon] Long, G.J., Marasinghe, G.K., Mishra, S., Pringle, O.A., Grandjean, F., Buschow, K.H.J., Middleton, D.P., 

Yelon, W.B., Pourarian, F., Isnard, O., “A Neutron Diffraction and Mössbauer Study of the Nd 2Fe (17–x)Si (x) 

Solid Solution”, Solid State Commun., 88(10), 761–764 (1993) (Crys. Structure, Experimental, 10) 

[1994Yan] Yan, Q.W., Zhang, P.L., Sun, X.D., Hu, B.P., Wang, Y.Z., Rao, X.L., Liu, G.C., Gou, C., Chen, D.F., 

Cheng, Y.F., “The Magnetic Structure of Nd 6Fe 13Si”, J. Phys., Condens. Matter, 6(16), 3101–3107, (1994) 

(Experimental, Crys. Structure, Magn. Prop., 10) 

[1995Yel] Yelon, W.B, “Neutron Investigations of Novel Magnetic Phases”, IEEE Trans. Magn., 31(6), 3689–3694 


[1995Zha] Zhang, X.D., Shumsky, M.G., James, W.J., “Anomalous Thermal Expansion in Substituted Nd 2Fe 17–xSi x 

and Nd 2Fe 17–xAl x Compounds”, IEEE Trans. Magn., 31(6), 3662–3664 (1995) (Crys. Structure, Experimental, 

10) 

[1995Zhu] Zhuang, Y., Pan, C., Li, J., “Phase Equilibria in the Fe-Rich Alloys of the Ternary System Nd-Fe-Si at 

500˚C”, J. Alloys Compd., 217, 161–163 (1995) (Experimental, Phase Relations, 10) 

[1996Gir] Girt, Er., Altounian, Z., Ming Mao, Swainson, I.P., Donaberger, R.L., “Neutron Diffraction Study of Fe 

Substitutions in Nd 2Fe 17–δX δ (X = Al, Si, Ga, Mo, W)”, J. Magn. Magn. Mater., 163, L251–L256 (1996) 

(Crys. Structure, Experimental, Magn. Prop., 15) 

[1996Lei] Leithe-Jasper, A., Skomski, R., Qi, Q., Coey, J.M.D., Weitzer, F., Rogl, P., “Hydrogen in RE 6Fe 13XH y 

Intermetallic Compounds (RE = Pr, Nd; X = Ag, Au, Si, Ge, Sn, Pb)”, J. Phys.: Condens. Matter, 8(19), 


[1996Sal] Salamakha, P.S., Stepen-Damm, J., Bodak, O., “Isothermal Section of the Nd-Fe-Si System at 870 K”, J. 

Alloys Compd., 242, L1–L2 (1996) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 12) 

[1996Yel] Yelon, W.B., Hu, Z., Chen, M., Luo, H., Ezekwenna, P.C., Marasinghe, G.K., James, W.J., Buschow, K.H.J., 

Middleton, D.P., Pourarian, F., “Neutron Diffraction and Magnetic Studies of Nd 2Fe 17–xT x (T = Si, Mn) 

Alloys”, IEEE Trans. Magn., 32(5), 4431–4433 (1996) (Crys. Structure, Experimental, 10) 

[1997Hua] Huang, M.Q., Wallace, W.E., “Structure and Magnetic Properties of RFe 13-xSi x (R = Pr, Nd or Gd, 

x = 2.5 - 5)”, J. Magn. Magn. Mater., 173, L225–L229 (1997) (Crys. Structure, Experimental, 10) 

[1997She] Shen, B.-G., Liang, B., Cheng, Z.-H., Gong, H.-Y., Zhan, W.-S., Tang, H., de Boer, F.R., Buschow, K.H.J., 

“Magnetic Properties of R 2Fe 14M 3 Compounds with M = Ga and Si; R = Y, Nd, Sm, Gd, Tb, Dy, Ho, Er 

and Tm)”, Solid State Commun., 103, 71–75 (1997) (Crys. Structure, Experimental, 10) 

[1998Gir] Girt, E., Altounian, Z., “Origin of Fe Substitution in Nd 2Fe 17–δX δ”, Phys. Rev. B, Cond. Matter, 57(10), 

5711–5714 (1998) (Calculation, Crys. Structure, Experimental, Thermodyn., 20) 

[1998Gro] Groot de, C.H., Buschow, K.H.J., Boer de, R.F., “Magnetic Properties of R 6Fe 13–xM 1+x Compounds and 

Their Hydrides”, Phys. Rev. B, Condens. Matter, 57(18), 11472–11482 (1998) (Crys. Structure, Experimental, 


[1998Mie] Miettinen, J., “Reassessed Thermodynamic Solution Phase Data for Ternary Fe-Si-C System”, Calphad, 

22(2), 231–256 (1998) (Calculation, Assessment, Thermodyn., 36) 

[1998Wel] Welter, R., Ijjaali, I., Venturini, G., Malaman, B., “X-Ray Single Crystal Refinement on Some CeFeSi 

type RTX Compounds (R = RE Elements; T = Mn, Fe, Co, Ru; X = Si, Ge). Evolution of the Chemical 

Bonds”, J. Alloys Compd., 265, 196–200 (1998) (Crys. Structure, Experimental, 16) 

[1999Art] Artigas, M., Fruchart, D., Gasdeblay, C., Isnard, O., Miraglia, S., “Structural, Magnetic and 

Hydrogenation Properties of R 2Fe 17–xSi x Compounds (R = Rare Earth Element). II. Effects of Hydrogen 

Insertion on the Magnetic Properties (R = Ce, Nd; 0 < x < 0.5”, J. Alloys Compd., 291, 282–288 (1999) 

(Crys. Structure, Experimental, Magn. Prop. 19) 

[2000Gir] Girt, E., Altounian, Z., “Model for Predicting Atomic Substitutions in Intermetallic Compounds”, J. 

Appl. Phys., 87(9), 4747–4749 (2000) (Calculation, Crys. Structure, 19) 

[2000Oka] Okamoto, H., Desk Handbook Binary Phase Diagrams, ASM International, Materials Park, Ohio, 611 

(2000) (Review, Phase Diagram, 1). 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_9 


15

16 9 

Fe–Nd–Si 

[2001Bou] Boulet, P., Weitzer, F., Hiebl, K., NoNl, H., “Structural Chemistry, Magnetism and Electrical Properties 

of Binary Nd Silicides”, J. Alloys Compd., 315(1-2), 75–81 (2001) (Experimental, Crys. Structure, Magn. 

Prop., 15) 

[2002Isn] Isnard, O., Ling, G.J., Hautot, D., Buschow, K.H.J., Grandjean, F., “A Neutron Diffraction and 

Mössbauer Spectral Study of the Magnetic Spin Reorientation in Nd 6Fe 13Si”, J. Phys.: Condens. Matter, 

14(47), 12391–12409 (2002) (Crys. Structure, Experimental, Magn. Prop., 33) 

[2002Taj] Tajabor, N., Alinejad, M.R., Pourarian, F., “Anomalies of Magnetostriction and Thermal Expansion 

in Nd 6Fe 13Si Solid Solution”, Physica B, 321(1-4), 60–62 (2002) (Experimental, Magn. Prop., Phys. 

Prop., 7) 

[2003Sor] Sorescu, M., Valeanu, M., Diamandescu, L., “Effect of Substitution on the Hyperfine Magnetic Field in 

Nd-based Intermetallics”, Intermetallics, 11(8), 749–754 (2003) (Crys. Structure, Experimental, Magn. 

Prop., Morphology, 8) 

[2003Svo] Svoboda, P., Vejpravova, J., Honda, F., Santava, E., Schneeweiss, O., Komatsubara, T., “The Analisis of 

the Specific Heat of RFe 2Si 2 Compounds”, Physica B, 328(1-2), 139–141 (2003) (Crys. Structure, 

Experimental, Thermodyn., 6) 

[2003Vej] Vejpravova, J., Svoboda, P., Sechovsky, V., Janecem, M., Komatsubara, T., “Crystal Growth and Basic 

Thermodynamic Properties of NdFe 2Si 2”, Physica B, 328(3-4), 173–178 (2003) (Experimental, Magn. 

Prop., Phase Relations, Thermodyn., 8) 

[2005Mec] Meco, H., Napolitano, R.E., “Liquidus and Solidus Boundaries in the vinicity of Order-Disorder 

Transitions in the Fe-Si System”, Scr. Mater., 52, 221–226 (2005) (Experimental, Calculation, Phase 


[2006Rog] Roger, J., Babizhetskyy, V., Jardin, R., Halet, J.-F., GuJrin, R., “Solid State Phase Equilibria in the 

Ternary Nd-Si-B System at 1270 K”, J. Alloys Compd., 415(1-2), 73–84 (2006) (Experimental, Crys. 

Structure, 41) 


(1990) 





MSIT 1

Iron – Nickel – Phosphorus 


Kostyantyn Korniyenko 

Introduction 

Phase relations in the Fe-Ni-P system are of great interest, in particular, for the basic study of 

meteoritic minerals, for applications in electronics etc. However, the amount of information 

available about the constitution of this system is insufficient at the present time. The available 

experimental data regarding phase equilibria were published quite long ago [1931Vog, 

1966Buc, 1970Doa, 1975Nor, 1980Rom, 1984Nar2]. The reaction scheme and liquidus surface 

projection of the Fe-Fe 2P-Ni 5P 2-Ni partial system as well as series of partial isothermal and 

vertical sections have been reported. However, data on the liquid-solid equilibria and the 

liquidus surface projection presented in [1931Vog] are in contradiction with later versions of 

the boundary binary Fe-Ni system and therefore, reinvestigation of this aspect of the phase 

diagram using physico-chemical analysis techniques is necessary. Moreover, expansion of the 

known concentration range involving the binary Fe-P and Ni-P phases with higher P contents 

is an important issue. 

Publications relating to experimental studies of phase relations, crystal structures and 

thermodynamics as well as the techniques applied are listed in Table 1. Information on 

thermodynamic properties, in the first instance concerning the activity of phosphorus in 

liquid iron with nickel additions, was obtained experimentally by [1969Sch, 1979Yam, 

1983Yam, 1984Ban]. Reviews of literature data relating to the phase equilibria of the 

Fe-Ni-P system are presented in [1949Jae, 1988Rag], crystal structures - in [1988Rag], 

thermodynamics - in [1979Yam, 1984Ban]. A thermodynamic description of the Fe-Ni-P 

system was derived by [1990Gus]. 


The Fe-P and Fe-Ni binary boundary systems are accepted from [2002Per] and [2008Kuz], 

respectively. The Ni-P boundary system is accepted from [Mas2]. 


Fe–Ni–P 10 

1 

Crystallographic data relating to the known unary and binary Fe-Ni-P phases and their 

concentration as well as temperature ranges of stability are presented in Table 2. The (γFe) 

and (Ni) phases form a continuous series of solid solutions in the binary Fe-Ni system, with 

little solubility of phosphorus in the Fe-Ni alloys [1965Kan2]. The P solubility in the (Fe,Ni) 

alloys increases with the Ni content of the alloy, which agrees with the quite high solubility of P 

in pure Ni. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_10 

ß Springer 2009

2 10 

Fe–Ni–P 

Two continuous series of solid solutions are reported to form between isostructural binary 

phases existing over the whole composition range and wide temperature ranges; namely the 

M 3P phase (Ni 3P type structure) and the M 2P phase (Fe 2P type) [1988Rag]. High solubilities 

of nickel in the FeP-based phase [1986Fje] as well as of iron in the NiP 3-based phase [2000Jei] 

exist. The crystal structures of the M 3P solid solutions, having the mineralogical names 

schreibersite and rhabdite, which have been extracted from Canyon Diablo, Morasko as well 

as Orange River meteorites, are reported in [2003Mor1, 2003Mor2, 2003Mor3], respectively. 

No ternary phase has been found in the system. 


It was concluded by [1931Vog] that the Fe 2P-Ni 5P 2 section is a quasibinary, probably of the 

simple eutectic type with eutectic temperature of about 990˚C. Position of the eutectic point e6 

is presented in Table 3. Solubilities of third component in the Fe2P- and Ni5P2-based phases 

were not established. 


Temperatures, types of reactions and compositions of the phases taking part in the invariant 

equilibria (that are available) for the partial Fe-Fe2P-Ni5P2-Ni system are listed in Table 3. A 

partial reaction scheme (Fig. 1) is compiled on the basis of data from [1931Vog] and 

[1970Doa] concerning the constitution of the liquidus surface, the character of the invariant 

equilibria in the partial Fe-Fe 2P-Ni 5P 2-Ni system and the constitution of the accepted boundary 

binary systems. It is essentially the same as that proposed in the assessment of [1988Rag]. 

The compositions of the phases taking part in the transition reaction L + αδ Ð γ +M 3P and 

the corresponding invariant temperature are taken from [1970Doa]. The remaining invariant 

equilibria are based on [1931Vog]. A maximum point (max), Table 3, corresponds to the 

change in character of the univariant process involving the liquid, M3P and Ni5P2 phases. 

Its composition is ~18.7Fe56.3Ni25P (at.%). 


The liquidus surface projection of the partial Fe-Fe 2P-Ni 5P 2-Ni system was constructed by 

[1931Vog] on the basis of experimental data obtained by using thermal analysis and metallographic 

techniques. The proposed diagram was reproduced in the review of [1949Jae]. But 

later, because of revision of the Fe-Ni boundary system, the necessity for a reinvestigation of 

the liquidus surface projection has arisen. Figure 2 presents the liquidus surface projection of 

the partial Fe-Fe 2P-Ni 5P 2-Ni system based mainly on the critical review of [1988Rag]. The 

positions of the invariant points E, e 6 and max given by [1931Vog] are preserved but the U 

point is placed in accordance with [1970Doa]. Univariant curves are drawn as dashed lines but 

their accurate location needs to be determined. The author of [1990Gus] proposed a calculated 

liquidus surface projection of the Fe-Fe 2P-Ni 5P 2-Ni partial system. This must be considered 

as speculative as no attempt was made to fit the experimental data of [1931Vog]. 



MSIT 1

The positions of the apexes of the invariant three-phase plane α-γ-M 3P existing on the 

solidus surface of the ternary system at 1000 ± 5˚C are listed in Table 3, taken from the work of 

[1970Doa]. Below 995˚C, the three-phase fields are L + γ +M 3P and L + γ + αδ; above 1005˚C, 

the three-phase fields are L + αδ + γ and L + αδ +M 3P. 



3 

A series of isothermal sections of the ternary Fe-Ni-P system were proposed on the basis of 

experimental data [1966Buc, 1970Doa, 1975Nor, 1980Rom, 1984Nar2] and calculated results 

[1990Gus]. 

Isothermal sections at the temperature of 1100˚C in the range of phosphorus content of up 

to about 20 at.% P were proposed independently by [1966Buc] and [1970Doa], but the latter 

work is preferable because the materials used in the investigation were of higher purity and the 

annealing times were longer than in the former work. This section is shown in Fig. 3 on the 

basis of [1970Doa], with amendments according to the constitution of the accepted binary 

systems. So, the L/(L + αδ) boundary from the side of the Fe-P binary is shifted in the direction 

of nickel corner. The isothermal section at 1100˚C for the same composition range calculated 

by [1990Gus] shows good agreement with the experimental data of [1966Buc, 1970Doa], 

except for the liquid phase composition (apex of the L-αδ-γ triangle corresponding to the 

composition of liquid is proposed to be at about Fe 75.6Ni 10.8P 13.6 (in at.%)). 

Partial isothermal sections at 1060 and 1010˚C constructed by [1970Doa] are shown in 

Figs. 4 and 5, respectively; with amendments according to the accepted Fe-P binary system 

(the L + αδ field in Fig. 4 is now narrower). One can see that above the Fe-P eutectic 

temperature, 1048˚C, the L + αδ field is separated from the L + γ field by a three-phase region 

(L + αδ + γ). Below 1048˚C, the αδ +M 3P field forms while the L + αδ field is still stable. 

[1970Doa] noted that these two-phase regions must be separated by a three-phase field (L + αδ 

+M 3P) but, their specimens didn’t contain these phases and therefore the (L + αδ +M 3P) field 

is estimated in Fig. 5. 

A partial isothermal section for 1000˚C was reported by [1966Buc] and later by [1970Doa]. 

Actually, the temperature of 1000 ± 5˚C is that of the invariant L + αδ Ð γ +M3P whose phase 

compositions are given in Table 3. The partial isothermal section at this temperature calculated 

by [1990Gus] shows good agreement with experimental data of [1966Buc] and [1970Doa], 

except for the liquid phase composition (given as about Fe 74.1Ni 10.7P 15.2 in at.%). 

In comparison with the section at 1000˚C, the partial isothermal section at 995˚C 

[1970Doa] shows two three-phase fields separated by a newly formed γ +M 3P region. No 

alloys with composition lying inside this three-phase field (L + γ +M 3P) were studied, and so 

the boundaries which enclose this region were defined by tie lines obtained within the L + M 3P 

and L + γ fields. An isothermal section for 975˚C in the range of phosphorus content of up to 

25 at.% and nickel content of up to about 15 at.% was constructed by [1975Nor] during a 

study of the ternary dissolution kinetics in the Fe-Ni-P system using diffusion couples. The 

section contains the three-phase field (M 3P+αδ + γ). The partial isothermal section for 970˚C 

proposed by [1966Buc] was presented as corresponding to the temperature of the four-phase 

invariant equilibrium L + αδ Ð γ +M 3P, but this was later corrected by [1970Doa]. Therefore, 

the section at 950˚C constructed by [1966Buc] should also be corrected. 

A partial isothermal section for 875˚C was reported by [1966Buc, 1970Doa] (the results of 

the latter work are presented in Fig. 6). An isothermal section for this temperature was also 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_10 

ß Springer 2009

4 10 

Fe–Ni–P 

calculated by [1990Gus]; quite good agreement with the experimental data of [1966Buc] and 

[1970Doa] is observed. All the reported isothermal sections in the Fe rich corner 

corresponding to this and lower temperatures are analogous with regard to the phase regions 

(three-phase field (M 3P+αδ + γ) and the adjacent fields corresponding to the (αδ + γ +M 3P) 

phases as well as two-phase regions αδ +M 3P, M 3P+γ and αδ + γ). This type of section 

contains the partial isothermal sections at 750, 650, 550, 450, 350˚C constructed by [1966Buc], 

partial isothermal sections at 750, 650, 550˚C [1970Doa], at 600 and 400˚C [1988Rag], partial 

isothermal sections at 700, 600, 500, 400 and 300˚C [1980Rom] as well as calculated 

partial isothermal sections at 750 and 650˚C [1990Gus]. Also, on the basis of the investigation 

of the growth of intergranular ferrite in Fe-Ni-P alloys, [1984Nar2] presented partial isothermal 

sections at phosphorus contents of up to about 2 at.% at 800, 720 and 700˚C. 


A series of schematic temperature-composition sections were proposed by [1931Vog] witha 

view to illustrate the conditions of crystallization in the ternary system. These sections, like the 

liquidus surface projection, need further verification using modern methods of physicochemical 

analysis. 


The effect of nickel on the activity coefficient of phosphorus in liquid iron alloys at different 

temperatures was studied by [1969Sch, 1979Yam, 1983Yam, 1984Ban]. It was reported by 

[1969Sch], that the addition of nickel up to 32 at.% to liquid Fe-P alloys at 1550˚C does not 

influence the activity of phosphorus, and therefore the interaction parameter ε P (Ni) = ∂ ln aNi / 

∂ ln x P) ~ 0. [1979Yam, 1983Yam] used a mass spectrometer equipped with a newly developed 

ion current measuring system combined with a Knudsen cell. For measurements carried out at 

1600˚C, a value of 0.7 ± 0.7 was obtained for the interaction parameter εP (Ni) . Later, the vapor 

pressure of phosphorus in liquid Fe-Ni-P alloys containing up to 28.3 mass% Ni was measured 

by [1984Ban] using the transportation method at 1400˚C. By applying the interstitial solution 

model of Chipman to the results, the effect of nickel on the activity coefficient of phosphorus 

in liquid iron was determined by assuming the nickel dissolves substitutionally. A value of 

ε P (Ni) = – 1.48 ± 0.88 at 1400˚C was reported. 

A thermodynamic description of the Fe-Ni-P system was derived by [1990Gus], and a 

partial liquidus surface projection and partial isothermal sections at 1100, 1000, 875, 750 and 

650˚C were calculated. According to [1998Mie], the value of the ternary parameter LFeNiP in 

the γ phase did not give good agreement between calculated and published experimental 

results, and hence, the value of this parameter needs to be re-optimized. A non-metal 

interaction model for the segregation of trace metals during solidification of the Fe-Ni-P 

alloys was proposed by [1990Jon]. A method for parameterizing solid metal - liquid metal 

partition coefficients for siderophile (iron-loving) elements as a function of the metallic liquid 

composition based on the theory of [1990Jon] was proposed in [2003Cha]. The interaction 

parameter in liquid iron at 1600˚C was evaluated by [1993Din] asε P (Ni) = 1.81. By consideration 

of the effect of various concentrations (up to 0.9 mass%) of added phosphorus on grain 

growth in Fe-50 mass% Ni for sintering temperatures ranging from 950 to 1250˚C [2002Chu], 



MSIT 1

three different grain growth mechanisms having different ratios of activation energy to grain 

growth exponent were identified. The ratios of activation energy to grain growth exponent for 

these three domains were 50, 202 and 72 kJ·mol –1 , respectively. It was reported by [2006Gao] 

that during the heating of an electrodeposited amorphous Fe 8Ni 69P 23 (at.%) alloy, six exothermic 

reactions take place continuously. Their temperatures are 248, 303, 322, 350, 376 and 

442˚C; the activation energies of the exothermic reactions were proposed. The amorphous 

Fe22Ni60P18 alloy crystallizes when heating beyond 250˚C. 



5 

The Fe-Ni-P and related alloys (complicated nickel-containing steels and ferronickel alloys) 

are of great interest for practical applications in modern technology. In addition to studies of 

Fe-Ni-P alloys as the basic component of meteoritic minerals, it was recently established by 

[2000Jei] that the NiP3-based phase with the addition of iron (Fe0.5Ni0.5P3) has the skutterudite 

type structure that exhibits useful electric and magnetic behavior. Information about 

phase relations in the Fe-Ni-P system is important also for clarification of the effect of the nonmetallic 

element phosphorus on the properties of the well-known industrial alloy, invar 

(Fe 64Ni 36 in mass% or Fe 65.1Ni 34.9 in at.%), which possesses a low thermal expansion coefficient 

and is used as the shadow mask in cathode ray tubes for color TV and as the structural 

material for liquid nitrogen gas tanks used in industry [1987Ina]. 

The experimental techniques applied and types of properties investigated are listed in 

Table 4. 

The variation of hardness during tempering was studied by [1966Buc] for different alloys 

containing up to 40 mass% Ni and 0.4 mass% P. It was noted that a considerable increase in 

hardness was experienced when phosphides precipitated from the austenite (γFe), but the 

hardness was seen to decrease considerably when the phosphides precipitated from the α/α 2 

phase. After heat treating a Fe-25Ni-0.4P (mass%) alloy (Fe 75.3Ni 24.0P 0.7) for extensive periods 

at 350˚C, a hardness peak developed, which has been tentatively ascribed to the order 

hardening reaction giving Fe 3Ni. It was reported by [1987Ina], that additions of P influence 

the thermal expansion coefficient of the invar alloy (Fe-36Ni (mass%)) in the following 

way: the thermal expansion coefficient α = (1/V)(∂V/∂T)P of the as-rolled specimen decreased 

slightly with an increase in phosphorus content up to 0.05 mass% P, which generates dislocations 

and vacancies. Above 0.05 mass% P, however, α increases monotonically. Both 0.2 % 

yield strength (σ 0.2) and tensile strength (σ B) increase rapidly with P additions of up to 0.05 

mass% P in the as-rolled specimens, whereas for the sample annealed at 780˚C, both σ 0.2 and 

σ B decrease with P contents up to 0.05 mass%. When the quantity of P added to the annealed 

specimen exceeds 0.05 mass%, however, both σ 0.2 and σ B increase monotonically. Experiments 

with high purity Fe-based alloys containing 0.21 or 0.22 mass% P and up to 0.95 mass% Ni 

have been performed by [1988Sai] in order to clarify the mechanism of reduction of the 

intergranular fracture (IGF) of Fe-P alloys owing to the presence of nickel. Among the factors 

affecting IGF and the ductile-to-brittle transition temperature (DBTT), the degree of phosphorus 

segregation and the grain size are independent of the bulk nickel concentration. Two 

other factors are the plasticity of the matrix and the interaction between nickel and phosphorus. 

It was shown that the solution-softening effect of Ni is the mechanism reducing the 

susceptibility of the Fe-P alloys to IGF. [1997Gao] reported that the thermostability of 

electrodeposited amorphous Fe-Ni-P alloys increased with increasing Fe content. According 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_10 

ß Springer 2009

6 10 

Fe–Ni–P 

to the data of [2001Wan], the microhardness of ternary Fe-Ni-P electroless alloy deposits 

increased when the heat treatment temperature was 400˚C or below, and was shown to be 

related to the precipitation of Ni 3P- and Fe 3P-based phases within the Fe-Ni solid solution 

matrix. 

Investigations of the magnetic properties of (Fe 1–xNi x) 2P solid solutions were carried out 

by [1969Fru, 1969Rog], revealing evidence that the substitution of nickel by iron produces a 

similar sharp increase in Curie temperature, which reaches a maximum of 342 K at x ≈ 0.08, 

decreasing rapidly with larger x up to 100 K at x = 0.5. The saturation magnetization was not 

measured. Later, magnetoelastic properties and the electronic structure of (Fe 1–xNi x) 2P solid 

solutions were studied by [2004Zac]. The values of local magnetic moments as derived from 

neutron diffraction refinements and the total saturation magnetization were found to be in 

fair agreement with total energy coherent potential approximation (KKR-CPA) calculations. It 

was suggested that strong electron polarization at the Fermi level (P ~ 90 %) as established 

theoretically for the (Fe1-xNix)2P compounds having the smallest nickel content, may be 

responsible for the marked magnetoelastic phase transition, as observed, for example, in 

(Fe 0.975Ni 0.025) 2P. 

Miscellaneous 

Ternary diffusion coefficients in the (αFe) and (γFe) phases at 1200, 1100, 1000 and 900˚C 

were determined by [1973Hey]. Cooling rates for twelve group IVA iron meteorites have 

been determined by [1979Mor] using a new ternary Fe-Ni-P system model that simulates the 

growth of the Widmanstaetten structure. It was proposed that the group IVA irons were 

accommodated at various depths in an asteroid-sized body. The diffusion of nickel in 

amorphous and crystalline Fe 65.5Ni 17P 17.5 and Fe 48.5Ni 34P 17.5 (units were not specified) alloys 

has been studied by [1983Gru] using the radioisotope absorption-kinetic method. The 

structural state is found to have an appreciable effect on diffusion in the amorphous alloy. 

Annealing at temperatures above the crystallization point of the amorphous alloy, results in 

the Ni diffusion slowing down. On the basis of the results obtained, it was supposed that the 

diffusibility of metalloid atoms is much slower and that of metal atoms is more rapid in 

amorphous alloys than in ordinary alloys. The diffusivity of Ni in Fe-Ni-P martensite was 

determined by [1981Rom] in the temperature range 700 to 300˚C using EMPA and STEM 

techniques. The lattice and grain boundary tracer diffusion coefficients in the Fe 98.87Ni 1.03P 0.1 

(at.%) alloy were measured by [1983Mat] in the temperature range from 659 to 882˚C. It was 

concluded that the effect of nickel on the lattice and grain boundary tracer diffusion coefficients, 

as compared to binary Fe-P alloys, is small. The equilibrium “intergranular segregation 

extent (ISE)” of phosphorus in Fe-Ni-P alloys was calculated in [1983Shi] using a model 

analogous to Ono’s discrete lattice approach based on a simple regular solution model 

assuming only nearest neighbor interactions. The ISE of phosphorus was defined as the 

monolayer thickness of a P-enriched bulk region adjacent to the grain boundary, where a 

normalized concentration of P is greater than one-tenth of that of the grain boundary. The 

nucleation of intergranular ferrite from austenite in Fe-Ni-P alloys containing 5 to 10 mass% 

Ni and up to 1 mass% P was studied by [1984Nar1] with a view to understand the development 

of the Widmanstaetten structure in iron meteorites. A series of alloy compositions were 

chosen to simulate the constitution of iron meteorites. In the investigated alloys, intergranular 

ferrite precipitates were found to have a rod-like morphology, intergranular ferrite and the 



MSIT 1

parent austenite have an orientation relationship close to that given by Kurdjumov-Sachs and 

phosphides act as nucleation sites for intergranular ferrite precipitation. At the same time, 

ferrite doesn’t precipitate in the absence of P. The authors of this work also used analytical 

electron microscopy (AEM) techniques to study the growth of intergranular ferrite in their 

specimens; the results were presented in [1984Nar2]. It was shown that the growth kinetics are 

dictated by the bulk diffusion of nickel in austenite; full equilibrium takes place during 

intergranular ferrite growth with full partitioning of Ni and P between austenite and ferrite, 

and chemical equilibrium occurs at the (αFe)/(γFe) interface in both phases. A numerical 

model to simulate ferrite growth was developed based on equilibrium growth considerations. 

The Ni concentrations and precipitate sizes predicted by the model agree well with those 

measured by AEM techniques in the experimental alloys. The computer model has been 

extended to predict the thermal histories of iron meteorites and their parent asteroidal bodies. 

In [1986Dea], the AEM technique was used to measure the interdiffusion coefficients in the 

Fe-Ni-P system (0.2 mass% P, up to 30 mass% Ni) between 925 and 610˚C in austenite and 

between 850 and 550˚C in ferrite. The results obtained were compared with the data obtained 

using binary Fe-Ni specimens. The possibilities of using atom probe tomography characterization 

of solute segregation to dislocations and interfaces were reported in [2006Mil]. A 

neutron irradiated Fe 98.375Ni 1.6P 0.025 (at.%) alloy and a neutron irradiated beltline weld 

from the Midland reactor were the subject of the investigation. It was concluded that this 

technique is best applied to materials with high dislocation densities due to the relatively 

limited volume of analysis. The level of solute segregation at the interfaces of nanometer scale 

precipitates may also be estimated using this technique. 

. Table 1 

Investigations of the Fe-Ni-P Phase Relations, Structures and Thermodynamics 


[1931Vog] Melting in Pythagor’s crucibles, thermal 

analysis, optical microscopy, chemical 

analysis 


Range Studied 

< 1500˚C, the Fe-Fe2P-Ni5P2-Ni region 

[1948Now] XRD (X-ray diffraction) The Fe3P-Ni3P and Fe2P-Ni2P sections 

[1965Kan1] Electrolytical isolation, XRD, chemical 

analysis 

2.5 mass% P in the alloys 

[1965Kan2] XRD, chemical analysis 1000, 900, 800˚C, 1 at.% Ni or 10 to 14 

mass% Ni 

[1966Buc] Sintering in hydrogen, XRD, Electron 

Microprobe Analysis (EMPA) 

≤ 1100˚C, ≤ 40 mass% Ni, ≤ 10 mass% P 

[1968Doe] XRD Fe2NiP [1969Fru] XRD (Seeman-Bohlin camera), Mössbauer 

spectroscopy 

The Fe2P-Ni2P section 

[1969Rog] XRD (Seeman-Bohlin camera), Mössbauer 

spectroscopy 



MSIT 1 


The Fe 2P-Ni 2P section 

7 

DOI: 10.1007/978-3-540-70890-2_10 

ß Springer 2009

8 10 

Fe–Ni–P 




Range Studied 

[1969Sch] Equilibrium P (vapor) – molten Fe with Ni 

additions 

1550˚C 

[1970Doa] EMPA, XRD, quantitative metallography 1100-550˚C, ≤ 16.5 mass% P, induction 

melting, heat treatment, quenching, 

[1970Doe] XRD Fe2NiP [1970Spr] Heat treatment, XRD 25 at.% P 

[1973Mae] XRD on powder, Mössbauer 

spectroscopy 

900˚C, the Fe2P-Ni2P section 

[1975Nor] Optical microscopy, EMPA, diffusion 

couples technique 

975-750˚C, the Fe3P-Ni3P section 

[1977Got] XRD The Fe3P-Ni3P section 

[1979Yam] Melting, Knudsen cell-mass spectrometry εP Ni in liquid phase, 1600˚C, 

≤ 10 mass% Ni 

[1980Rom] Induction melting, annealing, EMPA, STEM 700-300˚C, < 60 mass% Ni 

[1981Maa] XRD, Mössbauer spectroscopy FeNiP 

[1982Sas] XRD, EMPA, sealed-tube method 700˚C, phosphorus vapor at 0.1 MPa 

[1983Yam] Melting, Knudsen cell-mass spectrometry 1600˚C 

[1984Ban] Transportation method 

Ni 

εP in liquid phase, 1400˚C, ≤ 28.3 

mass% Ni 

[1984Nar2] Analytical electron microscopy (AEM), 

isothermal and nonisothermal heat 

treatments 

≤ 9.72 mass% Ni, ≤ 0.75 mass% P 

[1986Fje] XRD on powder, neutron diffraction 50 at.% P, 0 to 15 at.% Ni 

[1986Reu] Physico-chemical analysis techniques < 400˚C, < 58 mass% Ni 

[2000Jei] XRD on single crystal, energy-dispersive Xray 

analysis (EDX) 

FexNi1–xP3 (x = 0, 0.455, 0.555) 

[2000Wan] Electroless plating 38 at.% Fe 

[2001Wan] Electroless plating, X-ray diffraction 700-200˚C 

[2003Mor1] EMPA (Cameca SX 100), XRD (single crystals Fe1.7Ni1.3P (a Schreibersite extracted 

technique) 

from Canyon Diablo meteorite) 


technique) 

from Morasko meteorite) 


technique) 

from Orange River meteorite) 



MSIT 1



[2004Zac] Heat treatment, XRD, Rietveld profile 

refinement 

[2005Gei] TEM, TEM-EDX, X-ray diffraction, 

electron backscatter diffraction (EBSD) 


Range Studied 

420-80 K, (Fe 1–xNi x) 2P(x = 0.015, 0.02, 

0.025, 0.25) 

The Fe 3P-Ni 3P section 

[2006Gao] DTA, DSC, X-ray diffraction ≲ 25 at.% P 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 


Lattice 

Parameters 


9 

αδ, (αFe, δFe) cI2 dissolves 4.55 at.% P at 1048˚C, and 4 at.% 

Im3m 

P at 1000˚C [2002Per], dissolves 4.5 at.% P 

W 

at 1 at.% Ni, 1000˚C [1965Kan2] 

(δFe) (h) a = 293.15 pure Fe, at 1360˚C [V-C2] 

1538 - 1394 dissolves 3.8 at.% Ni at 1517˚C [2008Kuz] 

(αFe) (r) (ferrite) a = 286.64 pure Fe, at 20˚C [V-C2] 

< 912 dissolves 4.6 at.% Ni at 495˚C [2008Kuz] 

γ, (γFe,Ni), cF4 

(γFe) (austenite) Fm3m a = 364.68 pure Fe, 912˚C [Mas2] 

1394 – 912 Cu dissolves 0.56 at.% P at 1150˚C [2002Per] 

dissolves 1 mass% P at 10 to 14 mass% Ni, 

1000˚C [1965Kan2] 

dissolves 0.3 mass% P at 10 to 14 mass% 

Ni, 800˚C [1965Kan2] 

(Ni) a = 352.40 pure Ni, 25˚C [V-C2] 

< 1455 dissolves 0.32 at.% P at 870˚C [Mas2] 

FeNi3 cP4 

Pm3m 

AuCu3 a = 355.50 ordered γ(Fe,Ni) [1988Rag] 

α2, martensite tI4 - metastable, from quenched austenite 

I4/mmm 

α2, martensite 

[Mas2] 

γ´, FeNi3 cP4 a = 355.25 63 to 85 at.% Ni 

< 517 Pm3m 

AuCu3 [1991Swa, 2008Kuz] 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_10 

ß Springer 2009

10 10 

Fe–Ni–P 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 

Lattice 

Parameters 


FeP oP8 a = 519.3 [2002Per] 

≲ 1370 Pna21 b = 579.3 

MnP c = 309.9 

Fe1–xNixP a = 519 to 510.5 x = 0 to 0.3, room temperature, slowly 

b = 579.5 to 569.7 cooled samples [1986Fje] 

c = 309.5 to 325.3 

a = 510.5 to 517 

b = 569.7 to 578.2 

c = 325.2 to 327 

x = 0.3, T = 25 to 800˚C [1986Fje] 

FeP2 oP6 a = 497.29 66 to 67 at.% P [2002Per] 

Pnnm b = 565.68 


c = 272.30 

FeP4 mP30 a = 461.9 80 at.% P [2002Per] 

P21/c b = 1367.0 

FeP4 c = 700.2 

β = 101.48˚ 

βNi5P2 (h) 

1170 - 1000 

- - 28.6 at.% P [Mas2] 

αNi5P2 (r) hP168 a = 1322.0 ± 0.2 28.6 at.% P. Annealed at 700˚C 

< 1025 P3 

αNi5P2 c = 2463.2 ± 0.2 [1988Rag] 

βNi12P5 (h) 

1125 - 1000 

- - 29.4 at.% P [Mas2] 

αNi12P5 (r) tI34 a = 864.6 29.4 at.% P [1988Rag] 

< 1025 I4/m 

αNi12P5 c = 507.0 

M3P, (Fe1–xNix)3P tI32 0 ≤ x ≤ 1[1931Vog, 1948Now] 

I4 a = 910.8 x =0[2002Per] 

Ni 3P c = 445.5 

Fe 3P a = 904.0 x = 0.33 [1968Doe, 1970Doe] 

< 1166 c = 446.2 

Ni 3P a = 895.4 x =1[1988Rag] 

< 970 c = 438.6 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 

Lattice 

Parameters 


M2P, (Fe1–xNix) 2P hP9 0 ≤ x ≤ 1 

Fe2P P62m a = 586.6 ± 0.2 x =0[1969Fru, 1969Rog] 

< 1370 Fe2P c = 345.3 ± 0.3 

a = 584.07 

c = 344.4 

x = 0.25, T =10K[2004Zac] 

a = 584.46 

c = 345.75 

x = 0.25, T = 17˚C [2004Zac] 

Ni2P a = 586.4 ± 0.4 x =1[1969Fru, 1969Rog] 

< 1100 c = 338.6 ± 0.4 

Ni5P4 hP36 a = 678.9 44.4 at.% P [Mas2, V-C2] 

P63mc Ni5P4 c = 1098.6 single crystal data, annealed at 800˚C 

Ni1.22P - - 45 at.% P [Mas2, 1988Rag] 

NiP oP16 a = 605.0 50 at.% P [Mas2, V-C2] 

≲ 850 Pcba c = 488.1 single crystal data, annealed at 850˚C 

NiP c=689.0 

NiP2 mC12 a = 636.6 66.7 at.% P [Mas2, V-C2] 

C2/c c = 561.5 single crystal data, annealed at 900˚C and 

NiP2 c=607.2 

β = 126.22˚ 

slowly cooled 

NiP3 cI32 a = 780.8 75 at.% P [Mas2] 

Im3 single crystal data [2000Jei] 

FexNi1–xP3 CoAs3 a = 775.2 ± 0.2 x = 0.495 [2000Jei] 

. Table 3 




Fe 


Ni P 

L+αδ Ð γ +M3P 1000 ± 5˚C U L 69.4 10.0 20.6 

αδ 88.2 7.0 4.8 

γ 88.2 9.3 2.5 

M3P 66.9 6.7 26.4 



MSIT 1 

11 

DOI: 10.1007/978-3-540-70890-2_10 

ß Springer 2009

12 10 

Fe–Ni–P 



Fe 


Ni P 

L Ð M2P+Ni5P2 ~ 990 e6 L ~ 22.7 ~ 47.0 ~ 30.3 

L+M3P+Ni5P2 ~ 980 max L ~ 18.7 ~ 56.3 ~ 25.0 

L Ð M2P+Ni5P2 +M3P ~ 970 E L ~ 23.5 ~ 49.0 ~ 27.5 

. Table 4 

Investigations of the Fe-Ni-P Materials Properties 


[1966Buc] Vickers hardness tests Hardness 

[1969Fru] Thermomagnetic balance technique Magnetic moments, Curie 

temperatures, magnetic-transition 

temperatures 

[1969Rog] Thermomagnetic balance technique Magnetic moments, Curie 

temperatures, magnetic-transition 

temperatures 

[1977Got] Thermomagnetic balance, sample vibrating 

magnetometer techniques 

Magnetic transition point, saturation 

magnetic moment 

[1983Mat] Residual activity method Curie temperature 

[1986Fje] Differential scanning calorimetry (Mettler TA 

3000 system), conventional Faraday balance 

Magnetic susceptibility 

[1987Ina] Normal method (for thermal expansion), 

tensile tests 

[1988Sai] Charpy-type impact tests, tensile tests, optical 

microscopy, TEM 

57 

[1990Res] Fe Mössbauer spectroscopy, magnetic 

measurements 

[1997Gao] Differential scanning calorimetry, positron 

annihilation, electronic integrating instrument 

techniques 

Tensile stress, yield strength, thermal 

expansion coefficient 

Toughness, yield stress, grain size, 

dislocation configuration 

Hyperfine field distributions, 

magnetic phase diagram 

Magnetic properties, structure 

defects, thermostability 

[2000Wan] Corrosion resistance tests Corrosion resistance 

[2001Wan] Mechanical tests Microhardness 

[2004Zac] Neutron diffraction, magnetic susceptibility χac susceptibility, ferromagnetic- 

measurements at high pressure (up to 1.5 

GPa) 

paramagnetic phase transition 

[2006Gao] Improved four-ball wear tester Wear resistance 



MSIT 1

. Fig. 1 

Fe-Ni-P. Partial Reaction scheme 



MSIT 1 


13 

DOI: 10.1007/978-3-540-70890-2_10 

ß Springer 2009

14 10 

Fe–Ni–P 

. Fig. 2 

Fe-Ni-P. Partial liquidus surface projection 



MSIT 1

. Fig. 3 

Fe-Ni-P. Partial isothermal section at 1100˚C 



MSIT 1 


15 

DOI: 10.1007/978-3-540-70890-2_10 

ß Springer 2009

16 10 

Fe–Ni–P 

. Fig. 4 




MSIT 1

. Fig. 5 




MSIT 1 


17 

DOI: 10.1007/978-3-540-70890-2_10 

ß Springer 2009

18 10 

Fe–Ni–P 

. Fig. 6 




MSIT 1

References 


19 

[1931Vog] Vogel, R., Baur, H., “About the Iron-Nickel-Phosphorus Ternary System” (in German), Arch. 

Eisenhuettenwes., 5(5), 269–278 (1931/1932) (Morphology, Phase Diagram, Phase Relations, Experimental, 

10) 

[1948Now] Nowotny, H., Henglein, E., “Study of Ternary Alloys with Phosphorus” (in German), Monatsh. Chem., 

79, 385–393 (1948) (Crys. Structure, Experimental, Review, 18) 

[1949Jae] Jaenecke, E., “Ni-Fe-P” (in German) in “Kurzgefasstes Handbuch aller Legierungen”, Winter Verlag, 

Heidelberg, 648–649 (1949) (Phase Diagram, Phase Relations, Review, 1) 

[1965Kan1] Kaneko, H., Nishizawa, T., Tamaki, K., “Phosphide-Phases in Ternary Alloys of Iron, Phosphorous and 

Other Elements” (in Japanese), Nippon Kinzoku Gakkai-shi, 29(2), 159–165 (1965) (Morphology, Phase 

Diagram, Phase Relations, Experimental, Review, 24) 

[1965Kan2] Kaneko, H., Nishizawa, T., Tamaki, K., Tanifuji, A., “Solubility of Phosphorus in α- and γ-Iron” 

(in Japanese), Nippon Kinzoku Gakkai-shi, 29(2), 166–170 (1965) (Phase Relations, Experimental, 

Review, 20) 

[1966Buc] Buchwald, V.F., “The Fe-Ni-P System and the Structure of Iron Meteorites”, Acta Polytech. Scand., (51), 

1–46 (1966) (Crys. Structure, Morphology, Phase Diagram, Experimental, Mechan. Prop., 34) 

[1968Doe] Doenitz, F.D., “Crystal Structure of the Meteorite Mineral Rhabdite” (in German), Naturwissenschaften, 

55(8), 387–387 (1968) (Crys. Structure, Experimental, 4) 

[1969Fru] Fruchart, R., Roger, A., Senateur, J.P., “Crystallographic and Magnetic Properties of Solid Solutions of 

the Phosphides M 2P, M = Cr, Mn, Fe, Co, and Ni”, J. Appl. Phys., 40(3), 1250–1257 (1969) (Crys. 

Structure, Experimental, Magn. Prop., 45) 

[1969Rog] Roger, A., Senateur, J.-P., Fruchart, R., “Crystallographic and Magnetic Properties of Solid Solutions 

Among the Phosphides Ni 2P-Co 2P-Fe 2P-Mn 2P and Cr 2P” (in French), Ann. Chim. (Paris), 4(2), 

79–91 (1969) (Crys. Structure, Experimental, Phase Relations, Magn. Prop., 44) 

[1969Sch] Schenck, H., Steinmetz, E., Gitizad, H., “Activity of Phosphorus in the Molten Iron and its Control by 

Nickel, Manganese and Chromium” (in German), Arch. Eisenhuettenwes., 40(8), 597–602 (1969) 

(Thermodyn., Experimental, 24) 

[1970Doa] Doan, A.S., Jr., Goldstein, J.I., “The Ternary Phase Diagram Fe-Ni-P”, Metall. Trans., 1(6), 1759–1767 

(1970) (Morphology, Phase Diagram, Phase Relations, Experimental, #, 19) 

[1970Doe] Doenitz, F.-D., “The Crystal Structure of Meteoritic Rhabdite (Fe, Ni) 3P” (in German), Z. Kristallogr., 

131(3), 222–236 (1970) (Crys. Structure, Experimental, 17) 

[1970Spr] Spriggs, P.H., “An Investigation of the Variation of Lattice Parameters with Composition along the Tieline 

Ni 3P-Fe 3P”, Phil. Mag., 21, 897–901 (1970) (Crys. Structure, Experimental, 8) 

[1973Hey] Heyward, T.R., Goldstein, J.I., “Ternary Diffusion in the α and γ Phases of the Fe-Ni-P System”, Metall. 

Trans., 4(10), 2335–2342 (1973) (Morphology, Experimental, Interface Phenomena, Kinetics, 17) 

[1973Mae] Maeda, Y., Takashima, Y., “Mössbauer Studies of FeNiP and Related Compounds”, J. Inorg. Nucl. 

Chem., 35(6), 1963–1969 (1973) (Crys. Structure, Experimental, Electronic Structure, 12) 

[1975Nor] Norkiewicz, A.S., Goldstein, J.I., “Ternary Dissolution Kinetics in the Fe-Ni-P System”, Metall. Trans. 

A, 6A, 891–900 (1975) (Morphology, Phase Diagram, Phase Relations, Experimental, Interface Phenomena, 

Kinetics, 17) 

[1977Got] Goto, M., Tange, H., Tokunaga, T., Fujii, H., Okamoto, T., “Magnetic Properties of the (Fe 1–xM x) 3P 

Compounds”, Jpn. J. Appl. Phys., 16(12), 2175–2179 (1977) (Crys. Structure, Experimental, Magn. 

Prop., 16) 

[1979Mor] Moren, A.E., Goldstein, J.I., “Cooling Rates of Group IVA Iron Meteorites Determined from a Ternary 

Fe-Ni-P Model”, Earth Planet. Sci. Letters, 43(2), 182–196 (1979) (Morphology, Calculation, Theory) 

cited from abstract 

[1979Yam] Yamada, K., Kato, E., “Mass Spectrometric Determination of Activities of Phosphorus in Liquid Fe-P- 

Si, Al, Ti, V, Cr, Co, Ni, Nb and Mo Alloys” (in Japanese), Tetsu to Hagane (J. Iron Steel Inst. Jap.), 65 

(2), 273–280 (1979) (Thermodyn., Calculation, Experimental, Review, 40) 

[1980Rom] Romig, A.D., Jr., Goldstein, J.I., “Determination of the Fe-Ni and Fe-Ni-P Phase Diagrams at Low 

Temperatures (700 to 1300˚C)”, Metall. Trans. A., 11A, 1151–1159 (1980) (Crys. Structure, Morphology, 

Phase Diagram, Phase Relations, Experimental, 20) 

[1981Maa] Maaref, S., Madar, R., “Crystal Chemistry of M 12P 7 Phases in Relation with the M 2P Phosphides”, J. 

Solid State Chem., 40, 131–135 (1981) (Crys. Structure, Experimental, 11) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_10 

ß Springer 2009

20 10 

Fe–Ni–P 

[1981Rom] Romig, A.D., Jr., Goldstein, J.I., “Low Temperature Phase Equilibria in the Fe-Ni and Fe-Ni-P Systems: 

Application to the Thermal History of Metallic Phases in Meteorites”, Geochim. Cosmochim. Acta, 45 

(7), 1187–1197 (1981) (Morphology, Experimental, Interface Phenomena, Kinetics, 22) 

[1982Sas] Sasaki, Y., Iida, Y., Yokoo, A., Ueda, S., “High-temperature Phosphidation of Iron-Nickel Alloys by 

Phosphorus Vapor” (in German), Z. Anorg. Allg. Chem., 487, 232–240 (1982) (Crys. Structure, 

Morphology, Experimental, Interface Phenomena, Kinetics, 11) 

[1983Gru] Gruzin, P.L., Urytu, S.G., “Diffusion of Nickel in the Amorphous Alloy Iron-Nickel-Phosphorus” (in 

Russian), Ukr. Fiz. Zhurnal, (2), 255–258 (1983) (Morphology, Experimental, Interface Phenomena, 

Kinetics, 3) 

[1983Mat] Matsuyama, T., Hosokawa, H., Suto, H., “Tracer Diffusion of P in Iron and Iron Alloys”, Trans. Jpn. 

Inst. Met., 24(8), 589–594 (1983) (Morphology, Experimental, Interface Phenomena, Kinetics, Magn. 

Prop., 14) 

[1983Shi] Shinoda, T., “Theoretical Estimates of Phosphorus Concentration Profiles Across Grain Boundaries in 

Fe-P and Fe-Ni-P Systems”, Acta Metall., 31(12), 2051–2062 (1983) (Morphology, Calculation, Theory, 

Interface Phenomena, 15) 


Activity Coefficient of P in Liquid Iron”, Trans. Iron Steel Inst. Jpn., 23(1), 51–55 (1983) (Thermodyn., 

Calculation, Experimental, 16) 

[1984Ban] Ban-Ya, S., Maruyama, N., Kawase, Y., “Effects of Ti, V, Cr, Mn, Co, Ni, Cu, Nb, Mo and W on the 

Activity of Phosphorus in Liquid Iron” (in Japanese), Tetsu to Hagane, 70(1), 65–72 (1984) (Thermodyn., 

Calculation, Experimenta1, Review, 21) 

[1984Nar1] Narayan, S., Goldstein, J.I., “Nucleation of Intergranular Ferrite in Fe-Ni-P Alloys”, Metall. Trans. A., 

15A, 861–865 (1984) (Morphology, Experimental, 16) 

[1984Nar2] Narayan, S., Goldstein, J.I., “Growth of Intergranular Ferrite in Fe-Ni-P Alloys”, Metall. Trans. A., 15A, 

867–874 (1984) (Morphology, Phase Relations, Experimental, Interface Phenomena, Kinetics, 16) 

[1986Dea] Dean, D.C., Goldstein, J.I., “Determination of the Interdiffusion Coefficients in the Fe-Ni and Fe-Ni-P 

Systems below 900˚C”, Metall. Trans. A, 17A(7), 1131–1138 (1986) (Morphology, Experimental, 

Interface Phenomena, Kinetics, 22) 

[1986Fje] Fjellvag, H., Kjekshus, A., “Solid Solution Phases with MnP Type Structure: T 1–tNi tP (T = Ti-Co)”, 

Acta Chem. Scand., Ser. A, A40, 8–16 (1986) (Crys. Structure, Phase Relations, Experimental, Magn. 

Prop., 43) 

[1986Reu] Reuter, K.B., “Determination of the Iron-Nickel and Iron-Nickel-Phosphorus (Sat.) Phase Diagrams 

below 400˚C”, Ph. D. Thesis, Lehigh Univ., 1–309 (1986) (Phase Diagram, Experimental) as quoted by 

[1988Rag] 

[1987Ina] Inaba, M., Teshima, K., “Effects of Phosphorus and Sulfur on Thermal Expansion and Mechanical 

Properties of Fe-36Ni”, J. Mater. Sci. Letters, 6, 727–728 (1987) (Morphology, Experimental, Mechan. 

Prop., Phys. Prop., 9) 

[1988Rag] Raghavan, V., “The Fe-Ni-P System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Met., 

Calcutta, 3, 121–137 (1988) (Crys. Structure, Phase Diagram, Phase Relations, Assessment, Review, 

#, 16) 

[1988Sai] Saito, N., Abiko, K., Kimura, H., “Reduction of Intergranular Fracture in Fe-P Alloys by the Addition 

of Nickel”, Mater. Sci. Eng. A., 102, 169–174 (1988) (Morphology, Experimental, Interface Phenomena, 

Mechan. Prop., 10) 

[1990Gus] Gustafson, P., “Study of the Thermodynamic Properties of the C-Cu-Fe-P, Fe-Mo-P and Fe-Ni-P 

System”, Inst. Met. Res. (IM-2549), 1–50 (1990) (Phase Diagram, Thermodyn., Calculation, 52) 

[1990Jon] Jones, J.H., Malvin, D.J., “A Nonmetal Interaction Model for the Segregation of Trace Metals During 

Solidification of Fe-Ni-S, Fe-Ni-P, Fe-Ni-S-P Alloys”, Metall. Trans. B, 21B, 697–706 (1990) (Theory, 


[1990Res] Ressler, L., Rosenberg, M., “Magnetic Moments and Magnetic Transitions in the Low Iron 

Concentration Range of the Amorphous Fe xNi 80–xP 20 Alloys”, J. Magn. Magn. Mater., 83(1-3), 

343–344 (1990) (Morphology, Experimental, Magn. Prop., 9) cited from abstract 

[1991Swa] Swartzendruber, L.J., Itkin, V.P., Alcock, C.B., “The Fe-Ni (Iron-Nickel) System”, J. Phase Equilib., 12, 

288–312 (1991) (Crys. Structure, Phase Diagram, Thermodyn., Assessment, *, 255) 


(China), 29(12), B527–B532 (1993) (Thermodyn., Phase Relations, Calculation, Theory, 7) 



MSIT 1


21 

[1997Gao] Gao, C.H., Zhou, B.Y., “Effects of the Composition of Electrodeposited Fe-Ni-P Alloy on the 

Thermostability and Magnetic Properties”, J. Mater. Sci. Technol., 13(2), 137–140 (1997) (Morphology, 

Experimental, Phys. Prop.) cited from abstract 

[1998Mie] Miettinen, J., “Approximate Thermodynamic Solution Phase Data for Steels”, Calphad, 22(2), 275–300 

(1998) (Phase Diagram, Phase Relations, Thermodyn., Assessment, Calculation, 98) 

[2000Jei] Jeitschko, W., Foecker, A.J., Paschke, D., Dewalsky, M.V., Evers, Ch.B.H., Kuennen, B., Lang, A., 

Kotzyba, G., Rodewald, U.Ch., Moeller, M.H., “Crystal Structure and Properties of some Filled and 

Unfilled Skutterudites: GdFe 4P 12, SmFe 4P 12, NdFe 4As 12, Eu 0.54Co 4Sb 12, Fe 0.5Ni 0.5P 3, CoP 3, and NiP 3”, 

Z. Anorg. Allg. Chem., 626, 1112–1120 (2000) (Crys. Structure, Morphology, Experimental, 65) 

[2000Wan] Wang, L., Zhao, L., Huang, G., Yuan, X., Zhang, B., Zhang, J., “Composition, Structure and Corrosion 

Characteristics of Ni-Fe-P and Ni-Fe-P-B Alloy Deposits Prepared by Electroless Plating”, Surf. Coat. 

Technol., 126 (2-3), 272–278 (2000) (Crys. Structure, Morphology, Experimental, Phys. Prop.) cited 

from abstract 

[2001Wan] Wang, L., Zhao, L., Huang, G., Yuan, X., Zhang, B., Zhang, J., “The Structure and Microhardness of 

Ni-Fe-P and Ni-Fe-P-B Alloy Deposits Prepared by Electroless Plating”, Plating & Surface Finishing, 

88(6), 92–95 (2001) (Crys. Structure, Morphology, Experimental, Mechan. Prop.) cited from abstract 

[2002Chu] Chuang, M.-S., Lin, S.-T., “Effect of Phosphorous Addition on the Grain Growth of Fe-50 wt.% Ni 

Alloys”, Scr. Mater., 47(5), 321–326 (2002) (Morphology, Thermodyn., Experimental, Interface Phenomena, 

Kinetics, 12) 

[2002Per] Perrot, P., Batista, S., Xing, X., “Fe-P (Iron-Phosphorus)”, MSIT Binary Evaluation Program, in MSIT 

Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH, Stuttgart; Document 

ID: 20.16107.1.20, (2002) (Crys. Structure, Phase Diagram, Phase Relations, Thermodyn., 

Assessment, Phys. Prop., #, 23) 

[2003Cha] Chabot, N.L., Jones, J.H., “The Parameterization of Solid Metal-Liquid Metal Partitioning of 

Siderophile Elements”, Meteor. Planet. Sci., 38(10), 1425–1436 (2003) (Thermodyn., Experimental, 


[2003Mor1] Moretzki, O., Doering, Th., Geist, V., Morgenroth, W., Wendschuh, M., “Crystal Structure of Iron 

Nickel Phosphide, Fe 1.7Ni 1.3P, a Schreibersite Extracted from Canyon Diablo Meteorite”, Z. Kristallogr. 

NCS, 218(4), 391–392 (2003) (Crys. Structure, Experimental, 5) 


Nickel Phosphide, Fe 1.65Ni 1.35P, a Rhabdite Extracted from Morasko Meteorite”, Z. Kristallogr. NCS, 218 

(4), 393–394 (2003) (Crys. Structure, Experimental, 5) 


Nickel Phosphide, Fe 1.8Ni 1.2P, a Schreibersite Extracted from Orange River Meteorite”, Z. Kristallogr. 

NCS, 218(4), 395–396 (2003) (Crys. Structure, Experimental, 5) 

[2004Zac] Zach, R., Tobola, J., Sredniawa, B., Kaprzyk, S., Casado, C., Bacmanm, M., Fruchart, D., “Magnetoelastic 

Properties and Electronic Structure Analysis of the (Fe1–xNix)2P System”, J. Alloys Compd., 383, 

322–327 (2004) (Crys. Structure, Calculation, Experimental, Electronic Structure, Magn. Prop., 17) 

[2005Gei] Geist, V., Wagner, G., Nolze, G., Moretzki, O., “Investigations of the Meteoritic Mineral (Fe,Ni) 3P”, 

Cryst. Res. Technol., 40(1-2), 52–64 (2005) (Crys. Structure, Morphology, Experimental, Review, 

Electronic Structure, 41) 

[2006Gao] Gao, C.H., “Stability of Electrodeposited Amorphous Ni-Fe-P Alloys”, Trans. Nonferrous Met. Soc. of 

China, 16(6), 1325–1330 (2006) (Morphology, Phase Relations, Thermodyn., Experimental, Mechan. 

Prop.) cited from abstract 

[2006Mil] Miller, M.K., “Atom Probe Tomography Characterization of Solute Segregation to Dislocations and 

Interfaces”, J. Mater. Sci., 41, 7808–7813 (2006) (Morphology, Experimental, 21) 



Structure, Phase Diagram, Phase Relations, Assessment, #, 41) 


(1990) 





MSIT 1 

DOI: 10.1007/978-3-540-70890-2_10 

ß Springer 2009

Iron – Nickel – Sulphur 


Olga Fabrichnaya, Vasyl Tomashyk, Artem Kozlov 

Introduction 

Fe–Ni–S 11 

1 

Phase relations in the Fe-Ni-S ternary system are very important for geology as well as for 

metallurgy because phases found in this system are constituents of many ores [1991Tay]. The 

mineral phases (pyrrhotite, pyrite, pentlandite) in this system are both geologically widespread 

and economically important [1974Vau, 2004Dis]. This system is very complicated and, 

therefore, complex reactions occur in sulfide ores as they cool [1971Gra]. According to 

geophysical data, the core of the Earth consists of Fe-Ni alloy containing a light element 

(most probably sulphur). Therefore properties of Fe-Ni-S solid and liquid alloys are important 

for geophysical interpretations of seismic data [1997Nas]. The Fe-Ni-S alloys are the constituents 

of condrites and other meteorites [1998Ma]. The distribution of elements between solid 

and liquid metal helps to explain conditions of the formation of meteorites and terrestrial 

planet and therefore to explain some features of evolution of the solar system [1990Jon, 

2003Cha]. 

The considerable literature on this ternary system has been reviewed in the publications of 

[1943Haw, 1949Jae, 1963Kul1, 1964Kul, 1969Kul, 1970Sug, 1981Fit, 1982Hsi, 1988Rag, 

1989Bar, 1989Bat, 2004Rag, 2004Wal2, 2006Rag]. 

Many phases in the Fe-Ni-S system were found in nature as minerals. The ternary phases 

(Fe xNi 1–x)S 2, in which the Fe/Ni ratio is ≈1 (bravoite), FeNi 2S 4 (violarite) and (Fe 9–xNi x) 9S 8 

(pentlandite) are formed in the Fe-Ni-S ternary system [1964Kul]. However, later it was found 

that violarite is an end-member of the solid solution FeNi 2S 4-Ni 3S 4 with the spinel structure 

[1971Cra]. It was proved by [1963Cla] that bravoite is stable at temperatures below 137˚C, at 

higher temperatures it decomposes to pyrite and vaesite. Many experimental investigations 

were performed to study crystal structure and compositions of minerals from natural deposits 

[1955Eli, 1963Kul2, 1971Gra, 1972Har, 1972Nic, 1973Hal, 1973Raj]. 

According to the data of [1955Van] and [1957Van] FeNi4S5 is formed in the Fe-Ni-S 

ternary system but Fe 2Ni 3S 4 which was obtained by [1930Vog, 1938Ura] was not found. None 

of these compounds was confirmed in the later studies. The phase (Fe 0.66Ni 0.34) 2S, was 

detected to form at very reducing conditions by [1961Stu]. 

A liquidus surface of this system was constructed by [1930Vog, 1938Ura, 1955Van, 

1964Kul, 1983Van]. It was found that Fe 1–xS and Ni 1–xS form a continuos series of solid 

solutions at temperatures above 300˚C [1961Nis, 1974Vau, 1976Kas, 1981Oht, 1983Van]. 

Isothermal sections of the Fe-Ni-S ternary system were constructed at 1100, 1000, 900, 800, 

700, 600, 500, 460, 400, 300, 250 and < 135˚C [1947Lun, 1956Kul, 1960Cla, 1963Cla, 

1963Kul1, 1964Kul, 1967Nal, 1968Cra, 1970She, 1971Gra, 1973Cra, 1973Mis2, 1984Bee, 

1978Len, 1998Kar, 1998Ma, 2000Uen, 2001Sin1, 2006Sin]. Some temperature - composition 

sections were constructed by [1930Vog, 1938Ura, 1955Van, 1956Kul, 1957Van, 1964Kul, 

1966Nal, 1970She, 1971Cra, 1976Chi]. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

2 11 

Fe–Ni–S 

The mutual solubility of FeS 2 and NiS 2 was investigated by [1962Kle]. The reaction 

Ni 3S 2+2Fe Ð 2FeS+3Ni takes place at 1200˚C [1976Gul]. FeS and Ni 3S 2 form the pentlandite 

solid solution (τ 1) and Ni dissolves in Fe. According to the data of [1979Sha] iron interacts 

with Ni 3S 2 on heating forming Fe 1–xS and (Fe 1–xNi x) 3+yS 2 solid solutions and Fe-Ni solid 

solution at 600˚C. [1976Chi] studied reaction of Fe and Ni 3S 2 at 1100˚C and observed 

formation of Fe1–xS and Fe-Ni solid solution. 

The solubility and diffusion of S in the Fe-Ni alloys was studied by [1982Net, 1983Net1, 

1983Net2] by radiotrace method. In several works [1981Mar, 1984Mar1, 1984Mar2] the role 

of sulfur in the dissolution and passivation of Fe-Ni alloy was investigated using radiotrace, 

electrochemical method and X-ray photoelectron spectroscopy. 

Thermodynamic properties of the solid and liquid alloys in the Fe-Ni-S ternary system 

were investigated by [1955Cor, 1960Alc, 1968Chm, 1969Ban, 1969Vai, 1970Khe, 1970Vay, 

1972Bye, 1972Vay, 1973Buz, 1973Ven, 1974Khe, 1974Sig, 1981Fit, 1984Khe, 1989Bar, 

1998Kon, 1999Kon, 2003Kos]. 

Thermodynamic modelling in the Fe-Ni-S system was performed by [1983Chu1, 

1983Chu2, 1987Hsi1, 1987Hsi2, 1987Hsi3] using associate model for liquid and by 

[1999Kon, 2004Wal2, 2006Wal2] using modified quasichemical model for liquid. [1991Tay] 

presented a thermodynamic description for the Fe-Ni-S system with the liquid phase described 

by a two-sublattice model. Calculated isothermal section at 400˚C was presented by [1991Tay]. 

Magnetic properties of the phases in the Fe-Ni-S ternary system were investigated by 

[1930Vog, 1961Nis, 1970Kno, 1974Vau, 1976Kas, 1976Kno, 1977Nis, 1981Oht]. 

Table 1 lists the numerous experimental works on phase equilibria, crystal structure and 

thermodynamics of the Fe-Ni-S system. 


The phase diagrams of the Fe-S and Fe-Ni systems are accepted from the MSIT evaluations of 

[2008Fer] and [2008Kuz], respectively. At temperatures below 315˚C several superstructures of 

the NiAs type was reported [2008Fer]. The Ni-S system is accepted from the thermodynamic 

assessment of [2004Wal1] and [2006Wal1]. The phase diagram presented in [2006Wal1] isin 

agreement with [Mas2] except for the low temperature part, where the Ni 9S 8 phase was 

considered by [2004Wal1, 2006Wal1] based on data of [1987Fle] and [1994Sto]. The separation 

of the β phase to β 1 and β 2 was not taken into account in [2004Wal1], but in the later work 

of [2006Wal1, 2006Wal2] two different β phases are considered. 


The crystallographic data for solid phases are listed in Table 2. 

The ternary system Fe-Ni-S is dominated by ternary solid solutions. At high sulfur 

content, two solid solutions are formed based on pyrite (βFeS 2) and vaesite (ηNiS 2) with a 

limited mutual solubility. These solid solutions have the same structure, but they never join in 

one continuous solution. [1962Kle] found a quite large mutual solubility of ηNi 2S and βFe 2S. 

However later it was indicated by [1963Cla] that these values are too high being influenced by 

the metastable conditions. Also in this section, a low temperature Fe0.5Ni0.5S2 (bravoite) phase 



MSIT 1


3 

exists which was found to decompose into a mixture of NiS 2 and FeS 2 at a temperature of 

137˚C according to [1963Cla, 1977Nis]. 

The monosulfides γFe 1–xS (pyrrhotite) and δNi 1–xS (millerite) form a continuous solid 

solution (mineral pyrrhotite) [1961Nis, 1981Oht, 1983Van]. However, continuous solid solution 

Fe 1–xNi xS 1+y exists at the temperatures above 300˚C and at a lower temperature a 

miscibility gap appears [1973Mis2, 1973Cra]. Below 283˚C Ni-rich monosulfide decomposes 

to form FexNi3–xS4 (polydymite) and the low temperature millerite phases [1973Cra]. The 

c-axis lattice parameter of the Fe1–xNixS solid solution decreases as x increases [1976Kas]. This 

variation is divided into two regions, one where the c-axis lattice parameter decreases steeply 

with increasing x (0 ≤ x ≤ 0.50) and the other where the lattice decreases gently with a further 

increase in x (0.50 ≤ x ≤ 1.0). No lattice modification was found in the Fe 1–xS-Ni 1–xS system 

[1981Oht]. [1976Fra] studied pyrrhotite by TEM and found that ordering of metal vacancies 

distinguished various superstructures of monosulfide. 

In the binary Ni-S system separation of the high temperature modification of haezlewoodite 

(β) into β1 and β2 was confirmed by experimental data [2006Wal1]. Based on these data in 

the binary system, the existence of two phases β1 and β2 in the ternary system was assumed by 

[2006Wal2]. However, in the ternary system, there are no experimental data about the 

separation of the high temperature heazlewoodite into two phases. Therefore, in many 

works only one β phase is shown in the diagrams. A considerable solubility of iron in the β 

phase is supported by the experimental data [2006Wal2]. Therefore solubility of Fe in both β 

phases was assumed by [2006Wal2]. 

The violarite solid solution extends toward Ni rich compositions with decrease of temperature 

and becomes a continuous solid solution FexNi3–xS4 at 356˚C [1971Cra]. At a temperature 

of 461 ± 3˚C FeNi2S4 decomposes to form Fe1–xNixS2, NixFe1–xS2 and pyrrhotite 

containing Fe and Ni in the atomic ratio 1 : 2.4. 

The Ni 3S 2 phase dissolves 1.0-1.5 mass% Fe according to [1976Chi, 1976Gul]. 

The solubility of S in the Fe-Ni alloys at 950-1250˚C and at p(H 2S)/p(H 2) ratios from 

4·10 –4 to 8·10 –4 corresponds to the Siverts’ law [1983Net1, 1983Net2, 1989Bar]. The solubility 

of S as a function of temperature and p(H 2S)/p(H 2) ratio was presented in [1983Net1, 

1983Net2] and [1989Bar]. The maximal solubility of S in (αFe), (γFe) and (δFe) is 0.033, 

0.09 and 0.24 at.%, respectively [2008Fer], while solubility of S in solid Ni is negligible [Mas2]. 

A τ1 (Fe9–xNixS8+y) ternary compound (pentlandite) with a wide homogeneity range 

[1947Lun] starts to appear below 610˚C [1964Kul]. Pentlandite is stable below 610˚C, where 

it decomposes to (Fe xNi 1–x) 1–yS, containing less than 1.0 mass% Ni, and (Fe xNi 1–x) 3±xS 2 solid 

solution containing several mass% Fe [1964Kul]. 

According to calculations of [2004Wal2, 2006Wal2] maximal temperature of stability of 

the τ 1 phase is ~640˚C. 

Some other ternary compounds are found in nature as minerals. Probably they are 

metastable at room temperatures being formed in the conditions of the Earth interior. 

Many of them decompose with the temperature increase. FeNi2S4 corresponds to the mineral 

violarite. [1971Cra] noted that FeNi 2S 4 has a maximum thermal stability at 461 ± 3˚C and a 

composition of Fe 0.92Ni 2.08S 4. It was pointed out by [1971Cra] that violarite is an end-member 

of the solid solution extended towards Ni 3S 4 and forming continuous solution of FeNi 2S 4- 

Ni 3S 4 at 356˚C. A FeNi 4S 5 phase was found by [1955Van, 1957Van], however this phase was 

not confirmed in any later study. [1961Stu] indicated the existence of the (Fe 0.66Ni 0.34) 2S 

compound at very reducing conditions. However, such conditions were not studied later and 

the formation of this compound was never mentioned. The crystal structure of the mineral 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

4 11 

Fe–Ni–S 

FeNi 29S 27 is described in [1987Fle]. The structure of this orthorhombic phase contains 

elements of godlevskite Ni 7S 6, millerite NiS and pentlandite Fe 9–xNi xS 8+y. However, this 

compound was not confirmed in further experiments. 


A reaction scheme from [1982Hsi] taking into account data from [2004Kos] and corrected 

according to the accepted binary systems is presented in Fig. 1. The available data for the 

invariant reactions from [1982Hsi] and [2004Kos] are presented in Table 3. It should be 

mentioned that the reaction scheme and the data for the invariant reactions in [1982Hsi] are 

provisional and in case there are new experimental measurements we recommend to use these 

new data. In the work of [1982Hsi] the high-temperature heazlewoodite is considered as one 

single phase β. A three-phase monovariant reaction of the peritectic type between the β phase, 

pyrrhotite and liquid was studied by directional crystallization of melt in combination with 

DTA by [2004Kos]. It was found that this monovariant curve has a temperature maximum at 

875˚C, what is slightly higher than assumed by [1982Hsi]. The data for this maximum are 

taken from [2004Kos]. It should be mentioned that DTA measurements of [1999Sin] for the 

U 2 reaction are not taken into account since they disagree with most of experimental data and 

calculations of [2004Wal2]; the difference in temperature for the reaction U2 reported by 

[1982Hsi] and [1999Sin] is more than 200˚C. In this work we accepted temperature of 

reaction U 2 from [2004Wal2] equal to 800˚C. 


Liquidus surface was experimentally studied by [1930Vog, 1938Ura, 1955Van, 1978Len, 

1999Sin]. A wide region of liquid immiscibility extends across the S rich portion of the 

Fe-Ni-S ternary system at high temperatures [1964Kul, 1983Van]. 

The liquidus surface was calculated by [1987Hsi2] based on experimental data on liquidus 

[1978Len] and measurements of partial pressure of sulphur over the liquid phase and 

pyrrhotite [1987Con, 1987Hsi2, 1987Hsi3]. The liquidus surface from the work of 

[1987Hsi2] is presented in Fig. 2. 


Isothermal sections were experimentally studied in several works [1963Kul1, 1973Cra, 

1987Con, 1987Hsi4, 2000Uen, 2001Sin1]. 

The phase relations in the S rich part of the Fe-Ni-S ternary system in the 700-750˚C 

temperature range were given by [1964Kul]. The isothermal sections at 500 and 460˚C between 

0 and 50 at.% S were determined by the analysis of equilibrated ternary alloys and diffusion 

couples in [1984Bee]. At 500˚C the iron stabilized high-temperature modification βNi 3S 2 was 

found. A low temperature isothermal section (< 135˚C) was studied [1971Gra]. 

The phase relations involving the appearance of FeNi 2S 4 and development of the FeNi 2S 4- 

Ni 3S 4 solid solution at 500, 450, 400 and 300˚C were determined by [1971Cra]. Binary sulfides 

except Fe 1–xS are not in equilibrium with the iron phase in the Fe-Ni-S system at 950˚C 

[1963Kan]. 



MSIT 1

The calculated isothermal sections based on the Calphad-type assessments using quasichemical 

model [2004Wal2, 2006Wal2] reproduce experimental data at 600-1350˚C within 

uncertainty limits. The assessments based on the associate model [1987Hsi1, 1987Hsi2, 

1987Hsi4] also reproduce experimental isothermal sections at 700-1350˚C, but calculations 

[2004Wal2] seems to be in better agreement with experimental data. The isothermal section at 

400˚C was calculated by [1991Tay]. However, none of the available assessment works present 

isothermal sections at all the temperatures studied experimentally. Therefore, in the present 

study isothermal sections are presented based on the available calculations and experiments. 

Figures 3a to 3c present isothermal sections at 1350, 1300 and 1200˚C calculated in 

[2004Wal2], respectively. Figures 4a to 4c present isothermal sections calculated by 

[1987Hsi2] at 1100, 1050 and 1000˚C. Figures 5a to 5c present isothermal sections at 900, 

700˚C calculated by [2004Wal2] and at 600˚C [2006Wal2], respectively. As it was mentioned 

above, in [2006Wal2] two haezlewoodite phases β 1 and β 2 were considered. Because only 

one isothermal section was calculated based on the new thermodynamic description, the other 

isothermal sections are presented according to [2004Wal2]. Isothermal sections at 550, 500 

and 400˚C were constructed by [1963Kul1] based on experimental results. They are in a good 

agreement with later studies [1968Cra, 1970She] except for a wider homogeneity range of the 

pentlandite solid solution indicated by [1968Cra, 1970She]. Figures 6a and 6b present 

isothermal sections at 500 and 400˚C from [1970She] and [1968Cra], respectively. The lowtemperature 

phase relations at 200-300˚C were studied by [1973Cra] and [1973Mis2]. Miscibility 

gaps were found to appear in the monosulfide solid solutions: one below 263˚C and 

another at 225˚C [1973Cra]. Partial isothermal sections at 300 and 200˚C are presented in 

Figs. 7a and 7b from [1973Cra] and at the temperatures below 135˚C from [1971Gra] 

(Fig. 7c). Phase relations involving superstructures of NiAs [1992Gro] are not very well 

defined for the Fe-S system, therefore phase relations involving solid solution at 40 mass% S 

and Ni up to 7 mass% Ni being superstructure of NiAs are shown tentatively in Figs. 7a and 7b. 

At the temperatures below 135˚C the bravoite phase Fe 0.5Ni 0.5S 2 was found stable. 

It should be mentioned that isothermal sections at 400, 300, 200˚C and at the temperatures 

below 135˚C were slightly corrected to be consistent with accepted binary system Ni-S. 

According to [1994Sto] and [2004Wal1] Ni 9S 8 phase was accepted to be stable, while phase 

γ’Ni7S6 accepted in earlier studies (see evaluation of [Mas2]) was not considered as stable one. 

Therefore γ’Ni7S6 was changed to Ni9S8 phase at low temperature sections. 



5 

The phase diagram of the FeS 2-NiS 2 system was experimentally studied [1963Cla, 1998Kar]. 

Thirteen temperature - composition sections were constructed by [1930Vog, 1938Ura, 

1955Van, 1957Van]. Eleven of these sections cross the ternary system from the S corner to the 

Fe-Ni binary and two others (FeS-Ni6S5, FeS-Ni3S2) travers the system from FeS to the Ni-NiS 

subsystem [1955Van, 1957Van]. A section along the FeNi 2S 4-Ni 3S 4 join was determined by 

[1971Cra]. 

[2004Wal2] calculated isopleths in the Fe-Ni-S system at the constant Fe/Ni ratios of 

0.6722 and 1.0, vertical sections FeS-Ni 3S 2, FeS 2-NiS 2 and at a fixed concentration of sulfur 

equal to 0.471. The section FeS-Ni 3S 2 was recalculated by [2006Wal2] taking into account 

separation of β phase into β 1 and β 2. The calculated vertical sections from [2004Wal, 

2006Wal2] are presented in Figs. 8a to 8c. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

6 11 

Fe–Ni–S 

Vertical sections for Fe/Ni ratio equal to 0.6722 and 1 are not shown in present evaluation, 

because [2004Wal2] took into account only fcc and bcc phases in the Fe-Ni system. Therefore 

calculations of [2004Wal2] at temperatures below 600˚C are not consistent with accepted 

binary Fe-Ni system. At higher temperatures fine details of phase diagram are not possible to 

distinguish, because the diagrams are overloaded by experimental points. 

Potential Diagrams 

[1987Hsi1, 1987Hsi2, 1987Hsi4] calculated potential diagrams presenting log p(S 2) vs x(Fe)/ 

(x(Fe)+x(Ni)) ratio at temperatures 700-1100˚C. The calculations of [1987Hsi1] at 700, 800, 

900 and 1100˚C from [1987Hsi1] are presented in Figs. 9a to 9d. 


The activity of S in the liquid phase (matte) was measured by [1972Bye, 1987Con] using 

method of equilibration with H 2 and H 2S gas mixtures. However, the data of [1972Bye] and 

[1987Con] do not agree very well with each other. The data of [1972Bye] give higher activity 

values and they are quite scattered. In the work of [1987Con] the results obtained by 

equilibration technique were confirmed by vapor pressure measurements using Knudsen 

mass-spectrometer. The activities of Fe in the matte were reported in [1962Vay, 1969Vai, 

1972Vay], who used the emf method. Though the discrepancy between [1962Vay] and 

[1969Vai] was not explained by the authors, the data of [1969Vai] are in agreement with 

[1987Con]. The calculated S activities predicted by the model of [1999Kon] are consistent 

with the data of [1987Con]. The agreement between the predicted Fe activities [1999Kon] and 

those reported in [1969Vai] is very good. The calculated Fe and S activity in the liquid phase in 

the works of [1987Hsi2, 2004Wal2] are in good agreement with experimental results of 

[1969Vai] and [1987Con]. The results of calculation [2004Wal2] for the Fe and S activity in 

the liquid phase are presented in Figs. 10 and 11 and Figs. 12a to 12c. 

The activity of sulfur in the pyrrhotite solid solutions at different Fe/Ni ratios and S 

contents were measured by [1987Hsi4] using gas equilibration technique at 700-900˚C. The 

calculated results from [1987Hsi3, 2004Wal2] are in a good agreement with experimental data. 

The calculated S activity in the pyrrhotite solid solutions from [2004Wal2] are presented in 

Figs. 13a to 13e. 

The Gibbs energy (integral and partial) in the FeS-Ni 3S 2 system at 1150˚C were calculated 

in [1983Chu1], activity of both components at 1200˚C were calculated in [1983Chu1, 

1983Chu2] and at 1300˚C in [1987Hsi1]. Calculations of [1987Hsi1] for activity in the 

FeS-Ni3S2 join are presented in Fig. 14. Activities of Fe in the Ni3S2-Fe and FeS-Ni joins at 

1300˚C were calculated by [1969Vai, 1987Con, 1987Hsi1]. 

Isoactivities of Ni and Fe in the Fe-Ni-S system at 1300˚C were presented in the works of 

[1970Vay, 1972Vay, 1974Khe] based on experimental results obtained by emf measurements. 

[1987Hsi1] calculated isoactivity lines for (αFe), (αNi) and log 10p(S 2) 1/2 in liquid and liquid+γ 

regions at 1200-1400˚C. 

The sulfur activity in dilute Fe-Ni liquid solutions were measured by equilibration with H 2 

and H2S gas mixtures at 1600˚C [1955Cor] and at 1540˚C [1960Alc]. The activity coefficient of 



MSIT 1

sulfur in dilute liquid Fe-Ni alloys at 1540˚C were evaluated in terms of Wagner model and 

compared with experimental data of [1960Alc] in the work of [1981Fit]. Addition of Ni to Fe 

has a little influence on the dissolution energy of S in Fe-Ni alloys [1989Bar]. The excess Gibbs 

energy of S mixing in liquid Fe-Ni alloys at 1540˚C should be negative at the Ni rich end of the 

Fe-Ni system, reaching a maximum about –2.1 kJ·(g-at) –1 , but positive at the Fe rich end of 

this system [1960Alc]. Ni decreases slightly the activity coefficient of S in liquid Fe [1968Chm, 

1969Ban], while Fe increases activity coefficient of S in liquid Ni [1973Ven]. The first 

order interaction parameter up to 20 mass% Ni is equal e Ni S = – 0.003 and between 20 and 

32 mass% Ni its values are e Ni S = – 0.006 [1968Chm](e Ni S = 0.0 and e S Ni = – 0.0037 [1974Sig]; 

e Ni S = – 0.00006 at 1550˚C and up to 50 at.% Ni [1969Ban], e Ni S = – 0.005 [1973Buz]). The 

value of e Ni S obtained from the theoretical model is –0.49 [1981Fit]. The first order interaction 

parameters up to 35 at.% Fe at 1575˚C are equal e Fe S = + 0.005 [1968Chm]. The second order 

interaction coefficient r Ni S is equal zero [1974Sig]. 

The thermodynamic modelling was performed by [1983Chu1, 1987Hsi1, 1987Hsi2, 

1987Hsi3] using associated solution model for the liquid phase, statistical model for monosulfide 

solid solution and subregular model for other solutions. The liquidus projection, 

isothermal sections in the range 1350-700˚C, sulfur activity over liquid and monosulfide 

were calculated and compared with respective experimental data. Stability diagrams (potential 

diagrams) presenting partial pressure of sulfur versus composition were calculated at 

1100-700˚C. Two other assessments of thermodynamic parameters [2004Wal2, 2006Wal2] 

were published recently. Quasichemical model for short-range ordering was applied for 

ternary liquid and sublattice model was applied for description of solid solutions: monosulfide, 

pentlandite, pyrite, vaesite and high-temperature haezlewoodite. Based on those 

thermodynamic descriptions isothermal sections in the range 1350-600˚C, vertical sections, 

sulfur activity over liquid and monosulfide phase were calculated. As was mentioned before, in 

the description of [2006Wal2] two phases of haezlewoodite were considered, while the 

parameters for other phases were the same as in [2004Wal2]. 



7 

The solubility curve of FeS2 in NiS2 was applied in geological thermometry by [1963Cla]. An 

increase in S or FeS activity by addition of FeS may be effective in lowering the Ni content of 

the separating Fe-Ni alloys [1972Bye]. 

The magnetic order Ð disorder transition occurs in regions of the monosulfide solid 

solution (pyrrhotite) where it breaks on cooling [1974Vau]. Beyond this transition in the 

monosulfide compositions may exhibits weak temperature independent Pauli paramagnetism 

and metallic conductivity. [1976Kas] indicated that the magnetization of Fe xNi 1–xS ceramics 

reduces with increasing Ni content up to 50 at.%, increases between 50 and 60 at.% Ni and 

decreases again between 60 and 100 at.% Ni. The TC reduces with increasing Ni content up to 

50 at.% but was not measured for higher Ni contents at room temperature to 300˚C. The 

electrical resistivity reduces uniformly with decreasing Fe content of this ceramics. [1997Dre] 

noted that monosulfide within the range of composition (Fe 1–xNi x) 0.96S at x = 0-0.6 

are capable of forming magnetic structures like Fe 0.96S. Ni atoms create defects in the 

magnetic structure. The temperature of the magnetic - paramagnetic transition decreases 

with decreasing Fe:Ni ratio and the changes in the initial monosulfide are directed towards 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

8 11 

Fe–Ni–S 

moving Ni from the magnetic monosulfide into the nonmagnetic pentlandite. Magnetic 

measurement and DTA have been performed at 4.2-300 K for Ni 1–xFe xSby[1976Bar]. Metal 

- non-metal transition temperature decreased for 1% Fe and then increased for 2-3% Fe. 

Magnetic susceptibility was measured for Ni 0.99Fe 0.01S. 

According to the data of [1961Nis] the magnetic region in the Fe-Ni-S ternary system lies 

within the composition region enclosed by the line Fe-FeS-Fe9–xNixS8-Ni3S2-Ni. Specimens 

outside of this area were non-magnetic. The intensity of magnetization of the specimens 

decreases when the composition changes towards the line FeS-Fe 9–xNi xS 8-Ni 3S 2. The specimens 

whose S content is higher than this line were paramagnetic. 

The metal-semiconductor transition in the Fe 1–xS-Ni 1–xS system is accompanied by the 

drastic changes of electrical and magnetic properties, this being similar to that of pure NiS 

[1981Oht]. Transition temperature (T t) increases with increase in Fe content, but in the 

forward direction it shows a significant increase as high as 50˚C, when specimens were aged 

at a temperature below Tt. The reverse transformation is not affected by thermal history at all. 

This could be explained by the relaxation process in which the strain energy stored in the low 

temperature phase is relieved by aging [1981Oht]. 

Ni-doped FeS 2 is n type semiconductor [2006Leh]. Resistivity range from 2 to 17 Ω·cm, 

carrier concentration is similar for undoped and Ni doped FrS 2 ranging from 10 15 to 

10 16.6 cm –3 and Hall mobility is ranging from 60 to 270 cm 2 ·V –1 ·s –1 . 

[1977Nis] noted that the Ni atom in the Fe 0.5Ni 0.5S 2 solid solution has a magnetic moment 

of about 1 μ B at low temperatures. 

Pentlandite (τ1) Fe9–xNixS8 remains Pauli-paramagnetic down to 4.2 K with no resultant 

magnetic moments of the Me atoms [1970Kno, 1976Kno]. Fe1.22Ni1.81S3.97 is also Pauliparamagnetic 

with 0.13 μ B per FeNi 2S 4 molecule [1977Tow]. Thermal expansion of pentlandite 

Fe 4.5Ni 4.5S 8 was studied in the temperature range between 25 and 608˚C by XRD in 

[1964Mor]. 

The compressional wave velocity in molten Fe containing 5 mass% Ni and 10 mass% S 

increases with increasing temperature [1997Nas]. 10 mass% S enhances also sound attenuation 

by one or two orders of magnitude compared with liquid Fe. Such behavior at outer core 

pressures and temperatures would constrain the velocity gradient in the outer core and would 

enable the discrimination of potential light alloying elements. 

The temperature dependence of surface tension for the Fe-Ni melts containing the surface 

active element S was measured at 1600˚C by [1993Lee]. It was found to be positive and isosurface 

tension diagram for Fe-Ni-S melts at 1600˚C were presented by [1993Lee]. Sulfur 

decreases slightly the thermal expansion coefficient (α) of the as-rolled Fe-Ni alloy containing 

36 mass% Ni, whereas annealed specimens with addition of S below 0.05 mass% exhibit a 

value of α lower than that for zero addition [1987Ina]. S addition above 0.05 mass% make 

rolling of the sheet impracticable. Yield strength and tensile strength of such alloys rapidly 

increase for addition below 0.03 mass% S, which indicates that the work hardening, due to 

addition of S, is significant. 

Experimental studies of material properties are presented in Table 4. 

Miscellaneous 

Fe-Ni-S alloys are believed to be a possible component of the cores of planetary bodies such as 

Earth, Mars and Io [1997Nas]. 



MSIT 1


9 

The S diffusion coefficients in bulk Fe-Ni alloys, containing 25, 50 and 75 at.% Ni, have 

been determined in the 950 to 1200˚C temperature range by [1982Net]. The values of the 

activation energy have been experimentally found between 142 and 209 kJ·mol –1 . 

Fe xNi 1–xS solid solutions could be prepared by the metal oxide - carbon disulfide reaction 

sintering method [1976Kas]. 

Pentlandite (τ 1) is one of the main ores minerals and the biggest part of world Ni 

production is obtained from this mineral [1955Eli, 1974Vau]. It is likely that much hypogene 

violarite (FeNi2S4) is formed by exsolution from initially deposited monosulfide solid solution 

[1971Cra]. FeNi 2S 4 is also an important mineral quite common in natural Fe-Ni sulfide 

assemblages containing pentlandite [1977Tow]. 

FeS 2 crystals doped with Ni were synthesized using a chemical vapor transport with FeBr 3 

as a transport agent [2006Leh]. Ni concentration was ~200-1500 ppm. 

Physicochemical behavior of Ni, Fe and Pt group elements impurities at an early stage of 

crystallization of Fe-Ni melts with a small surplus of S relative to the total of metals indicates 

that under certain conditions Pt group element-bearing phases can form: (Pt, Fe, Ir)-alloy (at 

initial Fe >> Ni), RuS2 (at initial Ni > Fe), (Pt, Ni)S - in a specimen of pure Ni initial 

composition [2001Sin2]. 

As S is added to the Fe-Ni alloys, segregation coefficients (k) of trace constituents 

change dramatically [1990Jon]. If the composition of the metallic liquid is known, k may be 

predicted - even if the temperature, exact Fe/Ni ratio and information about the activity 

coefficient in the solid phase are unknown. 

Mössbauer study of iron sulfides doped with 3d-transition metals were performed by 

[2000Kim, 2005Nam] at temperatures ranging from liquid nitrogen to 600 K. 

Kinetic of exsolution of pentlandite (τ1) from monosulfide solid solution was studied by 

[2004Ets] by anneal/quench and in-situ cooling experiments. The extent of exsolution was 

monitored using powder neutron diffraction data. Mechanism of pentlandite formation was 

discussed by [2001Kos] based on results obtained by combination of directional crystallization 

with thermal analysis. According to the obtained results it form due to solid state reactions on 

cooling. Solidification behavior of Fe-41 Ni (mass%) alloys at 520-665˚C with flowing H 2/ 

H 2S/N 2 gas mixtures was investigated by [1989Orc1, 1989Orc2]. Reaction kinetics were 

irregular at 520˚C and parabolic at higher temperatures consistent with ratio of self-diffusion 

coefficient DFe/DNi=0.4. [1989Bat] calculated partition coefficient for nickel and sulfur in 

solid/liquid interaction based on parameters from binary systems. The poor agreement 

between calculations and experiments could be due to significant second-order S-S and 

Ni-S effect at higher sulfur concentrations. The electromagnetic levitation of sulfur in liquid 

iron, nickel and iron-nickel alloys was studied by [1986Jac]. By applying principle of local 

equilibrium at metal drop/gas interface, the activities of sulfur in liquid alloys were evaluated. 

Influence of sulfur to dissolution/passivation of Ni-25%Fe alloy was investigated by 

[1981Mar, 1984Mar1, 1984Mar2] using electrochemical and radiotrace technique. 

First-principle calculations of electronic structure and stability of pentlandite solid solution 

were performed by [2002Cha]. Lattice parameters, bulk modulus and heat of formations 

were predicted. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

10 11 

Fe–Ni–S 

. Table 1 

Investigations of the Fe-Ni-S Phase Relations, Structures and Thermodynamics 



Range Studied 

[1930Vog] DTA, metallography Up to 1500˚C / Fe-FeS-Ni3S2-Ni [1938Ura] DTA, metallography Up to 1300˚C / Fe-Ni-S 

[1947Lun] Phase equilibria, XRD 200, 400, 680˚C / Fe-Ni-S 

[1955Cor] Equilibration with gas mixtures 1600˚C / sulfur partial pressure over 

Fe-Ni liquid 

[1955Eli] XRD Room temperature / Fe9–xNixS8 [1956Kul] XRD 500˚C / Fe-Ni-S, 500-1000˚C / Fe/ 

Ni = 1 (Fe+Ni)/S from 7.5/8 to 9/8 

[1955Van] DTA, metallography Up to 1300˚C / Fe-FeS-Ni6S5-Ni [1957Van] DTA, metallography, microhardness 

measurement 

Up to 1400˚C / Fe-FeS-NiS-Ni 

[1960Alc] Equilibration with H2/H2S gas mixture 1540˚C / (Fe-Ni) + S, S activity 

[1960Cla] XRD 500-800˚C up to 40 mass% S, up to 

40 mass% Ni 

[1961Kno] XRD, neutron diffraction, pyknometry Pentlandite solid solutions 

[1961Nis] XRD, magnetization intensity 

measurements, thermomagnetic analysis 

Up to 1100˚C / Fe1–xS-Ni1–xS [1961Stu] XRD, EPMA, chemical analysis, 

metallography 

Room temperature / (Fe xNi 1–x) 2S 

[1962Vay] EMF measurements 1300˚C / up to 50 at.% S 

[1963Cla] Hydrothermal experiments, optical 

microscopy, XRD 

100-1000˚C / FeS 2-NiS 2, 50-100 

at.% S 

[1963Kan] XRD, chemical analysis 950˚C / Fe1–xS-Ni1–xS [1963Kul1] XRD 400-1100˚C / Fe-Ni-S isothermal 

sections 

[1963Kul2] DTA, high-temperature XRD 500-800˚C / pentlandite 

[1966Nal] 

[1967Nal] 

XRD 250-600˚C / 35-40 mass% S 

[1968Jos] Metallography, chemical analysis 1000˚C / (Fe + 10 mass% Ni) + S 

[1968Chm] Equilibrating with H2/H2S gas mixtures, 


Fe-Ni-S up to 32 mol% Ni 

[1968Cra] XRD, electron microprobe, optical 

microscopy 

[1969Ban] Equilibrating with H 2/H 2S gas mixtures, 


400˚C / Fe-Ni-S 

1550˚C / Ni-Fe-S 

[1969Vai] EMF measurement 1300˚C / Fe-Ni-S 



MSIT 1




Range Studied 

[1970Khe] EMF measurement 1300˚C / Fe-Ni-S at 40 at.% S 

[1970Kno] Mössbauer spectroscopy 4.2 K / Fe9–xNixS8 [1970She] XRD, optical microscopy 400-600˚C, 20-60 mass% S 

[1970Vay] EMF measurement 1300˚C / Ni-Fe-S 

[1971Cra] XRD, metallography 300-500˚C / FeS-FeS2-NiS2-NiS [1971Gra] EPMA < 135-500˚C / Fe-FeS2-NiS2-Ni [1972Bye] Gravimetry 1250˚C / (Fe-Ni-S) + H2S/H2 [1972Har] Electron microprobe Compositions of pentladites 

[1972Nic] Optical microscopy, electron microprobe Smithite (Fe,Ni) 3.3S4 associated with 

pentlandite and pyrrotite 

[1972Tay] XRD, EPMA Room temperature / Fe9–xNixS11 

[1973Buz] XRD, EPMA 1600˚C / Fe-Ni-S 

[1973Cra] XRD, electron microprobe, optical 

microscopy 

200-300˚C/ 25-60 mass% S 

[1973Hal] XRD Pentlandite (Ni,Fe) 9S 8 

[1973Mis1] XRD, electron microprobe, optical 

microscopy 

230-600˚C / up to 55 at.% S 

[1973Mis2] XRD Fe1–xS-Ni1–xS, pentlandite, Fe-Ni 

alloy (taenite) 

[1973Raj] XRD Pentlandite solid solutions 

[1973Ven] Chemical analysis, vapor pressure 

measurements 

1575˚C / Fe-Ni-S up to 35 at.% Fe 

[1974Khe] EMF measuring 1300˚C / Fe-Ni-S 

[1974Mis] Electron microprobe, single crystal XRD Composition and stability of 

(Fe,Ni)3S4 violarites 

[1974Vau] XRD, EPMA, Mössbauer spectroscopy 600˚C / Fe1–xS-Ni1–xS [1976Chi] DTA, metallography, dilatometry, X-ray 

spectrometry analysis 

138-1100˚C / Fe-Ni3S2 [1976Fra] TEM, EPMA 600˚C / (Fe,Ni) 1–xS up to 37 mass% 

Ni 

[1976Gul] DTA, X-ray spectrum analysis, 

microhardness measurements 

Up to 1200˚C / Cu2S+Fe [1976Kas] XRD, TGA, magnetic properties and 

electrical resistivity measurements 

[1976Kno] XRD, neutron powder diffraction, 

Mössbauer spectroscopy, magnetic 

susceptibility measurements 



MSIT 1 


20˚C / Fe 1–xS-Ni 1–xS 

Up to 600˚C / Fe 9–xNi xS 8 

11 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

12 11 

Fe–Ni–S 




Range Studied 

[1977Nis] Mössbauer spectroscopy 10-295 K / Fe 0.5Ni 0.5S 2 

[1977Tow] XRD, Mössbauer spectroscopy, magnetic 

susceptibility and thermoelectric power 

measurements 

[1978Len] Equilibrium study, microprobe and chemical 

analysis 

5-300 K / FeNi 2S 4 

1200-1400˚C / up to 25 mass% S, 

liquidus surface 

[1979Sha] SEM, metallography 600-813˚C / Fe-Ni 3S 2 

[1980Vol] XRD Synthesis 600-1000˚C / pressures 4 

GPa, Fe1–xS-Ni1–xS [1981Fit] Wagner model Sulfur activity in dilute Fe-Ni liquid 

solution at 1540˚C 

[1981Oht] XRD, DSC, magnetic susceptibility and 

electric resistivity measurements, 


110-373 K / Fe1–xS-Ni1–xS 

[1982Net, 

1983Net1, 

1983Net2] 

[1983Chu1] 

[1983Chu2] 

Radioisotope analysis 950-1200˚C / (Fe-Ni) + H2S/H2 

Calphad 1200˚C / FeS-Ni3S2, thermodynamic 

properties, liquidus 1200-1350˚C 

[1983Van] Dew point method 1000-1250˚C / Fe-Ni-S 

[1984Bee] XRD, EPMA, metallography 400-600˚C / Fe-Ni-S 

[1984Khe] Dew point method 800-1250˚C / Fe-Ni-S 

[1981Mar] Radiotracer 

[1984Mar1] 

[1984Mar2] 

35 S technique, electrochemical Ni-25Fe, dissolution/passivation 

measurements, X-ray photoelectron 

spectroscopy 

[1984Sel] Electron microprobe Fe-7.2Ni-1.15S (mass%) distribution 

of Ni during solidification 

[1987Con] Equilibration with H2/H2S gas mixtures, 

vapor pressure measurement with Knudsen 

effusion mass-spectrometry 

[1987Hsi1] Calphad, phase equilibration with H2/H2S gas mixtures 

1200-1400˚C / Fe/Ni = 0.25, 1, 4 

Activity of Fe and Ni over liquid 

Fe-Ni-S 

900-1400˚C / Fe-Ni-S, isoactivity 

diagrams, isothermal sections, 

stability diagrams 

[1987Hsi2] Calphad 900-1350˚C / Fe-Ni-S 

[1987Hsi3] Statistical thermodynamic model Monosulfide solid solution 

[1987Hsi4] Equilibration with H2/H2S gas mixtures, 700-900˚C / sulfur activity over 

thermodynamic calculations 

monosulfide solid solution 



MSIT 1



[1989Bar] Equilibration with H2/H2S gas mixture, 

radiotracer 35 S method 

[1989Orc1] XRD, microprobe analysis, electron 

microscopy 



Range Studied 

900-1250˚C / solubility and 

diffusion of S in Fe-Ni alloys 

520-665˚C / Fe-41mass%Ni at 

P S2 = 2·10 –5 -6·10 –1 Pa 

[1989Orc2] XRD, microprobe analysis 520-665˚C / Fe-41mass%Ni at 

PS2 = 2·10 –5 -6·10 –1 Pa 

[1990Jon] Thermodynamic modelling solid/liquid 

interaction 

Fe-Ni-S 

[1991Kes] XRD Room temperature / Ni3S4, FeNi2S4 

[1995Ma] Electron microscopy, microprobe analysis 400, 500˚C / Fe-30Ni-10S (mass%) 

[1997Dre] Differential Scanning Calorimetry (DSC) 20-305˚C / (Fe1–xNix) 0.96S 

[1998Ma] Electron microscopy, microprobe analysis 300-900˚C Fe-rich compositions 

with 2.5-30 mass% Ni, 10 mass% S 

[1998Kar] EPMA 900˚C / up to 70 at.% S 

[1998Sin] XRD, DTA 950-1200˚C / Fe0.96S-Ni0.96S 

liquidus, solidus 

[1999Kon] Calphad 1350-1250˚C / S up to 26 at.% 

[1999Nko] XRD Room temperature / Fe9–xNixS8 and 

Fe1–xS [1999Sin] XRD, optical, electron microscopy, DTA 470-1200˚C / 35-51 at.% S 

[2000Kim] XRD, Mössbauer spectroscopy 77-600 K / Ni0.025Fe0.975S [2000Uen] XRD, optical microscopy 400, 500˚C / Fe-Ni-S 

[2001Far] XRD, sulfur K-edge spectra Room temperature / 

Ni0.923S-Fe0.923S [2001Kos] Directional solidification from melt, XRD, TA, 26.65 at.% Fe, 26.65 at.% Ni and 

optical microscopy, microprobe analysis 46.7 at.% S 

[2001Sin1] XRD, optical, electron microscopy, 

microprobe analysis 

600˚C / 22-55 at.% S 

[2003Kos] S fugacity by equilibration technique 600˚C / Fe-FeS-NiS-Ni 

[2004Kos] Directional crystallization from melt, DTA 840-875˚C / 40-55 at.% S 

[2004Wal2] Calphad 600-1400˚C / Fe-Ni-S 

[2005Nam] XRD, Mössbauer spectroscopy 77-600 K / Ni0.025Fe0.975S [2006Leh] XRD, EPMA synchrotron XRD, mass 

spectrometry 

Room temperature / FeS2 +Ni 



MSIT 1 

13 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

14 11 

Fe–Ni–S 



[2006Sin] S fugacity by equilibration technique, XRD, 

microprobe analysis, optical microscopy, 

SEM 


Range Studied 

900˚C / Fe-FeS-NiS-Ni 

[2006Wal2] Calphad 600˚C / Fe-Ni-S, 300-1200˚C 

FeS-Ni 3S 2 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 

Lattice 

Parameters 


(δFe) cI2 a = 293.15 pure Fe [Mas2] 

1538 - 1394 Im3m 

W 

dissolves 3.8 at.% Ni at 1517˚C 

γ, (γFe,Ni) cF4 

(γFe) Fm3m a = 364.67 pure Fe at 915˚C [V-C2, Mas2] 

1394 - 912 Cu 

(Ni) a = 352.40 pure Ni at 25˚C [Mas2] 

< 1455 below critical temperature: 

γ1 - paramagnetic, Fe enriched 

γ2 – ferromagnetic, Ni enriched 


< 912 Im3m 

W 


(εFe) hP2 a = 246.8 at 25˚C, 13GPa [Mas2] 

P63/mmc Mg 

c = 396.0 

γ’FeNi3 cP4 a = 355.23 63 to 85 at.% Ni [1991Swa] 

< 517 Pm3m 

AuCu3 γ’’FeNi tP4 a = 357.9 [V-C2] 

metastable P4/mmm metastable ordering temperature 320˚C at 

AuCu 

51.2 at.% Ni [1984Ros] 

Fe3Ni cP4 a = 357.5 ± 0.1 metastable [V-C2, Mas2] 

? Fm3m 

Cu 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 


Lattice 

Parameters 


15 

(βS) mP64 a = 1102 [Mas2] 

115.22 - 95.5 P21/c b = 1096 

βS c = 1090 

β = 96.7˚ 

(αS) oF128 a = 1046.4 pure S at 25˚C [Mas2] 

< 95.5 Fddd b = 1286.60 

αS c = 2448.60 

Pyrr, 

hP4 Mineral pyrrhotite, 

Fe1–xNixS1±y P63/mmc 0 ≤ x ≤ 1, 0 ≤ y ≤ 0.1 

< 1182 NiAs 

a = 343.43 ± 0.7 

c = 558.20 ± 0.11 

x = 0.5 [V-C2] 

a = 344.0 ± 0.2 for composition (Fe0.75Ni0.25)0.923S 

c = 567.6 ± 0.3 [2001Far] 

a = 343.71 ± 0.08 for composition (Fe0.5Ni0.5) 0.923S 

c = 559.2 ± 0.1 [2001Far] 

a = 342.5 ± 0.2 for composition (Fe0.25Ni0.75) 0.923S 

c = 539.6 ± 0.3 [2001Far] 

γFe1–xS a = 344.36 ± 0.05 pyrrhotite, 50 to 55 at.% S [V-C2, Mas2] 

1188 - 315 c = 587.59 ± 0.05 

a = 345.3 ± 0.1 

c = 576.5 ± 0.2 

for composition Fe0.923S [2001Far] 

δNi1–xS a = 343.98 ± 0.03 millerite, 49.8 to 52.5 at.% S [V-C2, Mas2] 

< 1001 c = 534.82 ± 0.05 

a = 343.16 ± 0.07 for composition Ni0.923S [2001Far] 

c = 532.5 ± 0.1 

βFe1–xS hP24 a = 596.3 ± 0.1 troilite, at 21˚C [V-C2, Mas2], 

315 - 138 P62c c = 1175.4 ± 0.1 0 ≤ x ≤ 0.07 

Superstructure a = 586.1 

of NiAs-type c = 1157.7 ± 0.1 

a = 599.8 ± 1.1 

c = 1171 ± 1 

at 21˚C and 3.33 GPa [V-C2, Mas2] 

at 120˚C [V-C2, Mas2] 

β(Fe1–xNixS) a = 596.5 ± 0.2 

c = 1171 ± 5 

x = 0.025 [2005Nam] 

αFe1–xS P31c a = 596.6± 0.1 [2008Fer] 0≤ x ≤ 0.07 

< 138 Subgroup of 

P62c 

- 

c = 1176 ± 0.1 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

16 11 

Fe–Ni–S 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 

Lattice 

Parameters 


FeS oP8 high-pressure phase 

(II) Pnma a = 582.5 ± 0.2 at 190˚C [V-C2] 

? MnP b = 346.8 ± 0.1 

c = 693.5 ± 0.6 

a = 571.6 ± 0.9 

b = 334.7 ± 0.3 

c = 669.4 ± 0.9 

at 21˚C and 4.15 GPa [V-C2] 

a = 565 ± 1 

b = 331.6 ± 0.3 

c = 663.1 ± 0.8 

at 21˚C and 6.35 GPa [V-C2] 

FeS tP4 a = 376.8 Mackinawite [V-C2] 

? P4/nmm 

PbO 

c = 503.9 

Py, Fe1–xNixS2 cP12 

Pa3 

FeS2 Mineral pyrite, 0 ≤ x ≤ 0.15 

a = 541.79 ± 0.11 x =0[V-C2, Mas2] 

βFeS2 a = 534.8 ± 0.2 at 1.57 GPa [V-C2] 

< 743 a = 529.3 ± 0.2 at 2.87 GPa [V-C2] 

a = 525.5 ± 0.2 at 3.85 GPa [V-C2] 

V, FexNi1–xS2 cP12 

Pa3 

FeS2 Mineral vaesite, 0 ≤ x ≤ 0.22 

a = 566.8 x = 0.1 [V-C2] 

a = 568.65 ± 0.03 x =0[V-C2, Mas2] 

ηNiS2 

< 1022 a = 561.96 ± 0.06 at 3.2 GPa [V-C2] 

a = 557.45 ± 0.04 at 5.4 GPa [V-C2] 

a = 558.52 ± 0.04 at 4.9 GPa [V-C2] 

αFeS2 oP6 a = 444.1 Marcasite [V-C2, Mas2] 

≲ 444.5 Pnnm b = 542.5 

FeS2 (marcasite) c = 338.7 

a = 446.4 

b = 544 

c = 339 

at 327˚C [V-C2] 

Fe2S3 tP80 a = 1053 [V-C2] 

? P43212 - 

c = 1001 

Fe3S4 hR21 a = 347 ± 2 Smythite [V-C2] 

? R3m c = 3450 ± 2 

Fe3S4 a = 347 ± 0.1 

c = 3440.0 ± 0.1 for composition Fe9–xNixS11 [1972Tay] 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 

Lattice 

Parameters 


Fe3S4 cF56 a = 987.6 ± 0.2 Greigite [V-C2], probably metastable 

? Fd3m 

MgAl2O4 Fe1–xS hP* a = 596.5 ± 0.3 [2008Fer] 0≤ x ≤ 0.125 

< 315 Superstructure 

of 

NiAs type 

c = 1171.6 ± 0.8 

o** a = 1193.0 ± 0.4 [2008Fer] x = 0.1 

Superstructure 

of 

b = 688.8 ± 0.3 

NiAs type c = 2865.8 ± 0.35 

m** a = 1192.0 ± 0.2 [2008Fer] x = 0.125 

Superstructure 

of NiAs-type 

b = 585.8 ± 0.4 

c = 2285.2 ± 0.8 

β = 90.37 ± 0.6˚ 


β, Ni3S2 hR15 a = 573.1 ± 0.5 [V-C2] low-temperature heazlewoodite 

< 533 R32 

Ni3S2 c = 711.9 ± 0.7 

β1(Ni1–xFex)3S2 cF10 high temperature Heazlewoodite 

β1,Ni3S2 F43m 

a = 522.8 ± 0.9 

0 x ≤ 0.35 (36.7 to 42 at.% S) 

800 - 533 36.7 to 42 at.% S [V-C2, Mas2] 

β2(Ni1–xFex) 4S3 cP* - high temperature Heazlewoodite 

0 ≤ x ≤ 0.26 (42 to 44 at.% S) [Mas2] 

β2,Ni4S3 806 - 524 

42 to 44 at.% S [Mas2] 

γNi7S6 oC56 a = 327.4 ± 0.1 Godlevskite [V-C2, Mas2] 

573 - 400 Cmcm b = 1135.9 ± 0.4 

Ni7S6 

c=1615.7 ± 0.7 

γ’Ni7S6 m** a = 3238.8 ± 2.4 [V-C2, Mas2] 

< 400 b=2273.0 ± 2.0 

c=652.5 ± 0.7 

probably metastable 

Ni9S8 o* a = 932.5 ± 0.1 [1994Sto] 

< 436 C222 b = 1123.9 ± 0.1 

- c = 941.00 ± 0.1 

εNiS hP4 a = 344.56 ± 0.08 50 to 50.5 at.% S, 

< 379 P63mc NiS 

c = 540.5 ± 0.1 low temperature phase [V-C2] 



MSIT 1 

17 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

18 11 

Fe–Ni–S 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 

Lattice 

Parameters 


FexNi3–xS4 cF56 0 ≤ x ≤ 1 

Fd3m a = 946.4 ± 0.2 violorite, x =1[1991Kes] 

MgAl2O4 a = 946.5 x =1[V-C2] 

a = 945 for composition Fe1.22Ni1.81S3.97 [1977Tow] 

ζNi3S4 cF56 a = 948.9 Polydymite, [V-C2, Mas2] 

< 356 Fd3m 

Co3S4 Ni6S5 oC48 a = 325.4 [V-C2] 

Cmcm b = 1133.8 

Ni6Se5 c=1643.0 

Ni17S18 hP105 a = 1029.0 ± 0.2 [V-C2] 

P3121 Ni17S18 c = 1599.3 ± 0.3 

*τ1,Fe9–xNixS8+y cF68 Mineral pentlandite 

< 610 Fm3m 3.8 < x < 5.5 [2003Kos] 

Co9S8 

0

. Table 3 



Fe 


Ni S 

L1 +L2 Ð Pyrr + V 1005 U1 L1 5.95 36.21 57.84 

L2 0.04 0.29 99.67 

Pyrr 9.75 37.10 53.15 

V 1.26 33.47 65.27 

L1 + Pyrr Ð β 875 pmax L1 21.3 34.5 44.2 

Pyrr 34.9 13.9 51.1 

β 22.5 32.5 45.0 

L1 + Pyrr Ð β + γ 800 U2 L1 - - - 

L2 + Pyrr Ð Py + V 729 U3 L2 - - - 

Pyrr - - - 

Py 30.82 2.51 66.67 

V 9.46 23.83 66.67 

. Table 4 

Investigations of the Fe-Ni-S Materials Properties 


[1961Nis] Magnetic measurements, 

thermomagnetic analysis 


Magnetization, Curie temperature 

[1964Mor] XRD Thermal expansion for pentlandite 

[1974Vau] Mössbauer spectroscopy Magnetic properties 

[1976Bar] Magnetic measurement, DTA Metal - non-metal transition temperature, 

magnetic susceptibility at 4.2 to 300 K for 

Ni1–xFexSatx = 0.01-0.06 

[1976Chi] Microhardness measurements Microhardness in Fe-Ni3S2 system 

[1976Kno] Faraday method Magnetic susceptibility 

[1980Vol] XRD, resistivity measurements Electrical conductivity of monosulfide solid 

solution at high pressure and temperature 

[1987Ina] Stress-strain diagram method Thermal expansion, yield strength, tensile 

strength 



MSIT 1 

19 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

20 11 

Fe–Ni–S 



[1993Lee] Oscillating droplet method combined 

with electromagnetic levitation 

technique 

Surface tension 

[1997Nas] Ultrasonic interferometry Sound velocity and attenuation 

[2006Leh] Electrical measurements Resistivity, carrier concentration, Hall mobility 

(Electric properties) 



MSIT 1

. Fig. 1 

Fe-Ni-S. Reaction scheme 



MSIT 1 


21 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

22 11 

Fe–Ni–S 

. Fig. 2 

Fe-Ni-S. Liquidus surface projection 



MSIT 1

. Fig. 3a 

Fe-Ni-S. Calculated isothermal section at 1350˚C 



MSIT 1 


23 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

24 11 

Fe–Ni–S 

. Fig. 3b 




MSIT 1

. Fig. 3c 




MSIT 1 


25 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

26 11 

Fe–Ni–S 

. Fig. 4a 




MSIT 1

. Fig. 4b 




MSIT 1 


27 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

28 11 

Fe–Ni–S 

. Fig. 4c 




MSIT 1

. Fig. 5a 




MSIT 1 


29 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

30 11 

Fe–Ni–S 

. Fig. 5b 




MSIT 1

. Fig. 5c 




MSIT 1 


31 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

32 11 

Fe–Ni–S 

. Fig. 6a 

Fe-Ni-S. Experimental isothermal section at 500˚C 



MSIT 1

. Fig. 6b 




MSIT 1 


33 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

34 11 

Fe–Ni–S 

. Fig. 7a 




MSIT 1

. Fig. 7b 




MSIT 1 


35 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

36 11 

Fe–Ni–S 

. Fig. 7c 

Fe-Ni-S. Experimental isothermal section at < 135˚C 



MSIT 1


. Fig. 8a 

Fe-Ni-S. Calculated temperature-composition section for the FeS-Ni 3S 2 join 



MSIT 1 

37 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

38 11 

Fe–Ni–S 

. Fig. 8b 

Fe-Ni-S. Calculated temperature-composition section for the FeS 2-NiS 2 join 



MSIT 1


39 

. Fig. 8c 

Fe-Ni-S. Calculated temperature-composition section for a constant S concentration of x S = 0.471 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

40 11 

Fe–Ni–S 

. Fig. 9a 

Fe-Ni-S. Calculated potential diagram at 700˚C 



MSIT 1

. Fig. 9b 




MSIT 1 


41 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

42 11 

Fe–Ni–S 

. Fig. 9c 




MSIT 1

. Fig. 9d 




MSIT 1 


43 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

44 11 

Fe–Ni–S 

. Fig. 10 

Fe-Ni-S. Calculated Fe activity in the liquid phase (expressed as equilibrium partial pressure of Fe 

in the gas phase) at 1300˚C, values are x Ni 



MSIT 1


. Fig. 11 

Fe-Ni-S. Calculated Fe activity in the liquid phase for the Ni 3S 2-FeS and FeS-Ni joins 



MSIT 1 

45 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

46 11 

Fe–Ni–S 

. Fig. 12a 

Fe-Ni-S. Calculated S activity in the liquid phase (expressed as equilibrium partial pressure of S 2 

in the gas phase) at Fe/Ni ratio of 0.25 



MSIT 1


47 

. Fig. 12b 


in the gas phase) at Fe/Ni ratio of 1.0 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

48 11 

Fe–Ni–S 

. Fig. 12c 


in gas phase) at Fe/Ni ratio of 4.0 



MSIT 1


49 

. Fig. 13a 

Fe-Ni-S. Calculated S activity in the monosulfide phase (expressed as equilibrium partial 

pressure of S 2 in the gas phase) at various Fe/Ni ratios and temperatures around 700˚C; values 

indicate Fe/Ni ratio 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

50 11 

Fe–Ni–S 

. Fig. 13b 






MSIT 1


51 

. Fig. 13c 






MSIT 1 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

52 11 

Fe–Ni–S 

. Fig. 13d 


pressure of S 2 in the gas phase) at various Fe/Ni ratios and temperatures aroud 850˚C; values 




MSIT 1


53 

. Fig. 13e 






MSIT 1 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

54 11 

Fe–Ni–S 

. Fig. 14 

Fe-Ni-S. Calculated activity of FeS and Ni 3S 2 along the FeS-Ni 3S 2 join 



MSIT 1

References 


55 

[1930Vog] Vogel, R., Tonn, W., “About the Ternary System Iron-Nickel-Sulfur” (in German), Arch. Eisenhuettenwes., 

3(12), 769–780 (1930) (Experimental, Phase Relations, Magn. Prop., 5) 

[1938Ura] Urazov, G.G., Filin, N.A., “Investigation of Alloys of the Fe-Ni-S System” (in Russian), Metallurg, 2, 

3–19 (1938) (Experimental, Morphology, Phase Diagram, Phase Relations, 21) 

[1943Haw] Hawley, J.E., Colgrove, G.L., Zurbrugg, H.F., “The Fe-Ni-S System. An Introduction with New Data on 

the Crystallization of Pyrrhotite and Pentlandite”, Econ. Geol., 38(5), 335–388 (1943) (Crys. Structure, 

Experimental, Phase Diagram, Phase Relations, Thermodyn., 73) 

[1947Lun] Lundqvist, D., “X-Ray Studies in the Ternary System Fe-Ni-S”, Arkiv Kemi, Mineral. Geol., 24A(22) 

1–12 (1947) as quoted in [1973Mis2] 

[1949Jae] Jaenecke, E., “S-Fe-Ni” (in German) in “Kurzgefasstes Handbuch aller Legierungen”, Winter Verlag, 


[1955Cor] Cordier, J.A., Chipman, J., “Activity of Sulphur in Liquid Fe-Ni Alloys”, Trans. Amer. Inst. Min. Met. 

Eng., Inst. Metals Div., 203(8), 905–907 (1955) (Experimental, Phase Relations, 7) 

[1955Eli] Eliseev, E.N., “Chemical Composition and Crystal Structure of Pentlandite” (in Russian), Zap. Vses. 

Mineral. Obshchest., 84, 53–62 (1955) (Experimental, Crystal Structure, Phase Diagram, Phase Relations, 

21) 

[1955Van] Vanyukov, V.A., Vanyukov, A.V., Tarashchuk, N.T., “The Fe-Ni-S Constitution Diagram” (in Russian), 

Tsvet. Met., (4), 23–27 (1955) (Experimental, Phase Diagram, Phase Relations, 3) 

[1956Kul] Kullerud, G., “Subsolidus Phase Relations in the Fe-Ni-S System”, Carnegie Inst. Washington, Yearbook, 

55, 175–180 (1956) (Experimental, Phase Relations, 1) 

[1957Van] Vanyukov, V.A., Vanyukov, A.V., Tarashchuk, N.T., “Phase Diagram of the System Fe-Ni-S” (in 

Russian), Sb. Nauch. Tr. Moskovskii Inst. Tsvet. Metallov i Zolota, (26), 108–119 (1957) (Experimental, 


[1960Alc] Alcock, C.B., Cheng, L.L., “A Thermodynamic Study of Dilute Solutions of Sulphur in Liquid Iron, 

Cobalt and Nickel and Binary Alloys between these Metals”, J. Iron Steel Inst., 195(2), 169–173 (1960) 

(Experimental, Thermodyn., 18) 

[1960Cla] Clark, S.P., Kullerud, G., “The System Fe-Ni-S”, Carnegie Inst. Washington, Yearbook, 59, 141–144 


[1961Kno] Knop, O., Ibrahim, M.A., “Chalcogenides of the Transition Elements. II. Existence of the π Phase in the 

M 9S 8 Section of the System Fe-Co-Ni-S”, Canad. J. Chem., 39, 297–317 (1961) (Experimental, Phase 


[1961Nis] Nishimara, K., Kondo, Y., “Studies on the Ni Matte. I. The Ni-Fe-S System”, Mem. Fac. Eng. Kyoto 

Univ., 22, 242–263 (1961) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 25) 

[1961Stu] Stumpfl, E.F., “Some New Platinoid-Rich Minerals, Identified with the Electron Microanalyser”, 

Mineral. Mag., 32(254), 833–847 (1961) (Experimental, Morphology, Phase Relations, 19) 

[1962Kle] Klemm, D.D., “Investigations on Solid Solution Formation in the Ternary FeS 2-CoS 2-NiS 2 and its 

Relation to the Constitution of Natural “Bravoite”” (in German), Neues Jahrb. Mineral. Monatsh., 3–4 

(3-4), 76–91 (1962) (Experimental, Phase Relations, 61) 

[1962Vay] Vaysbrud, S.E., Verner, B.F., Heyfetz, V.L., “Activity of the Iron in the Fe-Ni-S Melts” (in Russian), Izv. 

Vyss. Uchebn. Zaved., Chern. Metall., (1), 59–67 (1962) (Kinetics, Phase Diagram, Phase Relations, 


[1963Cla] Clark, L.A., Kullerud, G., “The Sulfur-Rich Portion of the Fe-Ni-S System”, Econ. Geol., 58, 853–885 

(1963) (Experimental, Phase Relations, Thermodyn., 38) 

[1963Kan] Kaneko, H., Nishizawa, T., Tamaki, K., “Study on Phase Diagrams of Sulphides in Steels” (in Japanese), 

Nippon Kinzoku Gakkai Shi, 27(7), 312–319 (1963) (Experimental, Phase Relations, 23) 

[1963Kul1] Kullerud, G., “The Fe-Ni-S System”, Carnegie Inst. Washington, Yearbook, 175–189 (1963) (Experimental, 


[1963Kul2] Kullerud, G., “Thermal Stability of Pentlandite”, Canad. Mineral., 7, 353–366 (1963) (Experimental, 


[1964Kul] Kullerud, G., “Review and Evaluation of Recent Research on Geologically Significant Sulfide-Type 

Systems”, Fortschritte Mineral., 41(2), 221–270 (1964) (Phase Diagram, Phase Relations, Review, 109) 

[1964Mor] Morimoto, N., Kullerud, G., “Pentlandite: Thermal Expansion”, Carnegie Inst. Washington, Yearbook, 




MSIT 1 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

56 11 

Fe–Ni–S 

[1966Nal] Naldrett, A.J., Kullerud, G., “Limits of the Fe 1–xS-Ni 1–xS Solid Solution between 600 and 250˚C”, 

Carnegie Inst. Washington, Yearbook, 65, 320–326 (1966) (Experimental, Phase Relations, 1) 

[1967Nal] Naldrett, A.J., Craig, J.R., Kullerud, G., “The Central Portion of the Fe-Ni-S System and its Bearing on 

Pentlandite Exsolution in Iron-Nickel-Sulphide Ores”, Econ. Geol., 62, 826–847 (1967) (Experimental, 

Morphology, Phase Diagram, Phase Relations, Thermodyn., 36) 

[1968Chm] Chmelar, I., Buzek, Z., Hlineny, J., “Determination of the Sulfur Activity in the Fe-X-S Systems Using a 

Laboratory Electroslag Furnace” (in Czech), Sborn. Ved. Praci Vysoke Skoly Banske Ostrave, 14(3), 

175–181 (1965) (Experimental, Thermodyn., 8) 

[1968Cra] Craig, J.R., Naldrett, A.J., Kullerud, G., “The Fe-Ni-Sulphide System. 400˚C Isothermal Diagram”, 

Carnegie Inst. Washington, Yearbook, 66, 440–441 (1968) (Experimental, Phase Relations, 1) 

[1968Jos] Josey, G.A., Floridis, T.P., “Solubility of S in Fe Alloys at 1000˚C”, Trans. Met. Soc. AIME, 242, 161–162 


[1969Ban] Ban-ya, S., Chipman, J., “Sulfur in Liquid Iron Alloys: II – Effects of Alloying Elements”, Trans. Met. 

Soc. AIME, 245(1), 133–143 (1969) (Experimental, Thermodyn., 18) 

[1969Kul] Kullerud, G., Yund, R.A., Moh, G.H., “Phase Relations in the Cu-Fe-S, Cu-Ni-S, and Fe-Ni-S Systems”, 

Magmat. Ore Deposits, Symp., 4, 323–343 (1969) (Experimental, Phase Diagram, Phase Relations, 48) 

[1969Vai] Vaisbrud, S.E., Remen, T.F., Sheinin, A.B., “Thermodynamic Activity of Iron in System Iron-Nickel- 

Sulphur at 1300˚C”, Russ. J. Phys. Chem. (Engl. Transl.), 43(12), 1780–1781 (1969) (Experimental, Phase 

Relations, 4) 

[1970Khe] Khejfec, V.L., Vajsburd, S.E., Remen, T.F., “About Experimental Identification of the Metal Activity in 

the Multicomponent Melts” (in Russian), Tr. Proekt. Nauch.-Issled. Inst. “Gipronikel”, 46, 39–46 (1970) 

(Experimental, Kinetics, Thermodyn., 14) 

[1970Kno] Knop, O., Huang, C.-H., Woodhams, F.W.D., “Chalcogenides of the Transition Elements. VII. A 

Mössbauer Study of Pentlandite”, Amer. Mineral., 55(7-8), 1115–1130 (1970) (Experimental, Crys. 

Structure, Magn. Prop., 37) 

[1970She] Shewman, R.W., Clark, L.A., “Pentlandite Phase Relations in the Fe-Ni-S System and Notes on 

Monosulfide Solid Solution”, Canad. J. Earth Sci., 7, 67–85 (1970) (Experimental, Phase Relations, 

Physical Properties, Thermodyn., 28) 

[1970Sug] Sugaki, A., “Recent Studies on the Phase Equilibria of Sulphide Minerals” (in Japanese), Kozan 

Chishitsu, 20(101), 237–257 (1970) (Review, Phase Relations, 59) 

[1970Vay] Vaysbrud, S.E., Remen, T.F., Novikova, N.N., “Thermodynamic Properties of Liquid Slags and Mattes 

and Component Distribution between Them” (in Russian), Tr. Proekth. Nauchno-Issled. Inst. “Gipronikel”, 

46, 5–31 (1970) (Experimental, Thermodyn., 41) 

[1971Cra] Craig, J.R., “Violarite Stability Relations”, Am. Mineral, 56, 1303–1311 (1971) (Experimental, Phase 

Diagram, Phase Relations, Thermodyn, 13) 

[1971Gra] Graterol, M., Naldrett, A.J., “Mineralogy of the Marbridge No.3 and No.4 Nickel-Iron Sulfide 

Deposits”, Econ. Geol., 66, 886–900 (1971) (Experimental, Crys. Structure, Phase Diagram, Phase 


[1972Bye] Byerley, J.J., Takebe, N., “Thermodynamics of the Fe-Ni-S System at 1250˚C”, Metall. Trans., 3(2), 


[1972Har] Harris, D.C., Nickel, E.H., “Pentlandite Compositions and Associations in some Mineral Deposits”, 

Canad. Mineral., 11, 861–878 (1972) (Experimental, Phase Diagram, Phase Relations, 29) 

[1972Nic] Nickel, E.H., “Nickeliferous Smythite from Some Canadian Occurrences”, Canad. Mineral., 11, 

514–519 (1972) (Experimental, Morphology, 11) 

[1972Tay] Taylor, L.A., Williams, K.L., “Smythite, (Fe,Ni) 9S 11 - a Redefinition.”, Am. Mineral, 57(11-12), 

1571–1577 (1972) (Experimental, Phase Relations, Crys. Structure, 13) 

[1972Vay] Vaysbrud, S.E., Burylev, B.P., Zedina, I.N., Remen, T.F., “Thermodynamic Properties of Sulfide Melts 

and their Quantitative Description” (in Russian), Zhurn. Fiz. Khim., 46(6), 1528–1531 (1972) (Experimental, 


[1973Buz] Buzek, Z., “Effect of Alloying Elements on the Solubility and Activity of Oxygen and Sulphur in Liquid 

Iron at 1600˚C” in “Metall. Chem. – Appl. Ferrous Metall.”, Int. Symp., Sheffield, July 1971, Iron and Steel 

Inst., London, 173–177 (1973) (Experimental, Review, Crys. Structure, 8) 

[1973Cra] Craig, J.R., “Pyrite-Pentlandite Assemblages and Other Low Temperature Relations in the Fe-Ni-S 

System”, Amer. J. Sci., 273A, 496–551 (1973) (Experimental, Morphology, Phase Relations, 26) 



MSIT 1


57 

[1973Hal] Hall, S.R., Stewart, J.M., “The Crystal Structure of Argentian Pentlandite (Fe,Ni) 8AgS 8 Compared with 

the Refined Structure of Pentlandite (Fe,Ni) 9S 8”, Canad. Mineral., 12, 169–177 (1973) (Crystal Structure, 


[1973Mis1] Misra, K.C., Fleet, M.E., “Unit Cell Parameters of Monosulfide, Pentlandite and Taenite Solid 

Solutions Within the Fe-Ni-S System”, Mater. Res. Bull., 8, 669–678 (1973) (Experimental, Phase 


[1973Mis2] Misra, K.C., Fleet, M.E., “The Chemical Compositions of Synthetic and Natural Pentlandite 

Assemblages”, Econ. Geol., 68, 518–539 (1973) (Experimental, Phase Relations, Thermodyn., 89) 

[1973Raj] Rajamani, V., Prewitt, C.T., “Crystal Chemistry of Natural Pentlandites”, Canad. Mineral., 12, 178–187 

(1973) (Crys. Structure, Phys. Prop., Experimental, 26) 

[1973Ven] Venal, W.V., Geiger, G.H., “The Thermodynamic Behavior of Sulfur in Molten Nickel and Nickel-Base 

Alloys”, Metall. Trans., 4(11), 2567–2573 (1973) (Experimental, Thermodyn., 24) 

[1974Khe] Kheifets, V.L., Vaysbrud, S.E., “About some Properties of Sulfide Melts of Iron Group Metals” (in 

Russian) in “Elektrokhim. Rasplavy”, Nauka, Moscow, 118–122 (1974) (Review, Thermodyn., 21) 

[1974Mis] Misra, K.C., Fleet, M.E., “Chemical Composition and Stability of Violarite”, Econ. Geol., 69, 391–403 

(1974) (Crys. Structure, Experimental, Interface Phenomena, Morphology, Phase Relations, 33) 

[1974Sig] Sigworth, G.K., Elliott, J.F., “The Thermodynamics of Liquid Dilute Iron Alloys”, Met. Sci., 8, 298–310 

(1974) (Review, Thermodyn., 249) 

[1974Vau] Vaughan, D.J., Craig, J.R., “The Crystal Chemistry and Magnetic Properties of Iron in the 

Monosulphide Solid Solution of the Fe-Ni-S System”, Am. Mineral, 59(9-10), 926–933 (1974) (Experimental, 


[1976Bar] Barthelemy, E., Chavant, C., Collin, G., Gorochov, O., “Metal-Non Metal Transition of Ni 1–xS and NiS 

Substituted by Se, As and Fe: Transport Properties and Structural Aspect”, J. Physique, Colloq., 37, 17–22 

(1976) (Crys. Structure, Experimental, Phys. Prop., 21) 

[1976Chi] Chizhikov, D.M., Gulyanitskaya, Z.F., Blagoveshchenskaya, N.V., Blokhina, L.I., “The Ni 3S 2-Fe System”, 

Russ. J. Inorg. Chem., 21(7), 1052–1054 (1976), translated from Zh. Neorg. Khim., 21(7), 1913–1916 


[1976Fra] Francis, C.A., Craig, J.R., “Pyrrhotite: The nA (or 2A, 3C) Superstructure Reviewed”, Am. Mineral, 61, 

21–25 (1976) (Experimental, Phase Diagram, Phase Relations, Phys. Prop., 18) 

[1976Gul] Gulyanitskaya, Z.F., Blokhina, I.I., Blagoveshchenskaya, N.V., “Phase Composition and Transformations 

in Some Sulphide Systems” (in Russian), in “Tsvetn. Metall.”, Nauka, Moscow, 291–298 (1976) 

(Experimental, Phase Relations, 26) 

[1976Kas] Kasahara, Y., Nitta, T., Hayakawa, S., “Electrical and Magnetic Properties of Fe-Ni Sulphide Ceramics”, 

J. Am. Ceram. Soc., 59, 204–206 (1976) (Experimental, Crys. Structure, Electr. Prop., Magn. Prop., 7) 

[1976Kno] Knop, O., Huang, C.-H., Reid, K.I.G., Carlow, J.S., Woodhams, F.W.D., “Chalcogenides of the 

Transition Elements. X. X-Ray, Neutron, Mössbauer and Magnetic Studies of Pentlandite and the π 

Phases π (Fe, Co, Ni, S), Co8MS8 and Fe4Ni4MS8 (M = Ru, Rh, Pd)”, J. Solid State Chem., 16(1-2), 

97–116 (1976) (Experimental, Crys. Structure, Phase Relations, 38) 

[1977Nis] Nishihara, Y., Ogawa, S., Adachi, K., Tohda, M., “Mössbauer Study of Fe 0.5Ni 0.5S 2. Hyperfine Field 

at 57 Fe in Fe 0.5Ni 0.5S 2”, J. Phys. Soc. Jpn., 42(4), 1180 (1977) (Experimental, Crys. Structure, Magn. 

Prop., 13) 

[1977Tow] Townsend, M.G., Gosselin, J.R., Horwood, J.L., Ripley, L.G., Tremblay, R.J., “Violarite, a Metallic 

Natural Spinel”, Phys. Status Solidi, 40A, K25–K29 (1977) (Experimental, Crys. Structure, Magn. 

Prop., 8) 

[1978Len] Lenz, J.G., Conard, B.R., Sridhar, R., Warner, J.S., “The Liquidus Surface and Tie-Lines in the Iron- 

Nickel-Sulfur System Between 1473 and 1673 K”, Metall. Trans. B, 9(3), 459–462 (1978) (Experimental, 


[1979Sha] Shatynski, S.R., Hirth, J.P., Rapp, R.A., “Solid-State Displacement Reactions between Selected 

Metals and Sulfides”, Metall. Trans. A, 10A(5), 591–598 (1979) (Experimental, Phase Relations, 


[1980Vol] Vollstadt, H., Seipold, U., Kraft, A., “Structural and Electrical Relations of Monosulphide Solid 

Solution in the Fe-Ni-S System at High Pressures and Temperatures”, Phys. Earth Planet. Interiors, 22 

(3-4), 267–271 (1980) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 4) 

[1981Fit] Fitzner, K., Chang, Y.A., “The Activity Coefficient of Sulfur in Dilute Binary Liquid Metal Alloys”, 

Chem. Metal. - Tribute Carl Wagner, Proc. Symp., 119–135 (1981) (Review, Thermodyn., 45) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

58 11 

Fe–Ni–S 

[1981Mar] Marcus, P., Bouruet, A., Oudar, J., “Dissolution and Passivation of Nickel-Iron Alloys - Influence of 

Sulfur”, Mem. Sci. Rev. Metall., 78(9), 509–512 (1981) (Experimental, Thermodyn., 11) 

[1981Oht] Ohtani, T., Kosuge, K., Kachi, S., “Metal-Semiconductor Transition with Anomalous Thermal 

Hysteresis Observed in Hexagonal (Ni 1–xFe) 1–yS, (0 ≤ x ≤ 0.30, 0 ≤ y ≤ 0.035)”, Bull. Chem. Soc. Jap., 

54(2), 568–575 (1981) (Experimental, Electr. Prop., Kinetics, Magn. Prop., 35) 

[1982Hsi] Hsieh, K.-C., Chang, Y.A., Zhong, T., “The Fe-Ni-S System Above 700˚C”, Bull. Alloy Phase Diagrams, 

3(2), 165–172 (1982) (Phase Diagram, Phase Relations, Review, 17) 

[1982Net] Netter, P., Barbouth, N., Oudar, J., “Sulfur Diffusion in 25%, 50% and 75% Iron-Nickel Alloys” (in 

French), Compt. Rend. Acad. Sci. Paris, Ser. 2, 295(10), 867–869 (1982) (Experimental, Interface 


[1983Chu1] Chuang, Y.Y., Chang, Y.A., “A Thermodynamic Analysis of Ternary Cu-Ni-S and Fe-Ni-S” in “Adv. 

Sulfide Smel.”, Proc. Int. Sulf. Smel. Symp. Extr. Proc. Met. Soc. AIME, 1, 73–79 (1983) (Experimental, 


[1983Chu2] Chuang, Y.Y., Chang, Y.A., “Thermodynamic Behavior of Metal-Sulfur Melts” in “Molten Salt Chem. 

Technol.”, Proc. Int. Symp. Electrochem. Soc. Jpn., 1, 201–208 (1983) (Experimental, Phase Relations, 


[1983Net1] Netter, P., Barbouth, N., “Investigation of Sulfur Solubility in Iron-Nickel Alloys” (in French), Mem. 

Etud. Sci. Rev. Metall., 80(12), 701–703 (1983) (Experimental, Phase Relations, 10) 

[1983Net2] Netter, P., Barbouth, N., Oudar, J., “Thermodynamic Study of Iron-Nickel-Sulphur Solid Solutions”, 

Scr. Metall., 17(9), 1083–1085 (1983) (Experimental, Thermodyn., 7) 

[1983Van] Vanyukov, A.V., Khamin, A.G., Aleksandrov, M.E., Syromyatnikova, A.S., Asabin, A.N., “Phase 

Equilibrium in the Nickel-Iron-Sulphur System” (in Russian), Nauchn. Trudy Moskov. Inst. Stali i 

Splavov, 146(146), 50–54 (1983) (Experimental, Thermodyn., 6) 

[1984Bee] Beek, J.A., Kok, P.M.T., Loo, F.J.J., “Solid-State Displacement Reactions in the Iron-Nickel-Sulfur and 

Copper-Nickel-Sulfur Systems Between 400 and 500˚C”, Oxid. Met., 22(3–4), 147–160 (1984) (Experimental, 


[1984Khe] Khestanov, T.Kh., Kamyanov, V.K., Bystrov, V.P., “Equilibrium Vapour Pressure of Sulphur Over 

Sulphides of the Iron-Nickel-Sulphur System Near NiS” (in Russian), Izv. Vyss. Uchebn. Zaved., Tsvetn. 

Metall., (2), 54–59 (1984) (Experimental, Thermodyn., 5) 

[1984Mar1] Marcus, P., Teissier, A., Oudar, J., “The Influence of Sulfur on the Dissolution and the Passivation of a 

Nickel-Iron Alloy-1. Electrochemical and Radiotracer Measurements”, Corros. Sci., 24(4), 259–268 

(1984) (Experimental, Thermodyn., 11) 

[1984Mar2] Marcus, P., Olefjord, I., Oudar, J., “The Influence of Sulfur on the Dissolution and the Passivation of a 

Nickel-Iron Alloy-II. Surface-Analysis by ESCA”, Corros. Sci., 24(4), 269–278 (1984) (Experimental, 


[1984Ros] Rossiter, P.L., Jago, R.A., “Towards a True Fe-Ni Phase Diagram”, Mater. Res. Soc. Symp. Proc., 21, 

407–411 (1984) (Phase Diagram, Phase Relations, Review, 26) 

[1984Sel] Sellamuthu, R., Goldstein, J.I., “Measurement and Analysis of Distribution Coefficients in Fe-Ni Alloys 

Containing S and/or P: Part I. KNi and KP”, Metall. Trans. A, 15(9), 1677–1685 (1984) (Experimental, 

Morphology, Phys. Prop., Thermodyn., 11) 

[1986Jac] Jacob, K.T., Hajra, J.P., “Electromagnetic Levitation Study of Sulfur in Liquid Iron, Nickel and Iron- 

Nickel Alloys”, Trans. Ind. Inst. Met., 39(1), 62–69 (1986) (Experimental, Phase Relations, 35) 

[1987Con] Conard, B.R., Meyer, G.A., Timberg, L., Warner, J.S., Hynek, P., “Thermodynamic Activities of 

Components in Homogeneous Ni-Fe-S Mattes at 1473-1673K”, Canad. Metall. Quart., 26, 299–309 

(1987) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 32) 

[1987Fle] Fleet, M., “Structure of Godlevskite, Ni 9S 8”, Acta Crystallogr., C43, 2255–2257 (1987) (Crys. Structure, 


[1987Hsi1] Hsieh, K.-C., Kao, M.Y., Chung, A.Y. “Thermochemical Description of the Ternary Iron-Nickel-Sulfur 

System”, Can. Metall. Quart., 26(4) 311–327 (1987) (Thermodyn., Phase Diagram, Theory, 33) 

[1987Hsi2] Hsieh, K.-C., Vlach, K.C., Chang, Y.A., “The Fe-Ni-S System. I. A Thermodynamic Analysis of the 

Phase Equilibria and Calculation of the Phase Diagram from 1173 to 1623 K”, High Temp. Sci., 23, 

17–38 (1987) (Calculation, Experimental, Phase Diagram, Phase Relations, Thermodyn., 27) 

[1987Hsi3] Hsieh, K.-G., Schmid, R., Chang, Y.A., “The Fe-Ni-S System. II. A Thermodynamic Model for the 

Ternary Monosulfide Phase with the Nickel Arsenide Structure”, High Temp. Sci., 23, 39–52 (1987) 

(Thermodyn., Calculation, 8) 



MSIT 1


59 

[1987Hsi4] Hsieh, K.-Ch., Kao, M.-Y., Chang, Y.A., “A Thermogravimetric Investigation of the Fe-Ni-S System 

from 700 to 900˚C”, Oxid. Met., 27(3–4), 123–141 (1987) (Experimental, Phase Diagram, Phase 


[1987Ina] Inaba, M., Teshima, K., “Effects of Phosphorus and Sulphur on Thermal Expansion and Mechanical 

Properties of Fe-36Ni”, J. Mater. Sci. Lett., 6(6), 727–728 (1987) (Experimental, Mechan. Prop., 9) 

[1988Rag] Raghavan, V., “The Fe-Ni-S (Iron-Nickel-Sulphur) System” in “Phase Diagrams of Ternary Iron Alloys”, 

Indian Inst. Met., Calcutta, 2, 196 (1988) (Review, Phase Relations, 8) 

[1989Bar] Barbouth, N., Oudar, J., “Solubility and Diffusion of Sulfur in Pure Metals and Alloys” (in French), 

Mem. Sci. Rev. Metall., 86(12), 777–788 (1989) (Review, Thermodyn., Phase Relations, 60) 

[1989Bat] Battle, T.P., Pehlke, R.D., “Equilibrium Partition Coefficients in Iron-Based Alloys”, Metall. Trans. B, 

20B, 149–160 (1989) (Experimental, Thermodyn., 61) 

[1989Orc1] Orchard, J.P., Young, D.J., “Morphological Evolution During Sulfidation of an Iron-Nickel 

Alloy”, Oxid. Met., 31(1-2), 105–121 (1989) (Experimental, Interface Phenomena, Morphology, Thermodyn., 

17) 

[1989Orc2] Orchard, J.P., Young, D.J., “Sulfidation Behavior of an Iron-Nickel Alloy”, J. Electrochem. Soc., 136(2), 

545–550 (1989) (Experimental, Mechan. Prop., Phase Relations, Thermodyn., 32) 

[1990Jon] Jones, J.H., Malvin, D.J., “A Nonmetal Interaction Model for the Segregation of Trace Metals during 

Solidification of Fe-Ni-S, Fe-Ni-P, Fe-Ni-S-P Alloys”, Metall. Trans. B, 21B, 697–706 (1990) (Theory, 


[1991Kes] Kesler, Y.A., Smirnov, S.G., Pokholok, K.V., Viting, B.N., “Peculiarities of the Electronic Structure of 

Co, Ni-Thiospinel”, Inorg. Mater. (Engl. Transl.), 27, 977–980 (1991), translated from Izv. Akad. Nauk 

SSSR. Neorg. Mater., 27(6), 1162–1165 (1991) (Experimental, Crys. Structure, 18) 

[1991Swa] Swartzendruber, L.J., Itkin, V.P., Alcock, C.B., “Fe-Ni (Iron-Nickel)” in “Phase Diagrams of Binary 

Nickel Alloys”, Nash, P. (Ed.), ASM International, Materials Park, OH, 110–132 (1991) (Phase Diagram, 


[1991Tay] Taylor, J.R., Dinsdale, A.T., “Application of the Calculation of Phase Equilibria to the Pyrometallurgical 

Extraction from Sulphide Ores” in “User Aspects of Phase Diagrams”, Proc. Conf., Petten, Netherlands 

June 1990, Hayes, F.H. (Ed.), The Inst. Metals, UK, 209–224 (1991) (Calculation, Phase Diagram, Phase 


[1993Lee] Lee, H.-K., Frohberg, M.G., Hajra, J.P., “Surface-Tension Measurements of Liquid Iron-Nickel-Sulfur 

Ternary-System Using the Electromagnetic Oscillating Droplet Technique”, ISIJ Int., 33(8), 833–838 

(1993) (Experimental, Interface Phenomena, 37) 

[1994Sto] Stolen, S., Fjellvag, H., Gronvold, F., Seim, H., Westrum, E.F., “Phase Stability and Structural 

Properties of Ni 7±δS 6 and Ni 9S 8 Heat Capacity and Thermodynamic Properties of Ni 7S 6 at Temperatures 

from 5 K to 970 K and Ni 9S 8 from 5 K to 673 K”, J. Chem. Thermod., 26, 987–1000 (1994) 


[1995Ma] Ma, L., Williams, D.B., Goldstein, J.I., “Phase-Decomposition in the Iron-Rich Iron-Nickel-Sulfur 

System from 900 to 300˚C. - Application to Meteoritic Metal”, Meteoritics, 30(5), 538–539 (1995) 


[1997Dre] Drebushchak, V.A., Fedorova, Z.N., Sinyakova, E.F., “Decay of (Fe 1–xNi x) 0.96S - DSC Investigation”, J. 

Therm. Anal., 48(4), 727–734 (1997) (Experimental, Kinetics, Phase Relations, Magn. Prop., 12) 

[1997Nas] Nasch, P.M., Manghnani, M.H., Secco, R.A., “Anomalous Behavior of Sound Velocity and Attenuation 

in Liquid Fe-Ni-S”, Science, 277(5323), 219–221 (1997) (Experimental, Thermodyn., 32) 

[1998Kar] Karup-Moller, S., Makovicky, E., “The Phase System Fe-Ni-S at 900˚C”, Neues Jahrb. Mineral., 

Monatsh., 8, 373–384 (1998) (Experimental, Phase Relations, Thermodyn., 12) 

[1998Kon] Kongoli, F., Dessureault, Y., Pelton, A.D., “Thermodynamic Modelling of Liquid Fe-Ni-Cu-Co-S 

Mattes”, Metall. Mater. Trans. B, 29B, 591–601 (1998) (Assessment, Calculation, Phase Relations, 


[1998Ma] Ma, L., Williams, D.B., Goldstein, J.I., “Determination of the Fe-rich Portion of the Fe-Ni-S Phase 

Diagram”, J. Phase Equilib., 19(4), 299–309 (1998) (Experimental, Phase Relations, 28) 

[1998Sin] Sinyakova, E.F., Kosyakov, V.I., Shestakov, V.A., “Fe 0.96S-Ni 0.96S Join of the Fe-Ni-S System”, Inorg. 

Mater. (Engl. Trans.), 34(5), 432–433 (1998) (Experimental, Phase Relations, 9) 

[1999Kon] Kongoli, F., Pelton, A.D., “Model Prediction of Thermodynamic Properties of Co-Fe-Ni-S Mattes”, 

Metall. Mater. Trans. B, 30B, 443–450 (1999) (Calculation, Phase Relations, Thermodyn., 51) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

60 11 

Fe–Ni–S 

[1999Nko] Nkoma, J.S., Ekosse, G., “X-Ray Diffraction Study of Chalcopyrite CuFeS 2, Pentlandite (Fe, Ni) 9S 8 and 

Pyrrhotite Fe 1–xS Obtained from Cu-Ni Ore Bodies”, J. Phys.: Condens. Matter, 11, 121–128 (1999) 

(Experimental Crys. Structure, 10) 

[1999Sin] Sinyakova, E.F., Kosyakov, V.I., Shestakov, V.A., “Investigation of the Surface of the Liquidus of the 

Fe-Ni-S System at X S < 0.51”, Metall. Mater. Trans. B, 30B, 715–722 (1999) (Experimental, Phase 


[2000Kim] Kim, E.C., “Crystallographic and Magnetic Properties of Iron Sulfides Doped with 3d Transition 

Metals”, J. Mater. Sci. Letter., 19, 693–694 (2000) (Crys. Structure, Magn. Prop., Experimental, 8) 

[2000Uen] Ueno, T., Ito, S.-I., Nakatsuka, S., Nakano, K., Harada, T., Yamazuaki, T., “Phase Equilibria in the 

System Fe-Ni-S at 500 and 400˚C”, J. Mineral. Petrol. Sci., 95, 145–161 (2000) (Phase Diagram, Phase 

Relations, Experimental, 28) 

[2001Far] Farrell, S.P., Fleet, M.E., “Sulfur K XANES Study of Local Electronic Structure in Ternary Monosulfide 

Solid Solution {(Fe, Co, Ni) 0.923S}”, Phys. Chem. Miner., 28, 17–27 (2001) (Experimental, Crys. 

Structure, Electronic Structure, 56) 

[2001Kos] Kosyakov, V.I., Sinyakova, E.F., Nenashev, B.G., “A Mechanism of Pentlandite Formation in the Fe-Ni- 

S System” (in Russian), Dokl. Akad. Nauk, Geokhimiya, 381(9), 1113–1115 (2001) (Experimental, Phase 


[2001Sin1] Sinyakova, E.F., Kosyakov, V.I., “600˚C Section of the Fe-FeS-NiS-Ni Phase Diagram”, Inorg. Mater. 

(Engl. Trans.), 37(11), 1130–1137 (2001), translated from Neorg. Mater., 37(11), 1327–1335 (2001) 

(Experimental, Morphology, Phase Relations, Phase Diagram, 32) 

[2001Sin2] Sinyakova, E.F., Kosyakov, V.I., Kolonin, G.R., “Behavior of Platinum Group Metals on Crystallization 

of Melts of the Fe-Ni-S System (Fe xNi 0.49–xS 0.51 Section)” (in Russian), Geol. Geofiz., 42(9), 1354–1370 

(2001) (Experimental, Morphology, Phase Relations, 35) 

[2002Cha] Chauke, H.R., Nguyen-Manh, D., Ngoepe, P.E., Pettifor, D.G., Fries, S.G., “Electronic Structure and 

Stability of the Pentlandites Co 9S 8 and (Fe,Ni) 9S 8”, Phys. Rev. B, 66(15), 155105 (2002) (Crys. Structure, 


[2003Cha] Chabot, N.L., Jones, J.H., “The Parameterization of Solid Metal-Liquid Metal Partitioning of 

Siderophile Elements”, Meteor. Planet. Sci., 38(10), 1425–1436 (2003) (Experimental, Thermodyn., 46) 

[2003Kos] Kosyakov, V.I., Sinyakova, E.F., Shestakov, V.A., “Dependence of Sulfur Fugacity on the Composition 

of Phase Associations in the Fe-FeS-NiS-Ni System at 873 K”, Geochem. Int., 41(7), 660–669 (2003) 


[2004Dis] Distler, V.V., Yudovskaya, M.A., Mitrofanov, G.L., Prokofév, V.Y., Lishnevskii, E.N., “Geology, 

Composition, and Genesis of the Sukhoi Log Noble Metals Deposit, Russia”, Ore Geol. Rev., 24, 7–44 

(2004) (Phase Diagram, Phase Relations, Review, 61) 

[2004Ets] Etschmann, B., Pring, A., Putnis, A., Grguric, B., Studer, A., “A Kinetic Study of the Exsolution of 

Pentlandite (Ni,Fe) 9S 8 from the Monosulfide Solid Solution (Fe,Ni)S”, Am. Mineral., 89, 39–50 (2004) 

(Crys. Structure, Experimental, Kinetics, 42) 

[2004Kos] Kosyakov, V.I., Sinyakova, V.F., “Investigation of Monovariant Peritectic Reaction in the Fe-Ni-S 

Ternary System Using Oriented Crystallization Method” (in Russian), Zh. Neorg. Khim., 49(7), 


[2004Rag] Raghavan, V., “Fe-Ni-S (Iron-Nickel-Sulfur)”, J. Phase Equilib. Diffus., 25(4), 373–381 (2004) (Phase 


[2004Wal1] Waldner, P., Pelton, A.D., “Thermodynamic Modelling of the Ni-S System”, Z. Metallkd., 95(8) 

672–681 (2004) (Assessment, Phase Diagram, Thermodyn., 49) 

[2004Wal2] Waldner, P., Pelton, A.D., “Critical Thermodynamic Assessment and Modeling of the Fe-Ni-S System”, 

Metall. Mater. Trans. B, 35b(5), 897–907 (2004) (Assessment, Phase Diagram, Thermodyn., 35) 

[2005Nam] Nam, H.D., Kim, E.C., Han, J.S., “Mössbauer Study of Iron Sulfides Doped with 3d-Transition Metals”, 

Solid State Commun., 135(5), 327–329 (2005) (Experimental, Crys. Structure, Electronic Structure, 


[2006Leh] Lehner, S.W., Savage, K.S., Ayers, J.C., “Vapor Growth and Characterization of Pyrite (FeS 2) Doped 

with Co, Ni, and As: Variations in Semiconducting Properties”, J. Cryst. Growth, 286(2), 306–317 (2006) 

(Experimental, Electr. Prop., Semicond.,38) 

[2006Rag] Raghavan, V., “Fe-Ni-S (Iron-Nickel-Sulfur)”, J. Phase Equilib. Diffus., 27(3), 293–295 (2006) (Review, 

Calculation, Phase Diagram, Phase Relations, 4) 



MSIT 1


61 

[2006Sin] Sinyakova, E.F., Kosyakov, V.I., “Phase Relationships and Sulfur Fugacity in the System Fe-FeS-NiS-Ni 

at 900˚C” (in Russian), Russ. Geol. Geophys., 47(7), 835–846 (2006) (Experimental, Morphology, Phase 


[2006Wal1] Waldner, P., “Thermodynamic Analysis of High-Temperature Heazlewoodite”, Z. Metallkd., 97(1) 

17–21 (2006) (Calculation, Thermodyn., Phase Diagram, Phase Relations, 33) 

[2006Wal2] Waldner, P., Sitte, W., “Thermodynamic Modeling of High-Temperature Fe-Ni-Heazlewoodite”, Advanced 

Eng. Mater., 8(11), 1161–1164 (2006) (Calculation, Experimental, Phase Diagram, Phase Relations, 


[2008Fer] Ferro, R., Bochvar, N., Sheftel, E., Ding, J.-J., “Fe-S (Iron-Sulfur)”, MSIT Binary Evaluation Program, in 

MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services, GmbH, Stuttgart; 

to be published (2008) (Crys. Structure, Phase Diagram, Phase Relations, Assessment, 28) 





(1990) 





MSIT 1 

DOI: 10.1007/978-3-540-70890-2_11 

ß Springer 2009

Iron – Nickel – Antimony 


Marina Bulanova, Yulia Fartushna 

Introduction 

The Fe-Ni-Sb system is of practical importance for different fields of application. Thus, 

Sb-induced embrittlement of alloy steels results from antimony segregation at the grain 

boundaries of (αFe,Ni,Sb), which, in turn, strongly depend on the Ni content. Last two 

decades much attention is focused on skutterudite thermoelectric materials, where Fe-Ni-Sb 

is one of the boundary system. So, understanding of phase equilibria in this system gives 

possibilities to control the properties of Fe-Ni-Sb-based materials. 

First information on the system appeared in 1943, when [1943Age1, 1943Age2] reported a 

continuous solid solution between FeSb and NiSb. [1970Bje] found the ternary compound 

Fe 0.5Ni 0.5Sb 3 (τ) and a limited mutual solid solubility of FeSb 2 and NiSb 2. Later [2003Zha] 

reported on a new semi-Heusler phase FeNiSb, which seems to be metastable. 

Phase relations in the Fe-Ni-Sb system were studied by [1973Pan, 1997Ric1, 1997Ric2, 

2003Voi] and resulted in a partial liquidus surface [1997Ric1], isothermal sections at 1150 

[2003Voi] and 600˚C [1997Ric1], a number of vertical sections [1973Pan, 1997Ric1, 

1997Ric2], reaction scheme [1997Ric1]. Note, that the work of [1997Ric1] is the key-paper 

on phase relations in the system, giving the comprehensive information concerning the phase 

equilibria at more than 50 at.% Sb. Experimental data are given also for the samples with 35, 

42 and 46 at.% Sb, however phase equilibria in the concentration range < 50 at.% Sb are not 

established in details. Thermodynamics of alloys is given by [1997Ric2, 2003Voi]. 

Solubility of Sb in (αFe,Ni) and the nature of precipitates was studied by [1974Nag, 

1976Nag]. The grain boundary segregation and cosegregation in (αFe,Ni,Sb) is given by 

[1986Gas]. 

[1977Gal, 1980Gel] reported the structure and magnetic properties of the (Fe,Ni)Sb (ε) 

phase. Magnetic properties of metal-enriched monoantimonide (Fe 1–yNi y) 1+xSb are given by 

[1984Har]. [1973Kje] and [1974Kje] studied the Mössbauer effect in the ternary compound τ 

and in the FeSb 2-based phase Fe xNi 1–xSb 2, respectively. 

[1992Rag, 2004Rag1, 2004Rag2] reviewed the Fe-Ni-Sb system. 

The structure and properties of skutterudites were studied by [2003Mor, 2005Cha, 

2005Mi]. 

The experimental researches of phase relations and related questions in the ternary Fe-Ni- 

Sb system are summarized in Table 1. 


Fe–Ni–Sb 12 

1 

The Fe-Ni and Fe-Sb binary systems are accepted from [2008Kuz] and [1995Pei], respectively. 

The Ni-Sb phase diagram is taken basically from [Mas2]. The composition and temperatures 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_12 

ß Springer 2009

2 12 

Fe–Ni–Sb 

of invariant points of liquid in the Sb rich part are accepted from [1989Fes] to accord with 

experimental results of [1997Ric1] on the ternary system. 


The Fe-Ni-Sb solid phases are reported in Table 2. The ternary compound Fe0.5Ni0.5Sb3 (τ), 

first found by [1970Bje], forms by a P type peritectic reaction at 642˚C [1997Ric1] and 

crystallizes in a cubic CoAs 3 type structure. It has a narrow homogeneity range due to the 

mutual substitution of Fe and Ni, so that the formula can be written as Fe 0.5-0.46Ni 0.5-0.54Sb 3. 

Despite band calculations predicted unstable ferromagnetic state and crystal structure, 

[2003Zha] prepared a new semi-Heusler phase FeNiSb by melt-spinning technique and 

studied its electronic structure, magnetic and transport properties. The phase is ferromagnetic 

and melts at 991˚C without any phase transformation at lower temperatures. However, 

according to the preparation method, the phase might be metastable. 

[1943Age1, 1943Age2] reported a continuous solid solubility of FeSb and NiSb at 600˚C 

(ε phase). The metal-rich part of the solid solution is of interstitial type, the Sb rich part has a 

defect structure. Figure 1a shows the lattice parameters of the phase as measured by 

[1997Ric1] for the isoconcentrate 46 at.% Sb. The data are in reasonable agreement with 

data [1977Gal], Table 2. Essential narrowing of the homogeneity region of the phase in Sb 

content in a middle part (see isothermal section at 600˚C, Fig. 6) allowed [1997Ric1] to make 

an assumption of the possible arising of the miscibility gap at lower temperatures. 

Isostructural FeSb2 and NiSb2 do not form a continuous solid solution. According to 

[1970Bje], at 600˚C the solubility of Ni in FeSb 2 is about 16.7 at.%, the phase is written by the 

formula (Fe xNi 1–x)Sb 2 (0.5 < x < 1). This value is confirmed by [1997Ric1]. According to the 

last paper, the solubility of Fe in NiSb 2 is no more than 2 at.%. The concentration dependence 

of the lattice parameters of Fe xNi 1–xSb 2 is shown in Fig. 1b. [1997Ric1] has shown that the 

solubility of Fe in Ni 5Sb 2 at 600˚C is about 5 at.%. 


According to [1997Ric1, 1997Ric2], the Fe-Ni-Sb system is triangulated by the (Fe,Ni)Sb 

phase into two subsystems: Fe-FeSb-NiSb-Ni and FeSb-Sb-NiSb. Thus, the section FeSb-NiSb 

is quasibinary. However, the quasibinarity does not occur along the equiatomic isoconcentrate 

50 at.% Sb, but along the section passing via distectic points Fe 0.573Sb 0.427-Ni 0.511Sb 0.489. 

By the methods of thermal analysis, metallography and hardness measurements [1973Pan] 

constructed the section Fe-NiSb, which was claimed to be quasibinary. This, meanwhile, is not 

so, as (1) it does not go via the distectic point of NiSb; (2) if it was, extremes at the solidus 

surfaces (γFe,Ni)+ε and (δFe,Ni)+ε should take place, that is questionable. 


Four invariant equilibria were established [1997Ric1] at above 600˚C in the Sb rich subsystem. 

These are a P type equilibrium at 642˚C, two U type equilibria at 625 and 620˚C and a E type 

equilibrium at 616˚C. The compositions of the phases taking part in these equilibria were 



MSIT 1

determined. All the equilibrium points of liquid are located at more than 90 at.% Sb. Invariant 

equilibria, coordinates of invariant points, compositions of the coexisting solid phases are 

shown in Table 3. Based on the experimental data of [1997Ric1, 1997Ric2] and on the 

boundary binaries it is possible to propose the character of invariant equilibria with participation 

of the liquid for the Sb-poor subsystem, as well. Here two U type equilibria should 

occur: L + Ni 5Sb 2 ⊊Ð⊊ ε + γ and L + γ Ð ε + δα. The temperature decreases slowly from 

1072˚C in the eutectic l Ð⊊ Ni5Sb2+ε to 998˚C in the eutectic l Ð ε +(δFe). So, the 

temperature of the above four phase equilibria appears in this temperature interval, and the 

temperature 1000˚C declared by [1997Ric1] and [1973Pan] as the temperature of an invariant 

equilibrium (according to [1973Pan], of the invariant three-phase equilibrium l Ð εαffl + γ), 

might be the temperature of the monovariant equilibrium l ⊊Ð⊊ εαffl+ γ, which decreases very 

slowly. These equilibria are also shown in Table 3. The resulted reaction scheme is given in 

Fig. 2. Experimental results [1997Ric1] are given in solid, resulting of our assessment are given 

in dotted lines. The scheme is limited from below by the temperature 600˚C. 


Based on the boundary binary systems, [1991But] predicted full liquid miscibility in the 

system. This was confirmed later. By the DTA method [1997Ric1] constructed the liquidus 

isotherms via 20˚C at 40 to 90 at.% Sb, as shown in Fig. 3a. These are limited by the 

temperature 1140˚C. Coordinates of the invariant points of liquid, determined in this work, 

allowed [2004Rag1] to plot a liquidus projection in the Sb corner (>90 at.% Sb), Fig. 3b. Data 

[1997Ric1, 1997Ric2, 2003Voi] and the boundary binary systems allowed us to assess the 

liquidus projection for the Sb poor subsystem. It is shown in Fig. 4 together with few 

isotherms in the Sb rich field. According to the observations of [1973Pan], the monovariant 

curve l Ð⊊ εαffl + γ is located at about 30 at.% Sb. Isotherms of [1997Ric1, 2003Voi] are shown 

by solid curves, those assessed by us are given as dashed ones. 

The solidus surface of the Fe-Ni-Sb system was not specially studied. However, compositions 

of the phases taking part in invariant equilibria in the Sb rich subsystem [1997Ric1], 

Table 3, allowed us to plot a partial solidus surface, shown in Fig. 5. 

According to [1974Nag], 1 at.% Ni in the alloy Fe-4Sb decreases solubility at 600˚C of Sb in 

(αFe) from 2.5 to 1.6 at.% resulting in precipitation of the ε phase. [1976Nag] reported that 

after ageing at 550˚C for 120 h a precipitation takes place over the entire volume, in contrast to 

the Ni-free alloy. According to [1997Ric1], at 600˚C (αFe,Ni) and (γFe,Ni) dissolve, respectively, 

1 and 2 at.% Sb. 



3 

Two isothermal sections are reported in the Fe-Ni-Sb system. From X-ray diffraction and 

EPMA results [1997Ric1] constructed the isothermal section at 600˚C. To achieve equilibrium 

state the samples for EPMA examination were annealed at this temperature for 6 months. 

The section shown in the paper [1997Ric1] covers the composition interval 40 to 100 at.% Sb 

(Sb rich subsystem). However, the EPMA results given involve the whole concentration 

interval. This allowed us to plot the whole isothermal section at 600˚C. Three-phase regions 

δα + γ + ε and γ +Ni 5Sb 3 +Ni 3Sb are added by us. A similar plot was done by [2004Rag1]. 

However, it is somewhat inconsistent with the accepted here Fe-Ni binary system. The section 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_12 

ß Springer 2009

4 12 

Fe–Ni–Sb 

is shown in Fig. 6 due to experimental data [1997Ric1] (in solid) and our assessment (in 

dashed). 

By quenching from the solid-liquid state, and using the methods of metallography and 

EPMA, [2003Voi] constructed the isothermal section at 1150˚C. This involves equilibria of 

liquid with δα and with (γFe,Ni). In [2003Voi], however, the two modifications of the solid 

solution are not specified. [2004Rag2] includes this correction, as shown in Fig. 7. Solid curves 

correspond to the original work [2003Voi], dashed ones - to [2004Rag2]. 


[1997Ric1] constructed the isopleths below liquidus along the isoconcentrates 66.7, 70, 75 and 

85 at.% Sb, and [1997Ric2] reported the vertical section along FeNi-Sb at 40-90 at.% Sb. The 

sections at 70 and 85 at.% Sb and FeNi-Sb are shown in Figs. 8a to 8c. 


By isothermal isopiestic method [2003Voi] measured activities of Sb at 1150˚C, the isoactivity 

curves were constructed, showing negative deviation from the ideal behavior and a negative 

gradient against the Fe content, thus, specifying stronger chemical affinity for Ni-Sb than for 

Fe-Sb. By the Gibbs-Duhem integration method isoactivity lines for Fe and Ni were estimated. 

By the same method [1997Ric2] determined partial molar enthalpies and activities of Sb in 

the ε phase at Fe:Ni = 1:1 and 45.5-51.5 at.% Sb for 900˚C. 


[1977Gal, 1980Gel] studied magnetic properties of the monoantimonide phase along the 

sections FeSb-NiSb, Fe 1.2Sb-Ni 1.2Sb, Fe 1.2Sb-NiSb. Ferromagnetism was absent in the alloys 

along the first section, and had the highest level along the second one. It is accounted for by 

location of the metal atoms in the bipyramidal interstitials of the crystal lattice [1977Gal]. 

[1980Gel] has shown that magnetic moments of the Fe-atoms at the d-sites are ferromagnetically 

ordered. Substitution of Fe- by Ni-atoms at the a-sites results in collinear antiferromagnetism. 

By using X-ray diffraction and Mössbauer spectra of (Fe 1–yNi y) 1+xSb 

(0.02≤y≤0.42, 0.08≤x≤0.16), [1984Har] has shown that the Neel temperature decreases linearly 

when y increases. This results, as well, in two magnetic hyperfine fields, which are about 40 and 

80% lower than in the Fe 1–xSb. The value of the fields does not depend on Ni content. 

Magnetization vs temperature of a new semi-Heusler phase FeNiSb [2003Zha] is interpreted 

in the spin-wave theory, electrical resistivity follows a T 5 behavior. 

[1986Gas] gives diffusion parameters of Fe, Ni and Sb in (αFe,Ni,Sb). 

Miscellaneous 

[1973Kje] has shown the predominant covalent nature of the chemical bonding in the ternary 

compound τ. According to [1974Kje], an increase of the Ni content in Fe xNi 1–xSb 2 results in an 

increase of the Ni-Sb interatomic distances. 



MSIT 1

Nanostructured ternary unfilled skutterudite Fe 0.5Ni 0.5Sb 3 was synthesized at 240˚C for 48 

h by a solvothermal method [2005Mi] with particles size about 50 nm and metallic electrical 

properties. Neutron diffraction and transmission electron microscopy were used by [2005Cha, 

2003Mor], respectively, to study partially filled skutterudite structure in the Ce-Fe-Ni-Sb 

system. 

. Table 1 

Investigations of the Fe-Ni-Sb Phase Relations, Structures and Thermodynamics 


[1943Age1] Homogenization at 600˚C for three days, 

slow cooling; optical microscopy, 

electrical conductivity measurements, 

powder XRD 

[1943Age2] Homogenization at 600˚C for three days, 

slow cooling; optical microscopy, 

electrical conductivity measurements, 

powder XRD 

[1970Bje] Preparation from FeSb 2 and NiSb 2 by 

annealing, crashing and reanealling at 

600˚C for several times to reach 

homogeneity; powder XRD with KCl 

internal standard 

[1973Pan] DTA, optical microscopy, hardness and 

magnetic susceptibility measurements 

[1974Nag] Homogenization treatment 975˚C / 94 h 

+ 850˚C / 6 h; powder XRD 

[1976Nag] Homogenization treatment 975˚C / 94 h; 

optical microscopy, SEM, TEM 

[1977Gal] Heat treatment 600˚C/ 30 h; XRD; 

temperature-field dependencies, 

magnetic intensity, susceptibility 

measurements; Mössbauer spectra 

[1997Ric1] Synthesis in quartz ampoules at 1200˚C, 

homogenization at 900˚C / 3 weeks, or at 

600˚C / 6 weeks; DTA, metallography, 

XRD, EPMA 



MSIT 1 



Range Studied 

600˚C / FeSb-NiSb continuous solid 

solution 

600˚C / FeSb-NiSb continuous solid 

solution 

600˚C / FeSb 2-NiSb 2 section; ternary 

compound FeNiSb6 (τ) 

Vertical section Fe-NiSb 

975, 650, 600˚C / Fe-1Ni-4Sb / solubility of 

Sb in (αFe,Ni), lattice parameters 

Fe-1Ni-8.3Sb / solubility of Sb in (αFe,Ni) 

600˚C / (Fe,Ni)Sb phase along the 

sections Fe 1.2Sb-Ni 1.2Sb, FeSb-NiSb, 

Fe1.2Sb-NiSb, lattice parameters 

900˚C / ε phase (Fe yNi 1–y) 1±xSb / lattice 

parameters; 600˚C / isothermal section 

for Sb-subsystem / lattice parameters of 

ε phase and of (Fe,Ni)Sb 2; liquidus 

isotherms for Sb-subsystem, vertical 

sections at 66.7, 70, 75, 85 at.% Sb; 

reaction scheme 

5 

DOI: 10.1007/978-3-540-70890-2_12 

ß Springer 2009

6 12 

Fe–Ni–Sb 



[1997Ric2] Synthesis in quartz ampoules at 1100˚C, 

homogenization at 500˚C / 3 weeks; DTA, 

XRD; isopiestic method 

[2003Voi] Synthesis in quartz ampoules at 1200˚C, 

quenching from 1150˚C; metallography, 

EPMA; isopiestic method 

[2003Zha] Melt-spinning; XRD; DTA; magnetization 

and electrical resistivity measurements 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Range Studied 

Vertical section FeNi-Sb at 42-90 at.% Sb; 

antimony vapor pressure in 

(Fe 0.5Ni 0.5) 1±xSb at 45.4-51.5 at.% Sb at 

747-1037˚C; partial molar properties of Sb 

at 1150˚C 

1150˚C / isothermal section; isoactivity 

curves of Sb; calculated isoactivity curves 

of Fe, Ni 

FeNiSb semi-Heusler phase, electrical and 

magnetic properties, lattice parameters 

Lattice 

Parameters 


δα, (δFe,αFe) cI2 

Im3m 

(δFe) 

1538 - 1394 

W a = 293.15 [Mas2] 

(αFe) a = 286.65 at 25˚C [Mas2] 

< 912 a = 287.36 [V-C2], Fe0.96Sb0.04 a = 290.0 [V-C2], Fe0.95Sb0.05 

(αFe,Ni,Sb) a = 287.81 [1974Nag], in alloy 

Fe-1Ni-4Sb, 600˚C 

a = 288.03 [1974Nag], in alloy 

Fe-1Ni-4Sb, 650˚C 

a = 289.24 [1974Nag], in alloy 

Fe-1Ni-4Sb, 975˚C 


Fm3m 

(γFe) 

< 1394 - 912 

Cu a = 364.67 at 915˚C [V-C2, Mas2] 

(Ni) 

< 1455 

a = 352.40 at 25˚C [Mas2] 


P63/mmc Mg 

c = 396.0 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Lattice 

Parameters 


(Sb) hR6 a = 450.67 [Mas2] 

< 630.755 R3m 

αAs 

α = 57.11˚ 

γ’, FeNi3 cP4 a = 355.23 63 to 85 at.% Ni [1991Swa] 

< 517 Pm3m 

AuCu3 γ’’, FeNi tP4 a = 357.9 [V-C2], metastable. 

P4/mmm 

AuCu 

Metastable ordering temperature 320˚C at 

51.2 at.% Ni [1984Ros] 

(FexNi1–x)Sb2 oP6 0.5 ≤ x ≤ 1 

Pnnm a = 564.17 ± 0.09 x = 0.5 [V-C2] 

FeS2 b=644.02 ± 0.09 

c=338.55 ± 0.05 

FeSb2 

a = 583.28 ± 0.05 [V-C2] 

< 738 b=653.76 ± 0.05 

c=319.73 ± 0.03 

FeSb4 cP1 

Pm3m 

αPo 

- [Mas2], metastable 

Ni15Sb 

< 460 

- - [Mas2], ordering 

Ni3Sb oP8 a = 532.07 ± 0.08 [V-C2] 

< 715 Pmmm b = 428.08 ± 0.03 

βTiCu3 c=451.47 ± 0.04 

Ni5Sb2 mC28 a = 1294.58 [V-C2] 

1161 - 530 C2 b=542.71 

Ni5Sb2 c=1145.68 

β = 151.71˚ 

Ni7Sb3 

< 600 

t** - [Mas2] 

NiSb2 oP6 a = 518.23 ± 0.05 [V-C2] 

< 621 Pnnm b = 631.68 ± 0.07 

FeS2 c=384.03 ± 0.05 



MSIT 1 

7 

DOI: 10.1007/978-3-540-70890-2_12 

ß Springer 2009

8 12 

Fe–Ni–Sb 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


ε, (FexNi1–x)Sb hP4 a = 393.8 [1977Gal] 1) , x = 0.3 

P63/mmc c = 514.5 dpycn. = 8.531 g·cm –3 

NiAs a = 394.7 [1977Gal], x = 0.2 

c=514.2 dpycn. = 8.535 g·cm –3 

a = 393.8 [1977Gal], x = 0.1 

c=514.1 dpycn. = 8.544 g·cm –3 

(FexNi1–x) 1.2Sb a = 401.3 [1977Gal], x = 0.7 

c=520.1 dpycn. = 8.347 g·cm –3 

a = 397.3 [1977Gal], x = 0.5 

c=513.2 dpycn. = 8.441 g·cm –3 

a = 403.6 [1977Gal], x = 0.3 

c=518.4 dpycn. = 9.498 g·cm –3 

a = 395.9 [1977Gal], x = 0.2 

c=511.4 dpycn. = 8.537 g·cm –3 

a = 395.0 [1977Gal], x = 0.15 

c=514.2 dpycn. = 8.595 g·cm –3 

a = 396.9 [1977Gal], x = 0.1 

c=515.5 dpycn. = 8.637 g·cm –3 

Fe1.2xNi1–xSb a = 397.1 [1977Gal], x = 0.4 

c=513.5 dpycn. = 8.486 g·cm –3 

a = 402.9 [1977Gal], x = 0.6 

c=511.9 dpycn. = 8.411 g·cm –3 

FeSb a = 412.4 [V-C2], Fe0.56Sb0.44, 520˚C 

< 1019 c=517.3 

a = 515.3 [1974Nag], in alloy Fe-1Ni-4Sb, 650˚C; 

c=403.2 ε phase contains about 13 at.% Ni 

NiSb a = 393.25 [V-C2] 

< 1147 c=513.51 

*τ, Fe0.5Ni0.5Sb3 cI32 Fe0.5-0.46Cu0.5-0.54Sb3 Im3 a = 909.02 ± 0.05 [1970Bje] 

CoAs3 dpycn. = 7.411 g·cm –3 at 25˚C 

a = 909.04 ± 0.05 FeNiSb6 [V-C2] 

FeNiSb C1b a = 572 ± 2 [2003Zha] semi-Heusler phase, metastable 

1) Parameters a and c are replaced. 



MSIT 1

. Table 3 




Fe Ni Sb 

Reference 

L+ε + FeSb2 Ð τ 642 P L 3.5 2.5 94 [1997Ric1] 

ε 1.5 46 52.5 

FeSb2 16.7 16.7 66.7 

τ 12 13 75 

L+ε Ð NiSb2 + τ 625 

1) 

U3 L 0.5 4.5 95 [1997Ric1] 

ε 1 46 53 

NiSb2 0 33.3 66.7 

τ 11.5 13.5 75 

L + FeSb2Ðτ + (Sb) 620 

2) 

U4 L 1 3 96 [1997Ric1] 

FeSb2 22.8 10.5 66.7 

τ 12.5 12.5 75 

(Sb) 0 0 100 

L Ð NiSb2 + τ + (Sb) 615 E L 0 3 97 [1997Ric1] 

NiSb2 0 33.3 66.7 

τ 11.5 13.5 75 

(Sb) 0 0 100 

L+Ni5Sb2 Ð ε + γ 998

10 12 

Fe–Ni–Sb 

. Fig. 1a 

Fe-Ni-Sb. Lattice parameters of the monoantimonide (Fe xNi 1–x) 54Sb 46 as a function of Ni 

concentration 



MSIT 1


11 

. Fig. 1b 

Fe-Ni-Sb. Lattice parameters of the diantimonide (Fe,Ni)Sb 2 as a function of Ni concentration 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_12 

ß Springer 2009

12 12 

. Fig. 2 

Fe-Ni-Sb. Reaction scheme 

Fe–Ni–Sb 



MSIT 1

. Fig. 3a 

Fe-Ni-Sb. The liquidus isotherms in the Sb rich subsystem 



MSIT 1 


13 

DOI: 10.1007/978-3-540-70890-2_12 

ß Springer 2009

14 12 

Fe–Ni–Sb 

. Fig. 3b 

Fe-Ni-Sb. A fragment of the liquidus surface projection above 90 at.% Sb 



MSIT 1

. Fig. 4 

Fe-Ni-Sb. Assessed liquidus surface projection 



MSIT 1 


15 

DOI: 10.1007/978-3-540-70890-2_12 

ß Springer 2009

16 12 

Fe–Ni–Sb 

. Fig. 5 

Fe-Ni-Sb. Partial solidus surface projection 



MSIT 1

. Fig. 6 

Fe-Ni-Sb. Isothermal section at 600˚C 



MSIT 1 


17 

DOI: 10.1007/978-3-540-70890-2_12 

ß Springer 2009

18 12 

Fe–Ni–Sb 

. Fig. 7 

Fe-Ni-Sb. Isothermal section at 1150˚C 



MSIT 1

. Fig. 8a 

Fe-Ni-Sb. Vertical section at 70 at.% Sb 



MSIT 1 


19 

DOI: 10.1007/978-3-540-70890-2_12 

ß Springer 2009

20 12 

Fe–Ni–Sb 

. Fig. 8b 

Fe-Ni-Sb. Vertical section at 85 at.% Sb 



MSIT 1

. Fig. 8c 

Fe-Ni-Sb. Partial vertical sections along the FeNi – Sb join 



MSIT 1 


21 

DOI: 10.1007/978-3-540-70890-2_12 

ß Springer 2009

22 12 

Fe–Ni–Sb 

References 

[1943Age1] Ageev, N.V., Makarov, E.S., “Continuous Transition Between the Daltonide and the Berthollide Phases 

in the System Iron-Nickel-Antimony”, Compt. Rend. Sci. Acad. URSS, 38, 20–21 (1943), translated from 

Izv. Akad Nauk SSSR (Khim.), 161 (1943) (Experimental, Phase Relations, 6) 

[1943Age2] Ageev, N.V., Makarov, E.S., Zhur. Obshchey Khimii, 13, 242 (1943) 

[1970Bje] Bjerkelund, E., Kjekshus, A., “Compounds with the Marcasite Type Crystal Structure”, Acta Chem. 

Scand., 24, 3317–3325 (1970) (Crys. Structure, Experimental, 35) 

[1973Kje] Kjekshus, A., Nicholson, D.G., Rakke, T., “Compounds with the Skutterudite Type Crystal Structure”, 

Acta Chem. Scand., 27, 1315–1320 (1973) (Crys. Structure, Experimental, 19) 

[1973Pan] Panteleimonov, L.A., Babanskaya, I.A., “The Interaction Compound NiSb with Iron and Cobalt”, Vestn. 

Moskov. Univ., (Khim.), 14, 373 (Phase Relations, Phase Diagram, Experimental, 1973) 

[1974Kje] Kjekshus, A., Rakke, T., “Compounds with the Marcasite Type Crystal Structure. X. 57 Fe Mössbauer 

Studies of Some Ternary Pnictides”, Acta Chem. Scand., Ser. A, 28A(9), 1001–1010 (1974) (Crys. 


[1974Nag] Nageswararao, M., McMahon, C.J., Herman, H., “The Solubility and Solution Behaviour of Sb and Sn 

in α-Fe and the Effects of Ni and Cr Additions”, Metall. Trans., 5, 1061–1068 (1974) (Experimental, 


[1976Nag] Nageswararao, M., Herman, H., McMahon, C.J., “On the Decomposition of Supersaturated Fe-Sb, Fe- 

Sn, Fe-Sb-Ni Solid Solutions”, Met. Sci., 10(7), 249–252 (1976) (Experimental, Phase Relations, 9) 

[1977Gal] Galperina, T.N., Zelenin, L.P., Fedorova, T.A., Sidorenko, F.A., Geld, P.V., “The Magnetic Properties of 

the Mutual Solid Solutions of the Mono-Antimonides”, Phys. Met. Metallogr., 43, 183–185 (1977), 

translated from Fiz. Metal. Metalloved., 43(3) 661–663 (1977) (Experimental, Magn. Prop., 7) 

[1980Gel] Geld, P.V., Galperina, T.N., Babanova, E.N., Sidorenko, F.A., “Magnetic and Atomic Structure of the 

Monoantimonide Phases Fe 1+xSb and (Fe 1–yNi y) 1.2Sb”, Sov. Phys.-Dokl. (Engl. Transl.), 253, 545–546 

(1980), translated from Dokl. Akad. Nauk SSSR, 253, 85–87 (1980) (Experimental, Crys. Structure, 


[1984Har] Harchand, K.S., Kumar, R., Vishwamittar, Kumar, D., Chandra, K., “Influence of Nickel Substitution in 

an Fe-Sb Triangular Antiferromagnetic System”, Phys. Rev. B., 30(3) 1527–1533 (1984) (Phase Relations, 


[1984Ros] Rossiter, P.L., Jago, R.A., “Towards a True Fe-Ni Phase Diagram”, Mater. Res. Soc. Symp. Proc., 

21, 407–411 (1984) (Phase Diagram, Review, 26) 

[1986Gas] Gas, P., Poize, S., Bernardini, J., “Influence of Cosegregation on Grain Boundary Diffusion: 

Experimental Study in Ultra High Purity Fe-Ni-Sb Solid Solutions”, Acta Metall., 34(3), 395–403 (1986) 

(Phase Relations, Experimental, 17) 

[1989Fes] Feschotte, P., Lorin, D., “Binary Systems Fe-Sb, Co-Sb and Ni-Sb” (in French), J. Less-Common Met., 

155, 255–269 (1989) (Phase Diagram, Phase Relations, Experimental, 12) 

[1991But] Butt, M.T.Z., Bodsworth, C., “Liquid Immisicibility in Ternary Metallic Systems”, Mater. Sci. Technol., 

7(9), 795–802 (1991) (Experimental, Phase Relations, Phase Diagram, Review, 39) 

[1991Swa] Swartzendruber, L.J., Itkin, V.P., Alcock, C.B., “The Fe-Ni (Iron-Nickel) System”, J. Phase Equilib., 12(3), 

288–312 (1991) (Assessment, Phase Diagram, Phase Relations, 89) 

[1992Rag] Raghavan, V., “The Fe-Ni-Sb (Iron-Nickel-Antimony) System” in “Phase Diagrams of Ternary Iron 

Alloys”, Indian Inst. Met., Calcutta, 6B, 1061–1062 (1992) (Crys. Structure, Phase Diagram, Phase 


[1995Pei] Pei, B., Bjorkman, B., Sundman, B., Jansson, B., “A Thermodynamic Assessment of the Iron-Antimony 

System“, Calphad, 19(1), 1–15 (1995) (Phase Diagram, Phase Relations, Thermodyn., Assessment, 37) 

[1997Ric1] Richter, K.W., Ipser, H., “An Experimental Investigation of the Fe-Ni-Sb Ternary Phase Diagram”, 

J. Phase Equilib., 18(3), 235–224 (1997) (Experimental, Phase Relations, Review, #, 15) 

[1997Ric2] Richter, K.W., Ipser, H., “The Section (Fe 0.5Ni 0.5) xSb 1–x: Phase Relationships and Thermodynamic 

Properties”, Z. Metallkd., 88(11), 873–879 (1997) (Experimental, Phase Relations, Thermodyn., #, 19) 

[2003Mor] Morimura, T., Hasaka, M., “Partially Filled Skutterudite Structure in Ce fFe 8–xNi xSb 24“, Scr. Mater., 48, 


[2003Voi] Voisin, L., Hino, M., Itagaki, K., “Phase Relations and Activities in the Fe-Ni-As and Fe-Ni-Sb Systems 

at 1423 K”, Mater. Trans., 44(12), 2654–2658 (2003) (Phase Relations, Thermodyn., Experimental, 13) 



MSIT 1


23 

[2003Zha] Zhang, M., Liu, Zh., Hu, H., Cui, Y., Liu, G., Chen, J., Wu, G., Sui, Y., Qian, Zh., Li, Zh., Tao, H., Zhao, 

B., Wen, H., “A New Semi-Heusler Ferromagnet NiFeSb: Electronic Structure, Magnetism and 

Transport Properties”, Solid State Commun., 128(2-3), 107–111 (2003) (Calculation, Crys. Structure, 

Electr. Prop., Electronic Structure, Experimental, Magn. Prop., 26) 

[2004Rag1] Raghavan, V., “Fe-Ni-Sb (Iron-Nickel-Antimony)”, J. Phase Equilib. Diffus., 25(1), 89–91 (2004) (Phase 


[2004Rag2] Raghavan, V., “Fe-Ni-Sb (Iron-Nickel-Antimony)”, J. Phase Equilib. Diffus., 25(6), 553 (2004) (Phase 


[2005Cha] Chapon, L.C., Girard, L., Haidoux, A., Smith, R.I., Ravot, D., “Structural Changes Induced by Ce 

Filling in Partially Filled Skutterudites”, J. Phys.: Condens. Matter, 17, 3525–3535 (2005) (Crys. Structure, 

Experimental, Phase Relations, Phys. Prop., 21) 

[2005Mi] Mi, J.L., Zhao, X.B., Zhu, T.J., Tu, J.P., Cao, G.S., “Solvothermal Synthesis of Nanostructured Ternary 

Skutterudite Fe 0.5Ni 0.5Sb 3”, J. Alloys Compd., 399(1-2), 260–263 (2005) (Electr. Prop., Experimental, 






(1990) 





MSIT 1 

DOI: 10.1007/978-3-540-70890-2_12 

ß Springer 2009

Iron – Nickel – Silicon 


Elena Semenova 

Introduction 

Fe–Ni–Si 13 

1 

Fe-Ni-Si alloys belong to the group of soft magnetic materials having high permeability 

(permalloy effect). This and other special characteristics have led to these alloys being widely 

used in industry. As the properties of the alloys were found to depend on chemical composition, 

heat treatment and the method of preparation, their investigation has been accompanied, 

in many cases, by the study of their phase relationships. 

The constitution of the Fe-Ni-Si system was critically evaluated by [1988Ray]. The 

assessment covers all known investigations of phase relationships up to 1980 [1938Alt, 

1943Gre, 1955Tak, 1960Tak, 1960Iwa, 1961Wit, 1962Gla, 1965Mir, 1965Bor, 1965Bur, 

1968Dmi, 1968Mir, 1968Sid1, 1968Sid2, 1969Mir, 1970Gom, 1972Fro, 1977Nic, 1979Ind, 

1980Cha]. The isothermal section at 600˚C, hypothetical liquidus projection and scheme of 

possible reaction sequence were proposed by [1988Ray] as part of the review. A thermodynamic 

assessment of the system was undertaken by [1980Cha] who based their calculations on 

experimental studies which were later also considered by [1988Ray] in the critical evaluation. 

The reviews by [1994Rag, 2003Rag] added new information on the phase diagram of the 

system, including [1994Koz] and the experimental study of [1998Ike] and thermodynamic 

assessment of [1999Mie], which was based mainly on the data of [1998Ike]. 

[1943Gre] studied the constitution of ternary alloys in the Fe-Ni-Si system in the region 

50-100 at.% Fe. In addition to the phases based on the modifications of iron and on the FeSi 

binary compound, two ternary phases were found at 600˚C in the two-phase alloys where the 

second phase was α. They were indexed as cubic and tetragonal phases and regarded by 

[1943Gre] as only tentative. Seeking for an explanation for the striking magnetic properties 

observed for Fe-Ni-Si alloys, [1955Tak, 1960Tak] investigated the ternary phase diagram in the 

region of Fe rich alloys, and a phase of the composition Fe 11Ni 5Si 4 was found. [1960Iwa] 

determined the crystal structure of the Fe11Ni5Si4 ternary phase. The data presented by 

[1955Tak, 1960Tak, 1960Iwa] are consistent with one of the ternary phases found by 

[1943Gre]. The probable course of monovariant lines on the liquidus surface projection for 

Fe-Ni based alloys containing up to 40 at.% Si and a number of vertical sections were proposed 

by [1960Tak]. [1965Bor] observed a ternary phase which was determined to be isostructural 

with Au 4Al, in an alloy of the composition 50Fe-30Ni-20Si (at.%) after annealing at 800˚C, the 

composition being similar to that indicated by [1943Gre, 1955Tak, 1960Tak]. An isothermal 

section at 600˚C was proposed, and it was stated that the phase equilibria did not differ from 

those at 900˚C. The existence of a ternary phase with a tetragonal crystal structure, observed by 

[1943Gre], was not confirmed by [1965Bor]. The mutual solubility of mono- and disilicides in 

the Fe-Ni-Si ternary system was studied by [1961Wit, 1962Gla, 1965Bor, 1968Dmi, 1968Mir, 

1968Sid1, 1968Sid2, 1969Mir]. [1965Bur] determined the change in the position of the γ/γ+α 

and γ+α/α phase boundaries in the Fe-Ni-Si system with varying temperature. Two vertical 

sections of the ternary phase diagram were constructed at 4 and 5 mass% Si. The investigation 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_13 

ß Springer 2009

2 13 

Fe–Ni–Si 

by [1994Koz] of the Fe-Ni-Si ternary system in the Fe-rich region was carried out using 

experimental and theoretical methods. Two isothermal sections at 650˚C were proposed, based 

on microstructural analysis and calculation, respectively. Isothermal sections for 800, 1000, 

1100 and 1200˚C and vertical sections at 5, 10 and 15 at.% Ni were constructed, and the threephase 

equilibria involving the ternary phase, τ 1, at 800˚C and equilibria involving the liquid at 

1100 and 1200˚C were determined by [1998Ike]. 

Some information relating to the phase relations in the Fe-Ni-Si system were not considered 

in the reviews of [1988Ray, 1994Rag, 2003Rag]. [1990Li, 1991Zha] determined the Fe 

solubility in Ni 3Si, and [1975Ver] the Ni in Fe 3Si. Precipitation during the decomposition of 

martensite in Fe-Ni based alloys containing 1-5 mass% Si on ageing at 300-500˚C, the shape 

and crystal structure of the precipitates and the effect of annealing on atomic structure were 

studied by [1975Yas, 1982Yed, 1983Zay, 1980Rod]. The precipitates observed in a Fe-18Ni-5Si 

alloy after ageing at 350 and 400˚C were identified by [1975Yas] as the (Fe,Ni) 3Si phase, and 

those observed at 500˚C as the (Fe,Ni)5Si2 phase. [1998Lan] reported on the synthesis of a new 

ternary compound with the composition FeNiSi. Its crystal structure was determined as 

orthorhombic with the Co 2Si structure type. 

The component elements of this system are constituents of more complex nanocrystalline 

alloys that are expected to exhibit excellent magnetic properties. The influence of Ni on the 

formation of a nanocrystalline phase in Fe 735–xNi xCu 1Nb 3Si 13.5B 9 alloys was studied by 

[2001Duh]. The Fe 3NiSi 1.5 ternary phase, with a tetragonal crystal structure, was observed 

at 500-550˚C. Taking into account the fact that the magnetic permeability of Fe-Ni based alloys 

decreases with increase in the degree of order in the γ phase present, and in view of the 

importance of high magnetic permeability in these alloys, [2004Him] studied the influence of 

Si on the phase equilibria between the γ and γ’ phases in FeNi 3-Ni 3Si alloys. As a continuation 

of the studies of [1998Ike, 2002Him, 2004Him] into the stability of the phases based on the α 

and γ modifications of Fe, which can be affected by magnetic ordering, and considering alloys 

based on the Ni 3Si phase as having a potential application as high strength materials, 

[2005Him] investigated the phase relationships in the Ni rich portion of the Fe-Ni-Si system. 

Isothermal sections for 700, 800 and 900˚C were constructed and the α+γ+γ’ ternary equilibrium 

was determined. The metastable relationships were also shown. 

Experimental techniques and information on the composition and temperature intervals 

studied are shown in Table 1. 


The Fe-Si and Ni-Si binary systems are accepted from [Mas2]. The Fe-Ni system is taken from 

the recent MSIT assessment by [2008Kuz]. 


The details of crystallography and ranges of stability of the phases in the Fe-Ni-Si system are 

listed in Table 2. The ternary phase, τ 1, having a composition close to Fe 11Ni 5Si 4, a cubic 

crystal structure and being formed by a solid state reaction, was observed by [1943Gre, 

1955Tak, 1960Tak, 1960Iwa, 1994Koz, 1998Ike]. [1965Bor] found the ternary phase of the 

composition Fe5Ni3Si2 and indexed it also as cubic. Taking into account the same crystal 



MSIT 1


3 

structure, lattice parameter and close compositions that these two phases have, it is clear that 

they are the same phase. According to the observations of [1955Tak], τ 1 phase forms from the 

phase based on (αFe). [1960Tak] was more precise, suggesting that τ 1 phase forms by 

the peritectoid reaction, α + γ Ð τ 1, at about of 920˚C. [1965Bor] confirmed the formation 

of the ternary phase via a solid state reaction. Based on the findings of [1965Bor, 1955Tak, 

1960Tak, 1998Ike], the τ 1 phase lies on the 20 at.% Si composition line from 24 to 30 at.% Ni. 

A second ternary phase, τ2, with the composition Fe3NiSi1.5, was found by [2001Duh] on 

the decomposition of multicomponent nanocrystalline Fe735–xNixCu1Nb3Si13.5B9 alloys after 

annealing at 550-500˚C. This new phase appeared to be in equilibrium with the α 2 phase 

(Fe 3Si). The Fe 3NiSi 1.5 ternary phase is included in Table 2 although its existence as a stable 

phase should be confirmed through further investigations of the Fe-Ni-Si system. 

The interpretation by [1982Yed] that the precipitates appearing in Fe-Ni based alloys after 

ageing are a ternary phase of the composition (Fe,Ni) 22Si 7 with a cubic crystal structure, but 

without consideration of the reflection intensity, is questionable. These precipitates, as 

observed by [1975Yas], were identified as the phase known at that time as Ni5Si2. According 

to [Mas2], it is the Ni31Si12 phase. 

The solubility of Fe in the Ni 2Si phase with the Co 2Si crystal structure type, was found by 

[1938Alt, 1972Fro] to be about 33.3 at.%. It would therefore seem reasonable that the new 

phase with the Co 2Si crystal structure type observed by [1998Lan] in an equiatomic singlephase 

alloy can be interpreted as the limit of the homogeneity region of the Ni 2Si phase. The 

lattice parameters, shown in [1998Lan] and [1938Alt] for the equiatomic composition, 

confirm the suggestion that it falls into the homogeneity range of the Ni 2Si phase. The Fe 2Si 

phase dissolves about 3.3 at.% Ni at 1100˚C maintaining its cubic crystal structure, but at a 

composition of 20 at.% Ni this structure distorts trigonally [1938Alt, 1972Fro]. At the same 

time, Fe 2Si-30 mol% Ni 2Si alloys remained single-phase [1972Fro]. In order to accurately 

ascertain the limits of the two-phase region along the section Fe 2Si-Ni 2Si, additional investigations 

should be undertaken. 

The high silicides of the Fe-Ni-Si system, FeSi 2 and αNiSi 2, dissolve about 1.7 at.% Ni 

at 800˚C [1961Wit] and about 12 at.% Fe at 850˚C [1965Mir, 1968Mir, 1969Mir, 1968Sid2], 

respectively. The latter group of authors showed that the αNiSi 2 phase in the Ni-Si binary 

system had a true composition of Ni1.04Si1.93, and its homogeneity range in the ternary system 

has a complex shape having a width of less than 0.5% in the binary system, widening with 

respect to Si content with increasing Fe. The high Fe solubility in αNiSi 2 reported by [2002Fet] 

of about 30 at.% is an erroneous conclusion from their experimental results, which showed 

that an alloy with 9 at.% Fe was single-phase αNiSi 2, while an alloy with 13 at.% contained two 

phases at 750˚C. Actually, this study supported the value given above (about 12 at.%) for the 

homogeneity range of the αNiSi 2 phase. 

According to [1961Wit, 1965Bor], the mutual solubility of the equiatomic phases at 

600-800˚C is approximately 25 at.% Ni in FeSi and 5 at.% Fe in NiSi. [1968Dmi, 1968Sid1] 

confirmed that about 5 at.% Fe dissolves in NiSi and [1968Sid1] showed that about 20 at.% Ni 

could be dissolved in FeSi at 900˚C. The values of the mutual solubility of monosilicides given 

by [1962Gla] are substantially lower than those stated by [1965Bor, 1961Wit]. The solubility of 

Fe in Ni 31Si 12 at 800˚C, reported by [1979Ind] as being about 29 at.%, is not in conflict with 

the value of about 7.9 at.% at 900˚C given later by [2005Him], as the latter value was obtained 

from the analysis of a two-phase (ν+γ) sample and is related to an intermediate composition 

of the homogeneity range. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_13 

ß Springer 2009

4 13 

Fe–Ni–Si 

The homogeneity range of the Ni 3Si phase at 900˚C as determined by [1990Li, 1991Zha]is 

consistent with that shown by [2005Him] for 800˚C. Approximately 6.7 at.% Fe dissolves in 

Ni 3Si at 900˚C and 6.4 at.% Fe at 800˚C, Fe substituting for Ni and Si. 

The solubility of nickel in the α 1 phase at 1000˚C was given by [1975Ver] tobeupto15 

at.% along the 25 at.% Si concentration line, the lattice parameter of the phase increasing. The 

solubility was estimated by [1977Nic] as being 20-25 at.% at 25 at.% Si at room temperature. 

Further experimental studies by [1998Ike] showed that it was 17 at.% at 18 at.% Si when α1 

was in equilibrium with the γ and τ 1 phases at 800˚C. 

The Si solubility in the γ solid solution decreases with temperature decreasing from 900 to 

700˚C and with Fe content increasing up to 34 at.% in Ni rich alloys. For the Fe rich alloys, it 

increases with temperature in the interval 800-1100˚C and increasing Ni content up to about 

27 at.% [2005Him]. 


According to [1968Sid1], the FeSi-NiSi section is quasibinary at about 900˚C with a significant 

region of immiscibility, about 20-45 at.% Ni. 

The critical temperatures of the γ+γ’/γ’ and γ/γ+γ’ transitions for the FeNi 3-Ni 3Si alloys in 

the range of 0-20 at.% Si are plotted in Fig. 1 after [2004Him]. The transformation temperature 

of FeNi 3 increases on substitution of Si for Ni. The section can be considered as 

quasibinary in the range of temperature and compositions studied. 


The τ 1 phase forms by the peritectoid reaction, α + γ Ð τ 1, at about 920˚C [1960Tak]. The 

compositions of the phases taking part in the equilibrium at this temperature are shown in 

Table 3 according to the [1960Tak] data. 


A few experimental and calculated determinations of the liquidus surface of the Fe-Ni-Si 

system have been undertaken. A hypothetical projection of the Fe-Ni-Si liquidus surface of the 

whole composition range was given by [1988Ray]. It was based partly on the experimental data 

of [1960Tak] and partly deduced from available information on the Fe-Ni-Si phase diagram in 

the solid state. The applicability of this approach to the Fe-Ni-Si system is questionable for a 

number of reasons. Firstly, solidus equilibria considered by [1988Ray] were shown by 

[1965Bor] as only tentative and they included low temperature modifications of the FeSi 2 

and NiSi 2 phases which do not exist at subsolidus temperatures. An increase in temperature 

leads not only to a change in the crystal structure of these phases, but in the case of FeSi 2,toa 

change in the composition and homogeneity range (and stability) in the binary system 

[Mas2]. Hence, the equilibria including the high-temperature modifications are different 

from those existing at low temperature. Moreover, the low temperature studies of 

[1968Mir, 1968Sid2] not discussed by [1988Ray], present phase relationships between the 

mono- and disilicides different from those in [1988Ray]. For the above reasons, the liquidus 



MSIT 1

projection suggested by [1988Ray] is not reproduced here. Figure 2 presents monovariant 

curves separating the fields of primary crystallization of the α and γ, α and ε phases shown by 

[1960Tak] with corrections to the field of primary crystallization of the Fe 2Si phase to be 

consistent with the accepted Fe-Si binary system [Mas2]. 

A calculated projection of the primary crystallization surfaces of the α and γ phases made 

by [1998Mie] occurred in a reasonable correlation with the experimental data of [1960Tak]. 



5 

The temperature at which the portions for the Fe rich and Ni rich part of the Fe-Ni-Si ternary 

system were studied by [1998Ike, 1999Mie, 2004Him, 2005Him] and earlier by [1961Wit, 

1979Ind] was 800˚C. Taking this into account, together with the suggestion by [1965Bor] that 

the phase equilibria in the ternary system at 900˚C were little different from those at 600˚C, 

these data, along with those of [1965Bor, 1968Dmi, 1968Mir, 1968Sid1, 1968Sid2, 1969Mir] 

on the solubility of Fe and Ni along the FeNi-NiSi and FeSi2-αNiSi2 sections (shown for 

850˚C) are used in the construction of an isothermal section for 800˚C, which is presented in 

Fig. 3. Dashed lines are used for hypothetical phase boundaries where no data on phase 

relations exist. The Fe solubility in the Ni 2Si phase, up to the equiatomic composition in 

the ternary system was taken from [1972Fro]. The data relate to 1100˚C, and hence the phase 

relationships are only approximate at this temperature. The fragment of the section at 650˚C 

given by [1994Koz] showing the three-phase equilibrium α+γ+τ 1 does not contradict, in 

principle, the Fe rich region at 600˚C given by [1965Bor], although the phase compositions 

at the vertices of the α+γ+τ1 triangle are different. 

The results of the metallographic study of the solubility of Fe in the αNiSi 2 phase carried 

out by [1968Sid2] leads to an understanding of the phase diagram in relation to the ζ β and 

αNiSi 2 phases. There is a three-phase equilibrium FeSi 2+αNiSi 2+Si, for which the composition 

of the αNiSi 2 phase was determined to be between 11.6 and 13.5 at.% Fe along the FeSi 2-NiSi 2 

section. From the observation by [1968Mir, 1968Sid2] of the presence of the NiSi phase along 

with the αNiSi 2 and ζ β phases in an alloy with 13.5 at.% Fe lying on the FeSi 2-Ni 1.04Si 1.93 

section, it follows that the equilibrium FeSi2+αNiSi2+NiSi, rather than FeSi2+αNiSi2+FeSi as 

given in [1988Ray], is present in the ternary system. 

The position of the Ni 3Si+γ+ν three-phase triangle in Fig. 3 is given in accordance with the 

data of [2005Him]. It differs from that shown for 800˚C by [1979Ind, 1988Ray]. In other 

respects, the section is close to that proposed in [1988Ray] for 600˚C. 

[1980Cha] assessing the available experimental data, calculated partial isothermal sections 

for the Fe-Ni-Si system in the range up to 30 at.% Si at 427, 527 and 627˚C. Ternary 

interactions were not incorporated into the calculations. However, the ternary phase τ 1, did 

not appear in the results of the calculations. This was due to the fact that [1980Cha] used only 

data for the binary systems for an extrapolation into the ternary system. 

By using the new experimental data of [1998Ike] and thermodynamic data on silicon 

activity in liquid Fe-Ni-Si alloys presented by [1964Bow], [1999Mie] reassessed the thermodynamic 

description for the solution phases, improving the ternary interaction parameters for 

the liquid, α and γ phases that had been optimized in an earlier study, [1998Mie]. A series of 

isothermal sections for the Fe corner of the ternary diagram, at 1200, 1100, 1000 and 800˚C, as 

well as vertical sections at 4 and 5 mass% Si were calculated, which agree reasonably well 

with the data of [1998Ike] and [1965Bur], respectively, observing that the thermodynamic 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_13 

ß Springer 2009

6 13 

Fe–Ni–Si 

parameters obtained were valid only for the Fe-rich corner. These parameters did not 

represent a complete assessment of the system owing to the lack of experimental phase 

diagram data involving the silicides and liquid. 


The vertical sections of the Fe-Ni-Si phase diagram through the 71Fe-29Ni binary alloy and 

the 59.9Fe-10.1Ni-Si ternary alloy, and an isopleth at 10 at.% Ni given by [1998Ike] are shown 

in Figs. 4 and 5. The first section shows boundaries of the two- and three-phase regions 

including the τ 1 ternary phase, as well as two-stage atomic ordering taking place in the (αFe) 

based phase. The second one depicts the change in the γ+(αFe) based phase fields with respect 

to temperature. 


Thermodynamic data on silicon activity in liquid Fe-Ni-Si alloys has been presented by 

[1964Bow]. 

Thermodynamic assessments of the Fe-Ni-Si system were performed by [1980Cha] and 

[1999Mie], see discussion above in the section Isothermal Sections. 


Ageing Fe-Ni-Si alloys with 25-32 at.% Ni and 2.5-4.2 at.% Si at 400 and 500˚C after 

quenching from 1100˚C leads to an increase in the hardness of matrix, which increases with 

annealing time [2001Him, 2002Him]. This was due to the precipitation of γ’ particles at both 

temperatures. Ageing at 500˚C leads to the precipitation of ferrite and Ni 31Si 12 as well. The 

emergence of γ’ phase precipitates also contributed to a reduction in the martensitic transformation 

temperature of the alloy. A partial shape memory effect has been observed in a 

Fe-25.5Ni-4Si (at.%) alloy, the effect increasing with a decrease in the deformation temperature 

from –30˚C to –196˚C, when it reached 38% [2002Him]. The alloy with the composition 

40 at.% Fe-10 at.% Ni has the highest value of hardness at about 1170 kg·mm –2 (11474 MPa) 

[1965Bor]. This value decreases to 670 kg·mm –2 (6570 MPa) on reducing the iron content to 

10 at.% Fe. The maximum increase in hardness (ΔHv=30) for a Fe-18Ni-1.5Si (mass%) alloy 

was observed after heating at 400˚C [1983Zay]. Increasing the silicon content to 3% resulted in 

a shift in the hardness maximum occurring at a temperature between 475-500˚C. The study of 

the maraging kinetics of Fe-18Ni-(1.5-3)Si (mass%) alloys revealed a continuous additional 

increase in the hardness as well as the specific resistivity with time in the temperature range of 

400-450˚C, and a rapid growth in hardness and specific resistivity, even after short heating 

[1983Zay]; the higher the temperature, the greater the growth. The increase in hardness after 

heating at 450 and 500˚C for 1 min is 60 and 120 Hv (588.4 and 1177 MPa) respectively. 

Alloys with 3 and 5 mass% Si in Fe-(73-75)Ni-Si (mass%) alloys were shown by [1933Dah] 

to demonstrate a behavior of hardness, electrical resistivity and magnetic characteristics 

different from that of Fe-Ni binary alloys and of ternary alloys with lower Si contents. 



MSIT 1

Magnetic susceptibility is at a minimum in FeSi 2-Ni 1.04Si 1.93 alloys with an Fe content of 

about 13 at.% [1969Mir]. The change in the microhardness of FeSi 2-Ni 1.04Si 1.93 alloys experienced 

on increasing the Fe concentration correlates with the change in lattice parameter and 

falls to a minimum at about 7 at.% Fe. A minimum in the specific electrical resistivity of these 

alloys occurs at an Fe content of 5-7 at.%. On increasing the Fe content in a solid solution 

based on Ni 1.04Si 1.93, the coefficient of thermal expansion decreases [1968Sid2]. The specific 

resistivity of NiSi increases with the addition of FeSi, while thermoelectromotive force falls 

[1968Dmi]. 

Powders with an average grain size of 8-19 nm were synthesized by high-energy ball milling 

[2005Hos]. The grain size produced in a 85Fe-5Ni-10Si (at.%) alloy was found to decrease on 

increasing the milling time to 70 h. At the same time, the magnetic characteristics of the alloy 

(coercivity and saturation magnetization) reached a minimum and maximum, respectively. 

The 87Fe-10Si-5Ni (at.%) alloy was the optimal composition showing a fine particle structure 

and good soft magnetic properties in the Fe based metastable solid solution [2005Hos]. 

[1965Bur] observed an improvement in the ductility of Fe-(3-6)Si on increasing the Ni 

content up to 5.5-7.5 mass%. 

The values of the magnetization of a Ni-doped (1 at.%) ζ β single crystal were positive and 

quite small for the temperature range 5-300 K [2004Aru]. 

[1980Sri] studied properties of electrodeposited magnetic films. Fe-(1-15%)Si-(2-80%)Ni 

(Ni : Si ≥ 2) alloys were electroplated, and the deposits, containing 15% Si and 40% Ni, were 

found to possess a tensile strength of 50 kg f·mm –2 , an elongation of 10% and their corrosion 

rate was less than 0.1 mm /year in 95% H 2SO 4, 35% HCl, 70% HNO 3 or 30% NaOH. 

A strong relationship between the chemical and magnetic ordering of γ and γ’ phases in the 

Ni3Fe-Ni3Si subsystem was found by [2004Him]. The Curie temperature for the ordered γ’ 

phase was estimated to be 680˚C by extrapolating the T C value from the Ni 3Fe-Ni 3Si system. 

The paramagnetic γ/γ’ transition temperature for the Ni 3Fe phase was evaluated to be about 

330˚C [2004Him]. 

With the view to the potential use of Fe-Ni-Si ternary alloys in optoelectronic devices, 

[2002Fet] undertook ion implantation of two metals (Fe, Ni) into a silicon substrate and 

examined the phases formed. In parallel, the phase relationships in bulk alloys were studied. 

The phase compositions of alloys annealed at 750˚C was shown to depend on Fe (Ni) 

concentration. 

Miscellaneous 


7 

[1955Tak] attributed the striking Perminvar characteristics of Fe-(8-12)Ni-(14-18)Si (mass%) 

alloys to the precipitation of dispersed τ 1 ternary phases in the αFe matrix on cooling from 

about 900˚C. 

The small grain size and good ductility at 100˚C of Fe-Ni-Si alloys with 5 mass% Si and 

≥5.5 mass% Ni was achieved by [1965Bur] through hot rolling in the α+γ region. For the 

Fe-6.5Si composition, 2 or 4 mass% Ni was not found to be effective in improving the ductility 

of hot forged and hot rolled specimens [1976Nar, 1978Nar]. The maximum permeability of 

these alloys was found to decrease with increasing nickel addition and annealing temperature. 

By studying the effect of tensile fracture on the microstructure of a Fe-18Ni-55Si (mass%) 

alloy aged at 350-400˚C, [1975Yas] demonstrated the difficulty for cross slip, which results in 

stress concentration occurring at grain boundaries leading to embrittlement, while on ageing 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_13 

ß Springer 2009

8 13 

Fe–Ni–Si 

at the higher temperature of 450-500˚C, it was the precipitation of the Ni 31Si 12 based phase 

that brought about the embrittlement. 

Si substitutes for Ni in the Ni 3Fe superstructure because of its preferred interaction with Fe 

atoms, Si not affecting the value of the long-range order parameter [1970Gom]. Using 

electronic structure calculations, [1995Slu] concluded that Fe dissolving in Ni 3Si would 

preferentially substitute for Ni when magnetic effects were ignored, but when they were 

considered in the calculations, Fe was predicted to have no site preference. 

Magnetic ordering increases the stability of the γ’ phase (ordered) rather than γ phase 

(disordered), while chemical ordering stabilizes the ferromagnetic phase rather than paramagnetic 

[2004Him]. 

γ’ phase precipitates were observed to form in γ alloys during ageing at 700˚C, in 

compositions with more than 60 at.% Fe. The Ni 3Si phase field extended to the Fe 3Si phase 

(as well as to FeNi 3 phase), forming a metastable (Fe,Ni) 3Si phase [2005Him]. 

The activation energy of the maraging process in a Fe-16.3Ni-5.7Si (mass%) alloy, 

calculated from data on the variation of the resistivity with temperature, is 130 kJ·mol –1 at 

about 400˚C and around 150-170 kJ·mol –1 at about 600˚C [1983Zay]. The activation energy of 

the annealing process in a Fe-33.4Ni-4.9Si (mass%) alloy at temperatures below 500˚C, 

calculated from studies of the variation of the hyperfine magnetic field with temperature, 

was found by [1980Rod] to be about 96 kJ·mol –1 . 

According to [1968Sid1], the change in the lattice constant across the homogeneity region 

of FeSi based alloys with Ni substituting for Fe was not linear, while [1961Wit] reported on a 

smooth change in the lattice parameter in alloys of up to 25 at.% Ni. 

The equilibrium partition ratios of solutes in a 3.06 Fe-Ni-5.09Si (mass%) alloy quenched 

from the solid-liquid region were 0.51 for silicon and 1.18 for iron, indicating a preference for 

Fe to partition to the solid and Si to the liquid [1990Kag]. 

The calculated structural parameters of the ζ β phase were shown by [2002Tan] to depend 

on the sites replaced by Ni. Data obtained for the undoped ζ β phase and a (Fe 0.875Ni 0.125)Si 2 

alloy for two types of Ni positions are presented in Table 2. 

. Table 1 

Investigations of the Fe-Ni-Si Phase Relations, Structures and Thermodynamics 


Temperature/Composition/ 

Phase Range Studied 

[1943Gre] X-ray, chemical analysis (50-100)Fe-50Ni-50Si (at.%), 600˚C 

[1955Tak] Microscopic observation, magnetic, 

dilatometry, electric resistivity, intensity of 

magnetization 

Fe-(14-18) Ni-(8-12) Si (mass%) 

[1960Iwa] XRD, pycnometer method Fe-28.8Ni-11.0Si (mass%) 

[1960Tak] Microscopic observation, magnetic and 

dilatometry 

Fe-(5-60)Ni-(3-20)Si (mass%) 

[1961Wit] X-ray 800 to 1100˚C, FeSi-NiSi, FeSi 2-NiSi 2 

[1962Gla] Melting in corundum crucibles, X-ray, optical 

microscopy analyses 

FeSi-NiSi 



MSIT 1



[1965Bor] Melting in a resistance furnace, X-ray, 

microstructure and microhardness analyses 

[1965Bur] Vacuum melting, optical microscopy, tensile 

test 

[1965Mir] Induction melting, microstructure and X-ray 

analyses 

[1968Dmi] X-ray, microstructure, specific electrical 

resistivity, emf 

[1968Mir] Induction melting, optical microscopy, X-ray 

analyses 

[1968Sid1] Induction melting, X-ray, microstructure 

analyses 

[1968Sid2] Induction melting, microstructure and X-ray 

analyses 

[1969Mir] Induction melting, microstructure and X-ray 

analyses 



Fe-Ni-Si 600-900˚C 

Fe-(4.5-7.5)Ni-(5)Si (mass%) 700- 

1250˚C 

FeSi 2.3-NiSi 2 

FeSi-NiSi 

NiSi2-FeSi2 FeSi2 -Ni1.04Si1.93 

Fe 1.04Si 1.93-Ni 1.04Si 1.93 (0-40 mass% 

FeSi 2) at 850˚C 

FeSi-NiSi, 900˚C 

FeSi 2-Ni 1.04Si 1.93, FeSi 2-NiSi 2 

Fe1.04Si1.93-Ni1.04Si1.93 (up to 40 mol% 

FeSi) 

FeSi 2-Ni 1.04Si 1.93 FeSi 2-NiSi 2, 

Fe1.04Si1.93-Ni1.04Si1.93 

[1970Gom] Neutron diffraction (FeNi3) 1–xSix, 0.02 ≤ x ≤ 0.05 

[1972Fro] Induction melting, microstructure and X-ray 

analyses 

Fe2Si-Ni2Si, 1100˚C 

[1975Ver] Induction melting, optical microscopy, X-ray, 

homogenization at 1000˚C with slow cooling 

to room temperature 

(Fe 1–xNi x) 3Si, 0 ≤ x ≤ 1 

[1975Yas] TEM, SEM, tensile test Fe-18Ni-5Si (mass%) 

[1977Nic] X-ray diffraction Fe1–xNixSi, 0.8 ≤ x ≤ 1 

[1980Cha] Calculation Fe-Ni-(0-30)Si (at.%), 427, 527, 627˚C 

[1982Yed] Electron microscopy Fe-18Ni-3Si (mass%) 

[1983Zay] Induction melting, X-ray, nuclear γ resonance, 

calorimetry 

Fe-18Ni-(1.5-3)Si (mass%) 1000˚C 

[1990Li] Induction melting, EPMA 900˚C, Fe-Ni-(23.5-26)Si (at.%) 

[1991Zha] Induction melting, EPMA 900˚C, Fe-Ni-(23,5-26)Si (at.%) 

[1994Koz] Induction arc melting, TEM, calculation 650˚C up to 30 at.% Ni and to 20 Si 

(at.%) 

[1998Ike] Induction melting, modified solid diffusion 

couples, optical microscopy, EDS, TEM 

Fe-(0-39.5)Ni-(0-24.6)Si (at.%) 

[1998Lan] Induction melting in a copper boat, neutron 

diffraction 



MSIT 1 

FeNiSi 


9 

DOI: 10.1007/978-3-540-70890-2_13 

ß Springer 2009

10 13 

Fe–Ni–Si 



[1998Mie] 

[1999Mie] 



Calculation, substitutional solution model Fe-(0-25)Ni-(0-10)Si (mass%) 1200, 

1100, 1000, 800˚C 

[1999Sun] EPMA of solid and quenched liquid after 

isothermal annealing 

[2001Duh] TEM, ED, X-ray, electrical resistivity, Mössbauer 

spectrometry 

[2001Him] Induction melting, hot rolling, annealing, 

quenching, aging, DSC, optical microscopy, 

TEM, hardness testing 

[2002Fet] Induction melting, TEM, Mössbauer 

spectroscopy, XRD, RBSC 

[2002Him] Induction melting, optical microscopy, DSC, 

TEM, ED, electrical resistivity 

3.06Fe-Ni-5.09 Si (mass%) 

Fe 73.5–x-Ni xCu 1Nb 3Si 13.5B 9, x = 10, 20, 

30, 40 (at.%) 

Fe-2.5Ni-7.5Si (mass%) 400 to 700˚C 

Ni 1–xFe xSi 2, 0.28 ≤ x ≤ 0.97 1000˚C 

Fe-(24-30)Ni-(5-8)Si (mass%) 

[2002Tan] First principle pseudopotential calculations Lattice parameter (Fe 0.875Ni 0.125)Si 2 

[2004Him] Induction melting, optical microscopy, TEM, 

EPMA, XRD, DSC, electrical resistivity, vibrating 

magnetometry 

[2005Him] Induction melting, optical microscopy, EDX, 

EPMA, TEM, electrical resistivity 

Ni3Fe-Ni3Si, 500 to 900˚C 

Ni-(0-63.3)Fe-(7-22)Si (at.%), 500 to 

1300˚C 

[2005Hos] Mechanical alloying, XRD, SEM, VSM Fe-(3-10)Mi-(10-25)Si (at.%) 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


γ, Fe 1–x–yNi xSi y cF4 at x =0,0≤ y ≤ 0.038 [Mas2] 

< 1517 Fm3m at y=0, 0 ≤ x ≤ 1 

Cu at x + y =1,0≤ y ≤ 0.158 [Mas2] 

at 0 ≤ y ≤ 0.121 [2005Him] 

at 0 ≤ x ≤ 15 

maximum of Si solubility is at 1100˚C [1998Ike] 

(γFe) a = 364.67 at 915˚C [Mas2, V-C2] 

1394 - 912 

(Ni) a = 352.4 at 25˚C [Mas2, V-C2] 

< 1455 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Lattice 

Parameters 


11 

α, Fe1–x–yNixSiy cI2 at x =0,0≤ y ≤ 0.195 

Im3m at y =0,0≤ x ≤ 0.038 (δFe) 

W at y =0,0≤ x ≤ 0.046 (αFe) 

(δFe) 

1538 - 1394 

a = 293.15 at x =0,y = 0 and 1394˚C [Mas2, V-C2] 

(αFe) 

< 912 

a = 286.65 at x =0,y = 0 and 25˚C [Mas2, V-C2] 


P63/mmc Mg 

c = 396.0 

(Si) cF2 a = 543.06 at 25˚C [V-C2, Mas2] 

< 1414 Fd3m 

C (diamond) 

γ’, FeNi3 cP4 63 to 83 at.% Ni at 347˚C [2008Kuz] 

< 517 Pm3m a = 355.23 paramagnetic γ/γ’ transition temperature is 

AuCu3 about 330˚C [2004Him] 

a = 354.3 20Fe-75Ni-5Si (at.%) 

a = 351.4 3Fe-75Ni-22Si (at.%) at RT [2004Him] 

γ’’FeNi tP4 a = 357.9 [V-C2] 

metastable P4/mmm Metastable ordering temperature 320˚C at 51.2 

AuCu 

at.% Ni [2008Kuz] 

β, Fe2Si hP6 ~33.0 to ~34.3 at.% Si [1982Kub] 

1212 - 1040 P3m1 a = 405.2 ± 0.2 [V-C2] 

Fe2Si c = 508.55 ± 0.03 dissolves 3.3 at.% Ni at 1100˚C without changing 

the crystal structure [1972Fro] 

α1,Fe3Si cF16 ordered D03 modification of Fe with 11 to 30 

≲ 1235 Fm3m 

at.% Si [1982Kub, Mas2] 

BiF3 a = 565 [V-C2] 

dissolves about 20-25 at.% Ni at 800-1200˚C 

[1977Nic, 1998Ike] 

α2,Fe4Si cP2 ordered B2 modification of Fe with 10 to 22 at.% 

≲ 1280 Pm3m 

Si [1982Kub, Mas2] 

CsCl a = 281.0 [V-C2] 

dissolves 10-15 at.% Ni at 800˚C [1998Ike] 


1060 - 825 P63/mcm a = 675.9 ± 0.5 [V-C2] 

Mn5Si3 c = 472.0 ± 0.5 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_13 

ß Springer 2009

12 13 

Fe–Ni–Si 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


ε, FeSi cP8 49.6 to 50.8 at.% Si [1982Kub] 

< 1410 P213 a = 451.7 ± 0.5 [V-C2] 

FeSi dissolves 25 at.% Ni at 800˚C [1961Wit] and 

24 at.% Ni at 600˚C [1965Bor] 

ζβ, FeSi2(r) oC48 a = 986.3 ± 0.7 at 66.7 at.% Si [V-C2, Mas2] 

< 982 Cmca b = 779.1 ± 0.6 dissolves 1.7 at.% Ni at 800˚C [1961Wit] 

FeSi2 c = 783.3 ± 0.6 

a = 987.1 

b = 777.7 

c = 783.7 

calculated by [2002Tan] 

a = 997.5 

b = 779.8 

c = 787.4 

Fe0.875Ni0.125Si2 (FeIsite) a = 999.3 

b = 779.0 

c = 786.4 

Fe0.875Ni0.125Si2 (FeIIsite) [2002Tan] 

ζα, FeSi2(h) tP3 69.5 to 73.5 at.% Si [1982Kub] 

1220 - 937 P4/mmm a = 269.01 [V-C2] 

FeSi2 c = 513.4 

Ni4Si cP4 a = 350.6 at 23.5 at.% Si [2005Him] 

< 1035 Pm3m dissolves about 8 at.% Fe at 427˚C [V-C2] 

AuCu3 dissolves 6.7 at.% Fe at 900˚C, Fe substitutes for 

both Ni and Si atoms [1990Li, 1991Zha] 

dissolves 6.4 at.% Fe at 21.1 at.% Si and 800˚C 

[2005Him] 

β2,Ni3Si (h1) < 1115 - 990 

mC16 ~24.5-25.5 at.% Si [Mas2] 

β3,Ni3Si (h2) < 1170 - 1115 

mC16 ~24.5-25.5 at.% Si [Mas2] 

ν, Ni31Si12 hP43 a = 666.7 ± 0.2 [V-C2], hP14 in [Mas2] at 27.9 at.% Si 

< 1242 P321 c = 1228 ± 0.2 [Mas2] 

Ni31Si12 γ = 120˚ dissolves >7.9 at.% Fe at 800˚C [2005Him] 

δ, Ni2Si oP12 a = 502.2 ± 0.1 at 33.3 at.% Si [V-C2, Mas2] dissolves 33.3 at.% Fe 

< 1255 Pnma b = 374.1 ± 0.1 at 1100˚C [1972Fro] 

Co2Si c = 708.8 ± 0.1 

θ, Ni2Si hP6 a = 383.6 ± 0.1 [V-C2] 

1306 - 825 P6322 Ni2Si 

c = 494.8 ± 0.1 33.4 to 41 at.% Si [Mas2] 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


σ, Ni3Si2 oC80 a = 1222.9 [V-C2] 

< 830 Cmc2 b = 1080.5 oP80 in [Mas2] 

Ni3Si2 c = 692.4 39.0 to 41 at.% Si [Mas2] 

σ’, Ni3Si2 845 - 800 

39.2 to 41 at.% Si [Mas2] 

NiSi oP8 a = 562.8 ± 0.2 [V-C2] 

< 992 Pnma b = 519.0 ± 0.1 dissolves about 5 at.% Fe [1961Wit, 1968Dmi, 

1968Sid2] 

MnP c = 333.0 ± 0.1 

αNiSi2 cF12 a = 540.74 ± 0.05 Ni1.04Si1.93 [1968Mir, 1968Sid2] 

< 981 Fm3m 

CaF2 

dissolves 10 at.% Fe at 800˚C [1961Wit] and 

about 12 at.% Fe at 850˚C [1968Mir] 

βNiSi2 993 - 981 

- - [Mas2] 

* τ1,Fe11Ni5Si4 c* at 20 at.% Si, 24 to 30 at.% Ni 

< 920 a = 613.1 [1943Gre] 

a = 613.5 ± 0.4 [1965Bor] 

a = 614.8 [1960Iwa] 

54.8Fe-25.2Ni-20Si at.% [1955Tak, 1960Tak, 

1994Koz, 1998Ike] 

* τ2,Fe3NiSi1.5 t* a = 832.5 [2001Duh] 

~500 c = 903 the existence needs a confirmation 

. Table 3 




Fe 


Ni Si 

α + γ Ð τ1 920 p α 57.8 20.6 21.5 

γ 43.0 43.7 13.3 

τ1 54.8 25.2 20.0 



MSIT 1 

13 

DOI: 10.1007/978-3-540-70890-2_13 

ß Springer 2009

14 13 

Fe–Ni–Si 

. Fig. 1 

Fe-Ni-Si. Partial FeNi 3-Ni 3Si section 



MSIT 1

. Fig. 2 

Fe-Ni-Si. Partial liquidus surface projection in the Fe rich region 



MSIT 1 


15 

DOI: 10.1007/978-3-540-70890-2_13 

ß Springer 2009

16 13 

Fe–Ni–Si 

. Fig. 3 

Fe-Ni-Si. Isothermal section at 800˚C 



MSIT 1

. Fig. 4 

Fe-Ni-Si. Isopleth through the alloys 59.9Fe10.1Ni30Si - 71Fe-29Ni (at.%) 



MSIT 1 


17 

DOI: 10.1007/978-3-540-70890-2_13 

ß Springer 2009

18 13 

Fe–Ni–Si 

. Fig. 5 

Fe-Ni-Si. Isopleth through the 10 at.% Ni isoconcentrate 



MSIT 1

References 


19 

[1933Dah] Dahl, O., Pfaffenberger, J., “Contribution to the Knowledge on Iron-Nickel Alloys” (in German), 

Z. Metallkd., 25, 241–244 (1933) (Experimental, Mech. Prop., Magn. Prop., 4) 

[1938Alt] Altgauzen, O.N., Metallurg, (3), 3–14 (1938) as quoted by [1988Ray] 

[1943Gre] Greiner, E.S., Jette, E.R., Trans. Amer. Inst. Min. Met. Eng., 152, 48–63 (1943) (Crys. Structure, 

Experimental, Phase Diagram, *, 13) 

[1955Tak] Takeda, S., Iwama, Y., Muramoto, T., “Fundamental Research of Constant Permeability Alloys. I. On 

the Cause of Perminvar Characteristics of the Senperm Alloys of the Fe-Ni-Si system” (in Japanese), 

Nippon Kinzoku Gakkai-Si, 19, 123–136 (1955) (Phase Diagram, Experimental, Phys. Prop., *, 4) 

[1960Iwa] Iwama, Y., Takeda, S., “Fundamental Research on Constant Permeability Alloys. III. Crystal Structure”, 

Nippon Kinzoku Gakkai-Si, 24, 538–540 (1960) (Crys. Structure, Experimental, 4) 

[1960Tak] Takeda, S., Iwama, Y., Sakakura, A., “Fundamental Research on Constant Permeability Alloys. II. 

Equilibrium”, Nippon Kinzoku Gakkai-Si, 24, 534–538 (1960) (Morphology, Phase Diagram, Experimental, 

*, 7) 

[1961Wit] Wittmann, A., Burger, K.O., Nowotny, H., “Mono- and Disilicide Systems of the Fe Group”, Monatsh. 

Chem., 92(5), 961–966 (1961) (Crys. Structure, Phase Diagram, Experimental, 14) 

[1962Gla] Gladyshevskiy E.I., “Crystal Structure of Compounds and Phase Equilibria in Ternary System of Two 

Transition Metals and Silicon” (in Russian), Poroshk. Metall., 410, 46–49 (1962) (Crys. Structure, Phase 


[1964Bow] Bowles, P.J., Ramstad, H.F., Richardson, F.D., “Activities of Silicon in Metals and Alloys”, J. Iron Steel 

Inst., 202, 113–121 (1964) as quoted by [1999Mie] 

[1965Bor] Borusevich, L.K., Gladyshevsky, E.I., Kuzma Yu.B., Rozum, S.M., “The Fe-Ni-Si System” (in 

Ukrainian), Visn. Lviv. Derzh. Univ., Ser. Khim., (8), 83–87 (1965) (Crys. Structure, Phase Diagram, 

Experimental, *, 13) 

[1965Mir] Miroshnikov, L.A., Sidorenko, E.A., “The Quasibinary Section α-lebeauite-NiSi 2” (in Russian), Trudy 

Uralsk. Politekhn. Inst., (144), 78–81 (1965) (Crys. Structure, Phase Relations, Experimental, 3) 

[1965Bur] Burr, D.J., Butt, R.J., Wakeman, D.W., “Effect of Ni Additions on the Structure and Ductility of Fe-Si 

Alloys”, J. Iron Steel Inst., 203, 500–501 (1965) (Crys. Structure, Phase Relations, Calculation, Experimental, 


[1968Mir] Miroshnikov, L.A., Sidorenko, F.A., Gel’d, P.V., “To Solubility of FeSi 2 and CoSi 2 in Disilicide of Nickel” 

(in Russian), Tr. Ural’sk. Politekhn. Inst., (167), 65–68 (1968) (Phase Diagram, Experimental, 5) 

[1968Sid1] Sidorenko, A.F., Dmitriev, E.A., Apasova, E.A., “Crystal Lattice Constants in Some Quasibinary Alloys 

Based on FeSi” (in Russian), Tr. Ural’sk. Politekhn. Inst., (167), 124–127 (1968) (Crys. Structure, Phase 


[1968Dmi] Dmitriev, E.A., “Solid Solutions of FeSi in NiSi” (in Russian), Tr. Ural’sk. Politekhn. Inst., (167), 

127–128 (1968) (Phys. Prop, 2) 

[1968Sid2] Sidorenko, F.A., Miroshnikov, L.A., Geld, P.V., “Range of Homogeneity and Structural Characteristics 

of Solid Solutions of the Higher Silicides of Nickel and Iron” (in Russian), Poroshk. Metall., (4), 53–59 

(1968) (Crys. Srtucture, Phase Relations, Experimental, Phys. Prop., 6) 

[1969Mir] Miroshnikov, L.A., Sidorenko, F.A., Geld, P.V., “Electronic Structure and Phase Diagrams of Quasibinary 

Systems Based on the Higher Silicides of Nickel and Cobalt” in “Teor. Eksp. Metody Issled. Diagramm 

Sostoyaniya Metal. Sist.” (in Russian), Dokl. Soveshch., Ageev, N.V., Ivanov, O.S., Grigorovich, V.K., 

(Eds.), Nauka, Moscow, 25–28 (1969) (Crys. Structure, Phase Relations, Theory, Experimental, Magn. 

Prop., 6) 

[1970Gom] Goman’kov, V.I., Puzey, I.M., Mal’tsev, E.I., “Effect of Alloying Elements on the Superstructure of 

Ni 3Fe” (in Russian), Dokl. Akad. Nauk SSSR, 194(2), 309–311 (1970) (Crys. Structure, Experimental, 6) 

[1972Fro] Frolov, A.A., Sidorenko, F.A., Krentsis, R.P., Geld, P.V., “Structural Characteristics of Fe 2Si-Ni Silicide 

Solid Solutions” (in Russian), Zh. Neorg. Khim., 17, 2574–2575 (1972) (Crys. Structure, Phase Relations, 


[1975Yas] Yasunaka, T., Araki, T., “Effect of Microstructure on the Tensile Fracture in Fe-18Ni-5Si Alloy”, Trans. 

Nat. Res. Inst. Met., 17(5), 277–284 (1975) (Crys. Structure, Phase Relations, Experimental, Mechan. 

Prop., 17) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_13 

ß Springer 2009

20 13 

Fe–Ni–Si 

[1975Ver] Vereshchagin, Yu.A., “Procedure for Synthesis, Homogeneity Regions and Lattice Spacings of Fe” (in 

Russian), Fiz. Metody Issled. Tverdogo Tela, (1), 40 (1975) (Crys. Structure, Phase Relations, Experimental, 

9) 

[1976Nar] Narita, K., Enokizono, M., “Effects of Ni, Al and Mn Addition on the Mechanical and Magnetic 

Properties of 6.5% Si-Fe Sheets”, IEEE Trans. Magn., 12(6), 873–873 (1976) (Mechan. Prop., Magn. 

Prop., 0) 

[1977Nic] Niculescu, V., Budnick, J.I., “Limits of Solubility, Magnetic Properties and Electron Concentration in 

Fe 3–xT xSi System”, Solid State Commun., 24(9), 631–634 (1977) (Crys. Structure, Experimental, Magn. 

Prop., 17) 

[1978Nar] Narita, K., Enokizono, M., “Effect of Nickel and Manganese Addition on Ductility and Magnetic 

Properties of 6.5 % Silicon-Iron Alloy”, IEEE Trans. Magn., 14(4), 258–262 (1978) (Morphology, 

Experimental, Magn. Prop., Mech. Prop., 5) 

[1979Ind] Inden, G., “Zwischenbericht 4”, 1979, Düsseldorf, Max-Planck-Institut für Eisenforschung as quoted by 

[1988 Ray] 

[1980Sri] Srivastava, S.C., “Electrodeposition of Ternary Alloys: Developments in 1972 - 1978”, Surf. Technol., 

10, 237–257 (1980) (Review, Electrochemistry, Magn. Prop., 121) 

[1980Rod] Rodionov, Y.L., Isfandiyarov, G.G., Zambrzhitskiy, V.N., “Influence of Annealing on the Redistribution 

of Atoms in the Austenite of Fe-Ni-Mo and Fe-Ni-Si”, Phys. Met. Metallogr., 49(2), 94–100 (1980) 

(Experimental, Kinetics, 8) 

[1980Cha] Chart, T., Putland, F., Dinsdale, A., “Calculated Phase Equilibria for the Cr-Fe-Ni-Si System - I Ternary 

Equilibria”, Calphad, 4(1), 27–46 (1980) (Phase Diagram, Calculation, 75) 

[1982Kub] Kubaschewski, O., “Iron - Silicon” in “Iron Binary Phase Diagrams”, Springer Verlag, Berlin, 136–139 


[1982Yed] Yedneral, A.F., Rusanenko, V.V., Smirnova, A.V., “On the Structure of the Intermetallic Phase 

Precipitated During Maraging of the Alloy Fe -18% Ni - 3% Si”, Phys. Met. Metall., 53(3), 111–117 

(1982), (Crys. Structure, Experimental, 7) 

[1983Zay] Zaytseva, R.D., Zakharova, N.A., Perkas, M.D., Rusanenko, V.V., Shaposhnikov, N.G., “Investigation of 

the Maraging of Fe-Ni-Si Alloys and the Influence of Cobalt on the Process”, Phys. Met. Metall., 55(1), 

117–123 (1983), (Crys. Structure, Experimental, Kinetics, Phys. Prop., 11) 

[1988Ray] Raynor, G.V., Rivlin, V.G., “Fe-Ni-Si” in “Phase Equilibria in Iron Ternary Alloys”, Inst. Metals, London, 

416–432 (1988) (Crys. Structure, Phase Diagram, Assessment, 20) 

[1990Kag] Kagawa, A., Hirata, M., Sakamoto, Y., J. Mater. Sci., 25, 5063–5069 (1990) as quoted by [1999Sun] 

[1990Li] Li, Y., Zhang, T., Zheng, Z., Zhu, Y., “Solution Behaviour of Various Alloying Elements in Ni3Si” (in 

Chinese), Acta Metall. Sin., 26(3), A172–A176 (1990) (Phase Diagram, Experimental, 9) 

[1991Zha] Zhang, T., Li, Y., Zheng, Z., Zhu, Y., “Alloying Behavior of Ni 3Si and the 900˚C Isotherms of Several 

Ni-Si-X Systems at Ni-Rich Corner” in “High-Temp. Ordered Intermetallic Alloys IV”, Mater. Res. Soc. 

Symp. Proc., 213, 137–142 (1991) (Phase Diagram, Experimental, 7) 

[1994Rag] Raghavan, V., “Fe-Ni-Si (Iron-Nickel-Silicon)”, J. Phase Equilib., 15(6), 629–630 (1994) (Phase Diagram, 

Review, 4) 

[1994Koz] Kozakai, T., Miyazaki, T., “Experimental and Theoretical Investigations on Phase Diagrams of Fe 

Base Ternary Ordering Alloys”, ISIJ Int., 34(5), 373–383 (1994) (Phase Diagram, Calculation, Magn. 

Prop., 18) 

[1995Slu] Sluiter, M., Kawazone, Y., “Site Preference of Ternary Additions in Ni 3Si” in “High-Temperature 

Ordered Intermetallic Alloys VI”, Mater. Res. Soc.. Symp. Proc., 364(Pt.2), 1064–1069 (1995) (Experimental, 

Calculation, Theory, 13) 

[1998Ike] Ikeda, O., Himuro, Y., Ohnuma, I., Kainuma, R., Ishida, K., “Phase Equilibria in the Fe-Rich Portion of 

the Fe-Ni-Si System”, J. Alloys Compd., 268, 130–136 (1998) (Phase Relations, Experimental, *, 13) 

[1998Lan] Landrum, G.A., Hoffmann, R., Evers, J., Boysen, H., “The TiNiSi Family of Compounds: Structure and 

Bonding”, Inorg. Chem., 37(22), 5754–5763 (1998) (Crys. Structure, Experimental, 34) 


(1998) (Phase Relations, Assessment, Calculation, 83) 

[1999Sun] Sung, P.K., Poirier, D.R., “Liquid-Solid Partition Rations in Nickel-Base Alloys”, Metall. Mater. Trans. A, 

30A, 2173–2181 (1999) (Crys. Structure, Experimental, 41) 

[1999Mie] Miettinen, J., “Thermodynamic Description of Solution Phases of Systems Fe-Cr-Si and Fe-Ni-Si with 

Low Silicon Contents and with Application to Stainless Steels”, Calphad, 23(2), 249–262 (1999) (Phase 

Relations, Thermodyn., Calculation, 28) 



MSIT 1


21 

[2001Duh] Duhaj, P., Svec, P., Sitek, J., Janickovic, D., “Thermodynamic, Kinetic and Structural Aspects of the 

Formation of Nanocrystalline Phases in Fe 73.5–xNi xCu 1Nb 3Si 13.5B 9 Alloys”, Mater. Sci. Eng. A, 304–306, 


[2001Him] Himuro, Y., Ikeda, O., Kainuma, R., Ishida, K., “Effect of Ausaging on the Morphology of Martensite in 

an Fe-25%Ni-7.5%Si Alloy”, J. Phys. IV, France, 11(PR8), 205–210 (2001) (Phase Relations, Morphology, 

Experimental, Mechan. Prop., 14) 

[2002Tan] Tani, J.-I., Kido, H., “First Princple Calculation of the Geometrical and Electronic Structure of 

Impurity-Doped β-FeSi 2 Semiconductors”, J. Solid State Chem., 163, 248–252 (2002) (Crys. Structure, 

Calculation, Phys. Prop., 23) 

[2002Him] Himuro, Y., Kainuma, R., Ishida, K., “Martensitic Transformation and Shape Memory Effect in 

Ausaged Fe-Ni-Si Alloys”, ISIJ Int., 42(5), 184–190 (2002) (Phase Relations, Experimental, 21) 

[2002Fet] Fetzer, C., Dezsi, I., Vantomme, A., Wu, M.F., Jin, S., Bender, H., “Ternary Co xFe (1–x)Si 2 and 

Ni xFe (1–x)Si 2 Formed by Ion Implantation in Silicon”, J. Appl. Phys., 92(7), 3688–3693 (2002) (Crys. 

Structure, Phase Relations, Experimental, Electronic Structure, 27) 

[2003Rag] Raghavan, V., “(Iron-Nickel-Silicon)”, J. Phase Equilib., 24(3), 269–271 (2003) (Crys. Structure, Phase 

Diagram, Assessment, 14) 

[2004Aru] Arushanov, E., Nenkov, K., Eckert, D., Vinzelberg, H., Roessler, U.K., Behr, G., Mueller, K.-H., 

Schumann, J., “Magnetic and Electrical Properties of Cr- and Ni-doped β-FeSi 2 Single Crystals”, J. Appl. 

Phys., 96(4), 2115–2121 (2004) (Phase Relations, Experimental, Electr. Prop., Magn. Prop., 31) 

[2004Him] Himuro, Y., Tanaka, Y., Kamiya, N., Ohnuma, I., Kainuma, R., Ishida, K., “Stability of Ordered L12 

Phase in Ni 3Fe-Ni 3X (X: Si and Al) Pseudobinary Alloys”, Intermetallics, 12(6), 635–643 (2004) (Crys. 

Structure, Morphology, Phase Diagram, Experimental, Electr. Prop., Magn. Prop., *, 19) 

[2005Him] Himuro, Y., Tanaka, Y., Ohnuma, I., Kainuma, R., Ishida, K., “Phase Equilibrua and γ’-L1 2 Phase 

Stability in the Ni-rich Portion of Ni-Fe-Si and Ni-Fe-Al Systems”, Intermetallics, 13, 620–630 (2005) 

(Crys. Structure, Phase Diagram, Experimental, 19) 

[2005Hos] Hosseini Madaah, H.R., Bahrami, A., “Preparation of Nanocrystalline Fe-Si-Ni Soft Magnetic Powders 

by Mechanical Alloying”, Mat. Sci. Eng. B, 123, 74–79 (2005) (Morphology, Experimental, Magn. 

Prop., 17) 

[2008Kuz] Kuznetsov, V., “Fe-Ni (Iron-Nickel)”, MSIT Binary Evaluation Program in MSIT Workplace, G. (Ed.), 

MSI, Materials Sciens International Servises GmbH, Stuttgart, to be published (2008) (Crys. Structure, 

Phase Diagram, Phase Relations, Thermodyn., Assessment, Phys. Prop., #, 41) 


(1990) 





MSIT 1 

DOI: 10.1007/978-3-540-70890-2_13 

ß Springer 2009

Iron – Nickel – Titanium 


Gautam Ghosh 

Introduction 

Fe–Ni–Ti 14 

1 

A fairly large number of experimental studies have been carried out to establish the ternary 

phase equilibria [1938Vog, 1941Vog, 1963Spe, 1967Dud, 1981Loo, 1999Abr, 2006Ria]. The 

first comprehensive study of phase equilibria was carried out by [1938Vog]. They used 

metallography, thermal analysis and X-ray diffraction techniques. [1963Spe] reported partial 

isothermal sections, representing phase equilibria of Fe corner, at 700 and 1100˚C. [1967Dud] 

established a quasibinary section, TiFe-TiNi, using twenty-one ternary alloys prepared using 

elements of purity greater than 99.94%. They used metallography, thermal analysis, X-ray 

diffraction techniques to determine the phase equilibria. [1981Loo] employed diffusion 

couples technique to determine the isothermal section at 900˚C. They prepared alloys using 

elements of following purity: 99.95% Fe, 99.99% Ni and 99.97% Ti. Three types of diffusion 

couples, element/element, element/alloy, alloy/alloy, and fifteen in total, were prepared by 

solid state resistance welding. The couples were then sealed in evacuated silica tubes and 

annealed at 900˚C for up to 900 h. Except [1981Loo], other experimental studies were 

restricted to alloys containing less than 50 at.% Ti. The results of these phase equilibrium 

studies were reviewed earlier [1949Jae, 1985Gup, 1991Gup]. 

More recently, [1994Ali1] reported the phase equilibria of alloys containing more than 50 

at.% Ti. They used Armco Fe, N-00 grade electrolytic Ni, and iodide Ti to prepare alloys by arc 

melting in an inert atmosphere. They prepared a number of ternary alloys in the Ni and Fe 

atomic ratios of 1:3, 1:1, and 3:1. The phase equilibria were determined using thermal analysis, 

metallography and X-ray diffraction. [1994Ali2] carried out rapid solidification of ternary 

alloys containing up to 33.85 at.% Fe and 26.8 at.% Ni. The alloys were subsequently annealed 

at 900˚C for 25 h, and the microstructures were compared. [1994Jia] measured the partitioning 

of Fe and Ti between (Ni) and TiNi 3 (or the tie lines) at 1000, 1100 and 1200˚C. They 

prepared diffusion couples between 5Fe-Ni (mass%) and 21Ti-1Fe-Ni (mass%) alloys. The 

couples were annealed for up to 300 h followed by quenching into iced brine. The compositions 

of the phases were measured by electron probe microanalysis. 

[1999Abr] determined the isothermal section at 1000˚C using both bulk alloys and 

diffusion couples. They prepared bulk alloys using iodide grade Ti, electrolytic grade Ni and 

carbonyl grade Fe in an arc furnace. The bulk alloys were equilibrated at 1200˚C for 150 h. 

They also prepared a large number of couples using Fe-Ni, Fe-Ti and Ni-Ti alloys that were 

welded at 1200˚C and at a pressure of 19.6 MPa. The couples were subsequently annealed at 

1200˚C. The diffusion paths and phase compositions were established by means of electron 

probe microanalysis. Besides graphical representation, [1999Abr] tabulated the tie line and tie 

triangle compositions. Based on diffusion couple results, [1999Abr] identified six two-phase 

regions (TiNi-TiFe 2, TiNi-TiNi 3, TiNi 3-TiFe 2, γ(Fe,Ni)-TiNi 3, γ(Fe,Ni)-TiFe 2) and three 

three-phase regions (γ(Fe,Ni)-TiFe 2-TiNi 3,TiFe 2-TiNi-TiNi 3,(βTi)-TiFe-Ti 2Ni). 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_14 

ß Springer 2009

2 14 

Fe–Ni–Ti 

[2006Ria] studied phase relations in six ternary alloys, with composition along Ti 2Ni- 

Ti 2Fe, using SEM-EDS and DTA methods. The alloys were prepared by arc melting using 99.99 

mass% Fe, 99.99 mass% Ni and 99.98 mass% Ti. They were homogenized at 900˚C for 15 days. 

The authors reported phase compositions and a tentative isopleth. 

[1999Efi, 2000Efi] studied microstructures of TiFe/Ni diffusion couples annealed at 

1200˚C for up to 1.5 h. Based on the dynamics of interfacial microstructure, they derived 

the interdiffusion coefficients. 

Besides phase equilibria studies at high temperatures, the effect of Fe on the low temperature 

martensitic transformations of TiNi has also been studied extensively [1982Hwa1, 

1982Hwa2, 1982Nis, 1983Sav, 1984Ano, 1984Pus, 1985Goo, 1985Sav, 1986Edm, 1987Chu, 

1987Kha, 1987Sas, 1989Ano1, 1989Ano2, 1990Rao, 1991Pro, 1992Ruz, 1992Shi, 1993Mat, 

1995Air, 1995Gue, 1997Har, 1998Tam, 1999Zha, 2000Chu, 2000Lap, 2000Vor, 2000Xu, 

2001Mur, 2002Ish, 2005Cho, 2005Wan, 2006Fan, 2007Pro]. 

[2001Gup] reviewed some of the results of recent phase equilibria studies. Additional 

reviews have also been published by [2006Cac] and [2006Gho]. 

A summary of experimental studies on phase relations is given in Table 1. 


The Fe-Ti, Fe-Ni and Ni-Ti binary phase diagrams are accepted from [1991Mur], [2008Kuz] 

and [2008Ted], respectively. 


The solubility of Fe in (βTi) can be increased from 24 to 29.5 at.% by rapid solidification 

[1994Ali2] where the cooling rate was estimated to be 10 6 ˚C·s –1 . Rapid solidification also 

suppresses the eutectoid reaction (βTi) Ð (αTi) + TiFe. In the ternary alloys, up to 25.95 at.% 

Fe and 8.23 at.% Ni can be dissolved in (βTi) by rapid solidification. 

[1968Abr] reported the lattice parameter of two sets of austenitic alloys: Fe-27Ni (at.%) 

containing up to 10 at.% Ti and Fe-30Ni (at.%) containing up to 6 at.% Ti. Powders of these 

alloys were solution treated at 1024˚C and quenched to room temperature. Variation of lattice 

parameter gives the solubility limit of Ti in austenite at 1024˚C. For example, it is about 5.4 

at.% Ti in Fe-27Ni (at.%) alloy. 

Fcc to bcc martensitic transformation in Fe rich alloys has been investigated extensively 

[1963Yeo, 1969Abr, 1972Kok, 1974Whi, 1977Hal, 1978Uva, 1984Kab, 1984Tad]. With the 

addition of Ti in Fe-Ni alloys, the crystal symmetry of martensite changes from bcc to bct due 

to clustering and/or precipitation of metastable coherent precipitates (L12-Ni3Ti) [1969Abr, 

1974Whi, 1977Hal]. The c/a ratio of bct martensite increases linearly with Ti content in the 

alloy; however, the degree of tetragonality depends on the Ni content in the alloy. 

TiFe and TiNi form a continuous solution in the solid state [1967Dud, 1981Loo], and the 

lattice parameter decreases linearly from TiNi to TiFe [1967Dud]. Using a linear muffin-tin 

orbital method, [2002Boz] calculated the formation energies associated with dilute additions 

of Ni in B2-TiFe. In the dilute limit of Ni, the formation energy of (Fe,Ni) 0.5Ti 0.5 is predicted 

to be more negative than Fe0.5(Ti,Ni)0.5 implying that Ni atoms prefer to occupy the Fe 

sublattice in TiFe. 



MSIT 1

At 900˚C, TiFe 2 dissolves up to 28 at.% Ni, TiNi 3 dissolves up to 14 at.% Fe, and Ti 2Ni 

dissolves up to 26 at.% Fe [1981Loo]. The solubility of Fe in TiNi 3 increases to 15.4 ±⊊0.8 

at.% Fe at 1200˚C [1999Efi]. In TiNi 3 and NiTi 2, Fe resides primarily on the Ni sublattice. In 

TiFe 2, Ni resides primarily on the Fe sublattice. 

Binary B2-TiNi undergoes martensitic transformation at low temperature to a monoclinic 

structure, commonly known as B19’ martensite [1992Shi, 1995Gue]. However, at slightly Ni 

rich composition, the presence of dislocations, or the presence of metastable Ti3Ni4 precipitates 

are known to promote another displacive transformation to a rhombohedral structure 

preceding B19’ transformation, commonly known as the R phase [1987Sas, 1995Air, 1997Har, 

1998Tam, 2001Mur, 2002Ish, 2005Ste, 2006Cho, 2006Fan, 2006Yam]. Depending on the 

composition and thermal history of binary TiNi, and with the addition of Fe, the transformation 

temperatures B2 → R → B19’ may be well separated. The presence of the R-phase is very 

useful for shape memory applications which rely on small thermal hysteresis. 

[1994Jia] reported the partitioning ratio of Fe, defined by x Fe(TiNi 3)/x Fe(Ni), where x Fe is 

the mole fraction of Fe, between (Ni) and TiNi3. The partitioning ratios at 1000, 1100 and 

1200˚C were 0.41, 0.44 and 0.61, respectively. 

There is no ternary phase in this system. The details of the crystal structures and lattice 

parameters of the solid phases are listed in Table 2. 


Even though there are no true quasibinary sections, two sections have been reported as quasibinary. 

[1938Vog] reported the TiFe2-TiNi3 section with the eutectic reaction L Ð TiFe2 + 

TiNi 3 at 1320˚C. [1967Dud] established the section TiFe-TiNi, which is shown in Fig. 1. The 

continuous solid solubility between TiFe and TiNi was confirmed by lattice parameter and 

hardness measurements. [1967Dud] established only the solidus boundary. However, in the 

TiFe-end both liquid+TiFe 2 and liquid+TiFe 2+Ti(Fe,Ni) phase regions should appear due to 

formation of TiFe. The liquidus line expected by [1967Dud] appears to be inconsistent with 

the investigated solidus. Also, in agreement with the comments by [1991Gup] it is here 

reported with a minimum so that B2-Ti(Fe,Ni) melts congruently around 1270˚C. 


Figure 2 shows the reaction scheme involving five invariant (U 1,U 2,E 1,U 3,U 4) and a 

maximum (e 1) reactions. Among these, e 1,U 1 and E 1 were reported by [1938Vog] while U 3 

and U 4 were reported by [1994Ali1]. The invariant reaction U 2 has not been experimentally 

verified, but it was speculated by [1991Gup]. The composition of the phases participating in 

e1, U1, E1 and U3 are listed in Table 3. These compositions were read from the superimposed 

liquidus and projection diagrams provided by [1938Vog], [1994Ali1] and [2001Gup]. 



3 

The liquidus surface and projection diagram for the composition range Fe-TiFe 2-TiNi 3-Ni was 

presented by [1938Vog]. The superimposed liquidus surface and projection diagram for the Ti 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_14 

ß Springer 2009

4 14 

Fe–Ni–Ti 

corner was reported by [1994Ali1], and slightly modified by [2001Gup]. Using these results 

and the accepted binary phase diagrams, the liquidus surface shown in Fig. 3 was constructed. 


[1963Spe] reported partial isothermal sections of the Fe corner at 700 and 1100˚C; however, 

did not provide details of the experimental techniques and procedures. Figure 4 shows a 

partial isothermal section of the Fe rich corner at 1100˚C [1963Spe]. Figure 5 and 6 show 

isothermal sections at 1000 [1999Abr] and 900˚C [1981Loo], respectively. The results of 

[1981Loo] and [1999Abr] agree very well; however, a major discrepancy is that [1999Abr] 

observed very little solubility of Fe in Ti 2Ni while [1981Loo] reported that about 78 % Ni sites 

in Ti 2Ni can be substituted by Fe i.e., the solid solubility is about 26 at.% Fe. In another 

investigation, [1994Ali2] reported that only about 1.5 at.% Fe dissolves in Ti2Ni where rapidly 

solidified Fe-Ni-Ti alloys were annealed at 900˚C for only 25 h compared to up to 900 h by 

[1981Loo]. It is not clear if a short annealing treatment used by [1994Ali2] is responsible for 

the much lower solubility of Fe in Ti 2Ni compared to [1981Loo]. The continuous solubility of 

TiFe and TiNi observed by [1981Loo] and [1999Abr] confirms the earlier results of 

[1967Dud]. In Figs. 5 and 6, the widths of TiNi and TiNi 3 fields have been adjusted to make 

them consistent with the accepted Ni-Ti phase diagram. The solubility of Fe in TiNi 3 at 900˚C 

is about 15 at.% [1981Loo] which is much higher than reported by [1938Vog]. Figure 7 shows 

a partial isothermal section of the Fe corner at 700˚C [1963Spe]. 


Several temperature-composition sections have been reported. Figures 8, 9 and 10 show 

polythermal sections at 8, 12 and 14.4 mass% Ti [1938Vog], respectively, and Fig. 11 shows 

an isopleth at 66.67 at.% Ti [2006Ria]. While the later authors identified a two-phase field, 

Ti2(Fe,Ni)+Ti(Fe,Ni), in the isopleth based on the microstructural observations, this is most 

likely to have caused by non-stoichiometric alloy composition. To be consistent with the 

isothermal section at 900C in Fig. 6, the above mentioned two-phase field is considered as a 

single-phase field Ti 2(Fe,Ni) in Fig. 11. Figures 12 and 13 show temperature-composition 

sections at constant Fe:Ni mass ratios of 90:10 and 40:60, respectively [1938Vog]. The 

existence of two invariant reactions at 1200˚C (U 1) and at 1120˚C (E 1) is reflected in Figs. 8 

to 10. The partial isopleths of the Ti corner and at constant Fe:Ni atomic ratios of 1:3, 1:1 and 

3:1 are shown in Figs. 14, 15 and 16, respectively [1994Ali1]. On the basis of these three 

isopleths, [1994Ali1] gave a superimposed partial liquidus surface and projection diagram for 

the Ti corner. Due to the existence of (βTi)+Ti(Fe,Ni) phase field in Fig. 14, the original 

projection diagram was slightly modified by [2001Gup]. 


[1975Ost] reported the enthalpy of dissolution of Ti in Fe-Ni melts. [1991Lue] measured the 

enthalpy of mixing of liquid Tix(Fe0.89Ni0.11)1–x, 0.295 ≤ x ≤ 0.041, at 1600˚C using a highvacuum 

high-temperature calorimeter. They also modeled the molar heat of mixing of the 



MSIT 1

entire Fe-Ni-Ti system using various extrapolation methods. Subsequently, these experimental 

data were used to validate “thermodynamic adapted” power series for the extrapolation of 

thermodynamic quantities [1995Tom]. [1999Thi] also carried out calorimetric measurement 

of heat of mixing of liquid alloys in three composition ranges: (i) (Fe 84Ti 16) 1–xNi x, 0.02 < x < 

0.35 at 1621˚C, (ii) (TiFe 2) 1–xNi x, 0.02 < x < 0.4 at 1643˚C, and (iii) (TiNi) 1–xFe x, 0.02 < x < 

0.8 at 1645˚C. [1999Thi] used an associate model to describe the heat of mixing of ternary 

alloys. Two associates, TiNi3 and TiFe, were assumed to be present in the liquid. In the entire 

composition range, the model calculations agree very well with the experimental data implying 

that binary interactions are sufficient to describe the excess heat of mixing. Their model 

calculations also agree very well with the experimental data of [1991Lue]. The functional 

representation of experimental heat of mixing along four composition sections is provided in 

Table 4. Figure 17 shows the isoenthalpy (mixing) contours at 1643˚C [1999Thi]. [1991Lue] 

also reported isoenthalpy (mixing) contours by an extrapolation method, but their results 

differ significantly from [1999Thi]. 

[1990Kum] calculated phase boundaries involving bcc, fcc ((αFe), (γFe)) and Ti2Ni by 

CALPHAD method. They did not consider any ternary interaction parameter, and partial 

isothermal sections were calculated at 850, 950, 1050 and 1150˚C. Later, [1998Mie] also 

applied CALPHAD method to calculate phase equilibria involving liquid, (αFe) and (γFe) 

phases. He introduced asymmetric ternary interaction parameters for the liquid phase and a 

symmetric ternary interaction parameter for the bcc phase, but no ternary interaction 

parameter for the fcc phase. The calculated isothermal sections of Fe corner at 1100 and 

1200˚C were found to be in good agreement with the experimental data. 



5 

A summary of experimental investigation of properties is given in Table 5. 

Ti 0.5(Fe 1–xNi x) 0.5 alloys are known to exhibit shape memory effect [1999Zha, 2000Jia, 

2000Xu, 2005Wan, 2006Cho, 2007Pro]. [2000Xu] obtained a maximum shape recovery strain 

of 5.6% after deforming Ti 50Fe 2Ni 48 alloy at –70˚C. The damping behavior [2006Fan], 

resistivity [1987Chu, 2005Cho] and magnetic susceptibility [2005Cho, 2005Yam] ofB2-TiNi 

(Fe) alloys have also been reported. The hot deformation behavior and anomalous ductility of 

Ti 50Fe 2Ni 48 has been studied by Nishida et al. [2003Nis]. 

The single crystal elastic constants (c’ and c 44) ofB2-TiNi(Fe) alloys have been studied by 

ultrasonic resonance method [1987Kha, 1999Zha]. It has been shown that both c’ and c 44 

decrease sharply near the martensitic transformation temperature. 

Hydriding behavior of TiFe(Ni) phase has been investigated [1999Lee, 2003Miy, 2004Jan, 

2005Jan]. [1999Lee] studied hydriding behavior of TiFe 1–xNi x for x = 0.1, 0.15 and 0.2. They 

found that partial substitution of Fe by Ni in TiFe does not change the hydriding behavior, 

except that these alloys can be hydrided without the activation treatment. Nanocrystalline 

TiFe 0.25Ni 0.75 alloy has 1.5 times the discharge capacity of TiFe [2004Jan, 2005Jan]. 

C14-Ti(Fe 1–xNi x) 2 is antiferromagnetic, and the Néel temperature of C14-Ti(Fe 1–xNi x) 2 

decreases with increasing Ni content [2005Yam]. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_14 

ß Springer 2009

6 14 

Fe–Ni–Ti 

Miscellaneous 

Discontinuous precipitation in ternary metastable alloys has been studied several times 

[1963Spe, 1973Zem, 1979Fou, 1979Zem, 1981Zem, 1995Zem]. [1963Spe] investigated an 

Fe-5.8Ti-29.7Ni (mass%) alloy in the temperature range of 400 to 975˚C, and [1979Fou] 

investigated an Fe-6.5Ti-28.5Ni (mass%) alloy in the temperature range of 400 to 900˚C. 

[1979Zem] used Fe-(2 to 5)Ti-(25 to 26)Ni (mass%) alloys heat treated at 790˚C. According to 

[1963Spe], ternary alloys may exhibit two types discontinuous precipitations 

g ! g1 þ TiNi3 

g1 ! g2 þðFe; NiÞ2Ti; where γ 1 and γ 2 are austenitic solid solutions with different solute contents. Both 

[1979Fou] and [1979Zem] observed only the first discontinuous reaction where TiNi 3 is a 

metastable phase because the alloys lie in the γ+TiFe 2 phase field. The second discontinuous 

reaction is very sluggish [1963Spe]. 

[1988Sag, 1992Sag] studied the effect of severe plastic deformation of austenitic 2.6Ti-Fe- 

36Ni alloy containing equilibrium TiNi 3 (η, D0 24) and metastable TiNi 3 (γ’, L1 2) precipitates 

which were obtained by adjusting the aging treatments. Upon severe plastic deformation both 

types of precipitates dissolve in the matrix due to strong interaction with dislocations 

[2002Kuz]. 

[1995Ali] carried out rapid solidification of 29 alloys in the composition range Ti-TiFe- 

TiNi. They reported the phases present after rapid solidification and also after aging at 900˚C 

for 25 h. 

The hot deformation of austenitic alloys and the resulting properties were studied by 

[1989Gor, 1991Pro]. The martensitic transformation (γ→α) start temperature (M s) of 

Fe-22.5Ni (mass%) [1963Yeo], Fe-27Ni (mass%) [1969Abr] and Fe-29.5Ni (mass%) 

[1969Abr] alloys decreases with the addition of Ti. 

The effect of Fe on the martensitic transformations (B2 → R → B19’) in TiNi has been 

studied extensively [1982Hwa1, 1982Hwa2, 1982Nis, 1983Sav, 1984Ano, 1984Pus, 1985Goo, 

1985Sav, 1986Edm, 1987Chu, 1987Kha, 1987Sas, 1989Ano1, 1989Ano2, 1990Rao, 1991Pro, 

1992Ruz, 1992Shi, 1993Mat, 1995Air, 1995Gue, 1997Har, 1998Tam, 1999Zha, 2000Chu, 

2000Lap, 2000Vor, 2000Xu, 2001Mur, 2002Ish, 2005Cho, 2005Wan, 2006Fan, 2007Pro]. 

Addition of Fe decreases both pre-martensitic and martensitic transformation temperatures, 

and stabilizes the R phase (rhombohedral). 

[1999Efi] reported the interdiffusion coefficient of ternary solid solutions (γ) at 1200˚C 

with nickel contents of 87 to 99 at.%. 

[1985Val] found that the average magnetic moment of γ’FeNi 3 decreases when Fe is 

replaced by Ti. 



MSIT 1

. Table 1 

Investigations of the Fe-Ni-Ti Phase Relations, Structures and Thermodynamics 

Reference 


Method/Experimental 

Technique Temperature/Composition/Phase Range Studied 

[1938Vog] LOM, DTA Fe-Ni-Ni3Ti-Fe3Ti, vertical sections 

[1941Vog] LOM 900-1220˚C, Ni-17Fe-14Ti (mass%) 

[1963Spe] LOM, TEM, XRD Partial isothermal sections at 700 and 1100˚C, 

Fe-30Ni-6Ti (mass%) 

[1967Dud] DTA, XRD, hardness TiNi-TiFe 

[1968Abr] XRD Fe-(27-30) at.% Ni-(1-10) at.% Ti 

[1975Ost] Calorimetry 1600˚C, liquid 

[1981Loo] LOM, XRD, EPMA Isothermal section at 900˚C 

[1991Lue] Calorimetry 1600C, liquid 

[1994Ali1, 

1994Ali2] 

DTA, XRD, metallography Ti-TiFe-TiNi; vertical sections 

7 

[1994Jia] EPMA 1000 to 1200˚C, partitioning ratio between (Ni) and 

Ni3Ti [1995Ali] XRD 900C; Ti-TiFe-TiNi 

[1999Abr] EPMA Isothermal section at 1000˚C 

[1999Efi] EPMA, hardness 1200C, interdiffusion 

[1999Thi] Calorimetry 1624-1645˚C, liquid 

[2000Efi] EPMA, hardness 1100-1250˚C, interdiffusion 

[2006Ria] SEM-EDS, DTA Ti2Ni-Ti2Fe Landolt‐Börnstein 


MSIT 1 

DOI: 10.1007/978-3-540-70890-2_14 

ß Springer 2009

8 14 

Fe–Ni–Ti 

. Table 2 



Temperature 

Range 

[˚C] 

Pearson 

Symbol/ 

Group 

Space/ 

Prototype 



(δFe)(h2) cI2 a = 293.15 pure Fe at 1390˚C [Mas2] 

1538 - 1394 Im3m 

W 

γ, (γFe,Ni) cF4 a = 358.37 Fe71.74Ni27.07Ti1.19, at 20˚C [1968Abr] 

Fm3m a = 359.13 Fe68.27Ni26.96Ti4.77, at 20˚C [1968Abr] 

Cu a = 358.90 Fe68.32Ni30.38Ti1.3, at 20˚C [1968Abr] 

a = 359.39 Fe64.39Ni29.65Ti5.96, at 20˚C [1968Abr] 

a = 359.0 Fe31Ni63Ti6, at 20˚C [1981Loo] 


(γFe)(h1) 1394 - 912 

a = 364.67 pure Fe [Mas2] 

(Ni) 

< 1455 

a = 352.32 pure Ni at 20˚C [V-C2] 

(αFe)(r) cI2 a = 286.65 pure Fe at 20˚C [V-C2] 

< 912 Im3m 

W 

(εFe) hP2 a = 246.8 at 25˚C, 13 GPa [V-C2] 

P63/mmc Mg 

c = 396.0 

(βTi)(h) cI2 a = 330.65 [Mas2] 

1670 - 882 Im3m 

W 

(αTi)(r) hP2 a = 295.06 pure Ti at 25˚C [Mas2] 

≤ 882 P63/mmc Mg 

c = 468.25 

γ’FeNi3 cP4 a = 355.23 63 to 85 at.% Ni [2008Kuz] 

≤ 517 Pm3m 

AuCu3 TiFe2 hP12 a = 478.7 24.0 to 36.0 at.% Ti [V-C2] 

≤ 1427 P63/mmc c = 781.5 

MgZn2 dissolves up to 28 at.% Ni [1981Loo] 

Ti(Fe,Ni) cP2 a = 300.0 Fe10.2Ni39.8Ti50, at 20˚C [1967Dud] 

Pm3m a = 298.91 Fe25.3Ni24.7Ti50, at 20˚C [1967Dud] 

CsCl a = 298.18 Fe35.3Ni14.7Ti50, at 20˚C [1967Dud] 

TiFe 

≤ 1317 

a = 297.6 49.8 to 51.8 at.% Ti [V-C2] 

TiNi 

≤ 1311 

a = 299.8 to 301.0 49.5 to 57 at.% Ni [2008Ted] 



MSIT 1



Temperature 

Range 

[˚C] 

Pearson 

Symbol/ 

Group 

Space/ 

Prototype 



Ti2Ni cF96 a = 1127.8 to 1132.4 33 to 34 at.% Ni [2008Ted] 

≤ 984 Fd3m 

Ti2Ni dissolves up to 26 at.% Fe [1981Loo] 

TiNi 

(martensite) 

hP18 a = 735.8 Ni50.23Ti49.77, at 20˚C [1997Har]. 

P3 

- 

c = 528.55 X-ray diffraction. Known as R phase. 

TiNi 

(martensite) 

mP4 a = 289.8 Ni49.2Ti50.8, at 20˚C [1992Shi]. 

P21/m b = 410.8 Single crystal X-ray diffraction. Known as 

B19’ martensite. 

TiNi c = 464.6 

β = 97.78˚ 

TiNi3 hP16 a = 510.28 75 to 80.1 at.% Ni at 1300˚C [2008Ted] 

≤ 1380 P63/mmc 

TiNi3 c = 827.19 

a = 510.3 ± 0.5 

c = 832.0 ± 0.8 dissolves up to 14 at.% Fe [1981Loo] 


c = 846.8 Fe4Ni72Ti24, at 900˚C [1981Loo] 

. Table 3 


Reactions T [˚C] Type Phase 


Fe 


Ni Ti 

9 

L Ð TiFe2 + TiNi3 1320 e1 L 31.80 39.10 29.10 

TiFe2 52.46 16.61 30.93 

TiNi3 0.50 73.26 26.24 

L+(αFe) Ð (γFe) + TiFe2 1200 U1 L 66.46 17.55 15.99 

(αFe) 79.40 11.33 9.26 

(γFe) 76.94 13.90 9.16 

TiFe2 59.71 8.21 32.01 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_14 

ß Springer 2009

10 14 

Fe–Ni–Ti 


Reactions T [˚C] Type Phase 

Fe 


Ni Ti 

L Ð (γFe) + TiFe2 + TiNi3 1113 E1 L 36.35 40.61 23.04 

(γFe) 55.29 35.68 9.03 

TiFe2 52.46 16.61 30.93 

TiNi3 0.50 73.26 26.24 

L + Ti(Fe,Ni) Ð (βTi) + Ti2Ni 960 U3 L 0.91 24.03 75.06 

Ti(Fe,Ni) 18.02 28.57 53.41 

(βTi) 0.95 4.04 95.01 

Ti2Ni 1.11 32.64 66.25 

. Table 4 

Heat of Mixing (ΔH mix) of Fe-Ni-Ti Liquid Alloys. The Data Below are Due to Functional Representation 

of Experimental Data [1999Thi] 

Composition Section Temperature [˚C] ΔHmix, [kJ·(g-at.) –1 ] 

(Fe84Ti16)1–yNiy 

1621 

y = 0.0 –9.291 

y = 0.05 –9.843 

y = 0.10 –10.433 

y = 0.15 –10.787 

y = 0.20 –11.024 

y = 0.25 –11.083 

y = 0.30 –11.024 

y = 0.35 –10.945 

1645 

y = 0.0 –36.972 

y = 0.05 –34.507 

y = 0.10 –32.141 

y = 0.15 –30.169 

y = 0.20 –28.197 

y = 0.25 –26.127 

y = 0.30 –24.648 

y = 0.35 –23.070 

(NiTi) 1–yFe y 



MSIT 1


Composition Section Temperature [˚C] ΔHmix, [kJ·(g-at.) –1 ] 

(Fe 2Ti) 1–yNi y 

(Fe 89Ni 11) 1–yTi y 

1643 

y = 0.0 –17.362 

y = 0.05 –17.872 

y = 0.10 –18.191 

y = 0.15 –18.511 

y = 0.20 –18.511 

y = 0.25 –18.415 

y = 0.30 –18.670 

y = 0.35 –17.681 

1600 

y = 0.0 –1.892 

y = 0.05 –5.081 

y = 0.10 –8.108 

y = 0.15 –10.811 

y = 0.20 –13.514 

y = 0.25 –15.892 

y = 0.30 –17.946 

y = 0.35 –20.004 

. Table 5 

Investigations of the Fe-Ni-Ti Materials Properties 

Reference 



[1987Chu] Internal friction and 

resistivity 

Internal friction and electrical resistance of B2-TiNi(Fe) 

[1987Kha] Ultrasonic resonance Elastic properties of B2-TiNi(Fe) 

[1987Sas] Refraction and 

absorption 

Optical properties of B2-TiNi(Fe) 


[1989Gor] Mechanical tests Hardness, yield and tensile strengths, ductility and 

fracture toughness of austenitic steels 

[1991Pro] Mechanical tests Flow stress of B2-TiNi(Fe) 

[1999Zha] Ultrasonic resonance Single crystal elastic constants of B2-TiNi(Fe) 

[2000Jia] Mechanical tests Flow stress, shape memory behavior of B2-TiNi(Fe) 

[2003Miy] Electrochemical tests Charge/discharge capacity of TiFe1–xNix Landolt‐Börnstein 


MSIT 1 

11 

DOI: 10.1007/978-3-540-70890-2_14 

ß Springer 2009

12 14 

Fe–Ni–Ti 


Reference 



[2000Xu] Mechanical tests Shape memory behavior of B2-TiNi(Fe) 

[2003Nis] Mechanical tests Stress-strain behavior of B2-TiNi(Fe) 

[2004Jan, 

2005Jan] 

Electrochemical tests Charge/discharge capacity of TiFe0.25Ni0.75 [2005Cho] Resistivity, susceptibility Electrical resistivity, magnetic susceptibility, specific heat 

of B2-TiNi(Fe) 

[2005Wan] Dilatometry Two-way shape memory behavior of B2-TiNi(Fe) 

[2005Yam] Magnetometry Magnetization, Néel temperature of C14-Ti(Fe1–xNix) 2 

[2006Cho] Physical property 

measurement systems 

[2006Fan] Dynamic mechanical 

alalyzer 

Specific heat, Debye temperature of B2-TiNi(Fe) 

Damping behavior of B2-TiNi(Fe) 

[2007Pro] Mechanical tests Shape memory behavior of B2-TiNi(Fe) 



MSIT 1

. Fig. 1 

Fe-Ni-Ti. The TiNi-FeTi quasibinary section 



MSIT 1 


13 

DOI: 10.1007/978-3-540-70890-2_14 

ß Springer 2009

14 14 

. Fig. 2 

Fe-Ni-Ti. Reaction scheme 

Fe–Ni–Ti 



MSIT 1

. Fig. 3 

Fe-Ni-Ti. Liquidus surface projection 



MSIT 1 


15 

DOI: 10.1007/978-3-540-70890-2_14 

ß Springer 2009

16 14 

Fe–Ni–Ti 

. Fig. 4 

Fe-Ni-Ti. Partial isothermal section at 1100˚C 



MSIT 1

. Fig. 5 

Fe-Ni-Ti. Isothermal section at 1000˚C 



MSIT 1 


17 

DOI: 10.1007/978-3-540-70890-2_14 

ß Springer 2009

18 14 

Fe–Ni–Ti 

. Fig. 6 




MSIT 1

. Fig. 7 




MSIT 1 


19 

DOI: 10.1007/978-3-540-70890-2_14 

ß Springer 2009

20 14 

Fe–Ni–Ti 

. Fig. 8 

Fe-Ni-Ti. A polythermal section at a constant Ti content of 8 mass% 



MSIT 1

. Fig. 9 

Fe-Ni-Ti. A polythermal section at a constant Ti content of 12 mass% 



MSIT 1 


21 

DOI: 10.1007/978-3-540-70890-2_14 

ß Springer 2009

22 14 

Fe–Ni–Ti 

. Fig. 10 

Fe-Ni-Ti. A polythermal section at a constant Ti content of 14.4 mass% 



MSIT 1

. Fig. 11 

Fe-Ni-Ti. A polythermal section at a constant Ti content of 66.67 at.% 



MSIT 1 


23 

DOI: 10.1007/978-3-540-70890-2_14 

ß Springer 2009

24 14 

Fe–Ni–Ti 

. Fig. 12 

Fe-Ni-Ti. A polythermal section at a constant mass ratio of Fe:Ni=90:10 



MSIT 1

. Fig. 13 

Fe-Ni-Ti. A polythermal section at a constant mass ratio of Fe:Ni=60:40 



MSIT 1 


25 

DOI: 10.1007/978-3-540-70890-2_14 

ß Springer 2009

26 14 

Fe–Ni–Ti 

. Fig. 14 

Fe-Ni-Ti. Partial polythermal section along the line of constant Fe:Ni atomic ratio of 1:3 



MSIT 1


. Fig. 15 

Fe-Ni-Ti. Partial polythermal section along the line of constant Fe:Ni atomic ratio 1:1 



MSIT 1 

27 

DOI: 10.1007/978-3-540-70890-2_14 

ß Springer 2009

28 14 

Fe–Ni–Ti 

. Fig. 16 

Fe-Ni-Ti. Partial polythermal section along the line of constant Fe:Ni atomic ratio of 3:1 



MSIT 1

. Fig. 17 

Fe-Ni-Ti. Enthalpy of mixing (in kJ·(mol-atom) –1 ) of liquid alloys at 1643˚C 



MSIT 1 


29 

DOI: 10.1007/978-3-540-70890-2_14 

ß Springer 2009

30 14 

Fe–Ni–Ti 

References 

[1938Vog] Vogel, R., Wallbaum, H.J., “The System Fe-Ni 3Ti-Fe 2Ti” (in German), Arch. Eisenhuettenwes., 12, 

299–304 (1938) (Phase Diagram, Phase Relations, Experimental, #, *, 16) 

[1941Vog] Vogel, R., “About Observation of Enforced Precipitation in the Solid Solution” (in German), 

Z. Metallkd., 33, 376–377 (1941) (Experimental, Phase Relations, 1) 

[1949Jae] Jaenecke, E., “Ni-Fe-Ti” (in German) in “Kurzgefasstes Handbuch aller Legierungen”, Winter Verlag, 


[1963Spe] Speich, G. R., “Cellular Precipitation in an Austenitic Fe-30Ni-6Ti Alloy”, Trans. Met. Soc. AIME, 227, 

754–762 (1963) (Crys. Structure, Experimental, Phase Relations, #, *, 31) 

[1963Yeo] Yeo, R.G.B., “The Effects of Some Alloying Elements on the Transformation of Fe-22.5%Ni Alloys”, 

Trans. Met. Soc. AIME, 227, 884–890 (1963) (Experimental, Phase Relations, 13) 

[1967Dud] Dudkina, L.P., Kornilov, I.I., “An Investigation of the Equilibrium Diagram of the TiNi-TiFe System”, 

Russ. Metall., (4), 98–101 (1967), translated from Izv. Akad. Nauk SSSR, Met., (4), 184–187 (1967) 

(Experimental, Phase Relations, Phase Diagram, #, *, 13) 

[1968Abr] Abraham, J.K., “Lattice Parameters as a Function of Ti in Austenitic Fe-Ni-Ti Alloys”, Trans. Met. Soc. 

AIME, 242, 2365–2369 (1968) (Crys. Structure, Experimental, 10) 

[1969Abr] Abraham, J.K., Pascover, J.S., “The Transformation and Structure of Fe-Ni-Ti Alloys”, Trans. Met. Soc. 

AIME, 245, 759–768 (1969) (Crys. Structure, Experiment, 13) 

[1972Kok] Kokorin, V.V., Gorbach, V.G., Samsonov, Yu.I., “Martensitic Transformations in Aged Alloys of 

Fe-Ni-Ti” (in Russian), Metallofizika, (42), 87–96 (1972) (Crys. Structure, Experimental, 20) 

[1973Zem] Zemtsova, N.D., Malyshev, K.A., “Continuous Decomposition of a γ-Solid Solution in Iron-Nickel- 

Titanium Alloys”, Phys. Met. Metallogr. (Engl. Transl.), 35(5), 108–114 (1973) (Crys. Structure, 


[1974Whi] Whiteman, J.A., Sarma, D.S., “Structure of Martensites in Fe-Ni-Ti Alloys”, Metall. Mater. Trans. A, 5 


[1975Ost] Ostrovskii, O.I., Dyubanov, V.G., Stomakhin, A.Ya., Grigoryan, V.A., “Enthalpy of Dissolution of 

Titanium in Iron-Nickel Melts”, Izv. Vyss. Uchebn. Zaved., Chern. Metall., (7), 67–70 (1975) (Experimental, 


[1977Hal] Hall, M.M., Winchell, P.G., “Tetragonality of Fe-Ni-Ti Martensite”, Acta Metall., 25(7), 735–750 (1977) 

(Crys. Structure, Experimental, 27) 

[1978Uva] Uvarov, A.I., “Martensite Transformation, Induced by Stressing, and the Mechanical Properties in 

Iron-Nickel Based Aged Alloys” (in Russian), Metallofizika, (74), 109–111 (1978) (Crys. Structure, 


[1979Fou] Fournelle, R.A., “Discontinuous Coarsening of Lamellar Cellular Precipitates in an Austenitic Fe- 

30Ni-6Ti Alloy”, Acta Metall., 27, 1135–1145 (1979) (Experimental, 18) 

[1979Zem] Zemtsova, N.D., Mabyshev, K.A., Starchenko, Ye.I., “Cellular Decomposition in Undeformed Metastable 

Fe-Ni-Ti Alloys”, Phys. Met. Metallogr., 48(2), 128–135 (1979) (Experimental, Thermodyn., 11) 

[1981Loo] van Loo, F.J.J., Vroljik, J.W.G.A., Bastin, G.F., “Phase Relations and Diffusion Paths in the Ti-Ni-Fe 

System at 900˚C”, J. Less-Common Met., 77, 121–130 (1981) (Experimental, Phase Relations, #, *, 11) 

[1981Zem] Zemtsov, N.D., Starchenko, Ye.I., “Structure Mechanism of the Decomposition of Precipitation 

Hardened Austenitic Iron-Nickel-Titanium Alloys”, Phys. Met. Metallogr. (Engl. Transl.), 52(4), 


[1982Hwa1] Hwang, C.M., Meichle, M., Salmon, M.B., Wayman, C.M., “Transformation Behavior of Ti 50Ni 47Fe 3 

Alloy: I. Incommensurate and Commensurate Phases”, J. Phys., 43(12), C4-231–C4-236 (1982) (Crys. 


[1982Hwa2] Hwang, C.M., Salmon, M.B., Wayman, C.M., “Transformation Behavior of Ti 50Ni 47Fe 3 Alloy: 

I. Martensitic Transformation”, J. Phys., 43(12), C4-237–C4-242 (1982) (Crys. Structure, Experimental, 

5) 

[1982Nis] Nishida, M., Honma, T., “Phase Transformations in Ti 50Ni 50-xFe x Alloys”, J. Phys., 43(12), C4-225–C4- 


[1983Sav] Savvinov, A.S., Sivokha, V.P., Khachin, V.N., “Martensitic Transformations in B2-Type Titanium 

Compounds” (in Russian), Metallofizika, 5(6), 30–36 (1983) (Crys. Structure, Electr. Prop., Experimental, 




MSIT 1


31 

[1984Ano] Anokhin, S.V., Lotkov, A.I., “Change in Electronic Structure and Crystal Structure in Ti(Ni, Fe) Alloys 

Just before the Martensitic Transformation”, Sov. Phys.- Dokl.(Engl. Transl.), 34(8), 734–735 (1984) 


[1984Kab] Kabanova, I.G., Zemtsova, N.D., Sagaradze, V.V., “Parameters of Shear Strain During γ-α and α-γ 

Martensitic Transformations in an Aged Austenitic Fe-Ni-Ti Alloy”, Phys. Met. Metallogr. (Engl. 

Transl.), 58(2), 120–130 (1984), translated from Fiz. Metal. Metalloved., 58(2), 344–454, 1984 (Crys. 


[1984Pus] Pushin, V.G., Khachin, V.N., Savvinov, A.S., Kondratev, V.V., “Structural Phase Transformations and 

Properties of the Alloys NiTi and NiTiFe”, Sov. Phys.- Dokl. (Engl. Transl.), 29(8), 681–683 (1984), 

translated from Dokl. Akad. Nauk SSSR, 277, 1388–1391 (1984) (Crys. Structure, Experimental, 

Kinetics, 11) 

[1984Tad] Tadaki, T., Asayama, K., Shimizu, K., “Some Observations of Ausageing Effects on the Martensitic 

Transformation in an Fe-Ni-Ti Alloy”, Trans. Jpn. Inst. Met., 25(2), 80–88 (1984) (Crys. Structure, 


[1985Goo] Goo, E., Sinclair, R., “The B2 toR Transformation in Ti 50Ni 47Fe 3 and Ti 49.5Ni 50.5”, Acta Met., 33(9), 


[1985Gup] Gupta, K.P., Rajendraprasad, S.B., Jena, A.K., Sharma, R.C., “The Iron-Nickel-Titanium System”, J. 

Alloy Phase Diagrams, 1, 59–68 (1985) (Phase Diagram, Phase Relations, Review, #, *, 21) 

[1985Sav] Savvinov, A.S., Sivokha, V.P., Khachin, V.N., “Martensitic Transformations in B2-Type Titanium 

Compounds”, Phys. Metals, 5(6), 1107–1118 (1985), translated from Metallofizika, 5(6), 30–36 (1983) 

(Crys. Structure, Electr. Prop., Experimental, Phase Relations, 7) 

[1985Val] Valiyev, E.Z., Men’shikov, A.Z., Panakhov, T.M., “The Structural State of Alloys Ni 3(Fe 1–xTi x) and 

Ni 3(Fe 1–xNb x) During Atomic Ordering”, Phys. Met. Metallogr., 59(1), 123–129 (1985) (Crys. Structure, 


[1986Edm] Edmonds, K.R., Hwang, C.M., “Phase Transformations in Ternary TiNiX Alloys”, Scr. Metall., 20(5), 

733–737 (1986) (Experimental, Phase Relations, 7) 

[1987Chu] Chui, N.-Y., Huang, Y.-T., “A Study of Internal Friction, Electric Resistance and Shape Change in a 

Ti-Ni-Fe Alloy During Phase Transformation”, Scr. Metall., 21, 447–452 (1987) (Crys. Structure, 


[1987Kha] Khachin, V.N., Muslov, S.A., Pushin, V.G., Chumlyakov, Yu.I., “Anomalies in the Elastic Properties of 

TiNi-TiFe Single Crystals”, Sov. Phys. – Dokl., 32(7), 606–608 (1987) (Crys. Structure, Experimental, 

Phys. Prop., 7) 

[1987Sas] Saskovskaya, I.I., Pushin, V.G., “Optical Properties and Structure of TiNi and TiNiFe Alloys During 

the B2-R Temperature and Concentrational Transformation”, Phys. Met. Metallogr. (Engl. Transl.), 64 

(5), 56–64 (1987), translated from Fiz. Met. Metalloved. 64(5), 896–904 (1987) (Crys. Structure, 

Experimental, Optical Prop., 12) 

[1988Sag] Sagaradze, V.V., Makozov, S.V., “Dissolution of Spherical and Platelike Intermetallics in Fe-Ni-Ti 

Austenitic Alloys During Cold Plastic Deformation”, Phys. Met. Metallogr., 66(2), 111–120 (1988) 


[1989Gor] Gorbach, V.G., Jelenkowski, J., Filipiuk, J., “Microstructure and Mechanical Properties of Duplex 

Martensitic-Austenitic Fe-Ni-Ti Steels”, Mat. Sci.Technol., 5(1), 36–39 (1989) (Experimental, Mechan. 

Prop., 20) 

[1989Ano1] Anokhin, S.V., Grishkov, V.N., Lotkov, A.I., “Martensitic Transformations in Ti(Ni,Fe) Alloys”, Sov. 

Phys. J., 32(12), 961–964, (1989) (Crys. Structure, Experimental, 8) 

[1989Ano2] Anokhin, S.V., Lotkov, A.I., “Change in Electronic Structure and Crystal Structure in Ti(Ni,Fe) Alloys 

Just before the Martensitic Transformation”, Sov. Phys. – Dokl., 34(8), 734–735 (1989) (Crys. Structure, 


[1990Kum] Kumar, K.C.H., Raghavan, V., “BCC-FCC Equilibrium in Ternary Iron Alloys-IV”, J. Alloy Phase 

Diagrams, 6(1), 31–49 (1990) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 49) 

[1990Rao] Rao, J., He, Y., Ma, R., “Study of Phase Transition in Ti 50Ni 47.5Fe 2.5 Alloy”, Metall.Trans., 21A, 


[1991Gup] Gupta, K.P., “The Fe-Ni-Ti (Iron-Nickel-Titanium) System” in “Phase Diagrams of Ternary Nickel 

Alloys”, Indian Institute of Metals, Calcutta, India, 321–343 (1991) (Phase Diagram, Phase Relations, 

Review, #, *, 12) 

[1991Lue] Lueck, R., Wang, H., Predel, B., “Thermodynamic Investigation of Liquid Iron-Nickel-Titanium 

Alloys” (in German), Z. Metallkd., 82, 805–809 (1991) (Experimental, Thermodyn., 17) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_14 

ß Springer 2009

32 14 

Fe–Ni–Ti 

[1991Mur] Murray, J.L., “Fe-Ti (Iron-Titanium)” in “Phase Diagrams of Binary Iron Alloys”, ASM International, 

Metals Park, Ohio, 414–425 (1991) (Phase Diagram, Review, #, *, 112) 

[1991Pro] Prokoshkin, S.D., Kaputkina, L.M., Bondareva, S.A., Tikhomirova, O.Yu., Fatkullina, L.P., Oleynikova, 

S.V., “Structure of Hot-Deformed Austenite and Properties of a Ti-Ni-Fe Alloy after HTMT”, Phys. 

Met. Metallogr. (Engl. Transl.), 71(3), 143–148 (1991) (Experimental, Mechan. Prop., 4) 

[1992Ruz] Ruzhang, M., “Mössbauer Studies of Ti-Ni-Fe Shape-Memory Alloy”, Philos. Mag. A, 65(1), 123–130 

(1992) (Experimental, 10) 

[1992Sag] Sagaradze, V.V., Morozov, S.V., “Mechanical Alloying of Fe-Ni-Ti Austenite During Low-Temperature 

Deformation”, Mater. Sci. Forum, 88–90, 147–154 (1992) (Crys. Structure, Experimental, Phase Relations, 

3) 

[1992Shi] Shimizu, K., Tadaki, T., “Recent Studies on the Precise Crystal-Structural Analyses of Martensitic 

Transformation”, Mater. Trans., JIM, 33(3), 165–177 (1992) (Crys. Structure, 101) 

[1993Mat] Matveeva, N.M., Klopotov, A.A., Kormin, N.M., Sazanov, Y.A., “Lattice Parameters and the Sequence 

of Transformations in Ternary TiNi-TiMe Alloys”, Russ. Metall. (Engl. Transl.), (3), 216–220 (1993), 

translated from Izv. RAN, (3), 233–237 (1993) (Experimental, Phase Relations, Crys. Structure, 10) 

[1994Ali1] Alisova, S.P., Budberg, P.B., Barmina, T.I., Lutskaya, N.V., “Ti-TiFe-TiNi System”, Russ. Metall. (Engl. 

Transl.), (1), 117–121 (1994), translated from Izv. RAN, (1), 158–163 (1994) (Experimental, Phase 

Relations, 9) 

[1994Ali2] Alisova, S.P., Kovneristyi, Yu.K., Lutskaya, N.V., Budberg, P.B., “Structure of the Rapidly Solidified Ti- 

TiFe-TiNi Alloys”, Russ. Metall. (Engl. Transl.), 146–149 (1994), translated from Izv. RAN Met., (1), 

158–161, 1994 (Experimental, Phase Relations, 5) 

[1994Jia] Jia, C.C., Ishida, K., Nishizawa, T., “Partitioning of Alloying Elements Between γ(A1) and θ(D0 24) 

Phases in The Ni-Ti Base Systems” in “Experimental Methods Phase Diagram Determination”, Morral, J. 

E., Schiffman, R.S., Merchant, S.M., (Eds.), The Minerals, Metals and Materials Society, Warrendale, 

PA, 31–38 (1994) (Experimental, Phase Diagram, 8) 

[1995Air] Airoldi, G., Carcano, G., Riva, G., Vanelli, M., “X-Ray Powder Diffraction Study of the R-Phase in a 

Ti 50Ni 48Fe 2 Alloy by a New Calibration Method”, J. Phys., Colloq., 5(C2), 281–286 (1995) (Crys. 


[1995Ali] Alisova, S.P., Kovneristyi, Yu.K., Lutskaya, N.V., Budberg, P.B., “Structure of the Rapidly Solidified Ti- 

TiFe-TiNi Alloys”, Russ. Metall. (Engl. Transl.), (1), 146–149 (1995), translated from Izv. Ross. Akad. 

Nauk Met., (1), 158–161, 1995 (Experimental, Phase Diagram, 5) 

[1995Gue] Guerin, G., “Martensitic Transformation and Thermomechanical Properties”, Key Eng. Mater., 

101–102, 339–392 (1995) (Crys. Structure, Phys. Prop., Review, 73) 

[1995Tom] Tomiska, J., Wang, H., “On the Algebraic Evaluation of the Ternary Molar Heat of Mixing H E from 

Calorimetric Investigations”, Ber. Bunsen-Ges. Phys. Chem., 99(4), 633–640 (1995) (Thermodyn., 27) 

[1995Zem] Zemtsova, N.D., “Discontinuous Precipitation as a Factor Increasing the Plasticity of Aging Fe-Ni-Ti 

Alloys”, Phys. Met. Metallogr., 79(3), 336–341 (1995) (Experimental, Kinetics, 10) 

[1997Har] Hara, T., Ohba, T., Okunishi, E., Otsuka, K., “Structural Study of R-Phase in Ti-50.23Ni (at.%) and 

Ti-47.75Ni-1.50Fe (at.%) Alloys”, Mater. Trans., JIM, 38(1), 11–17 (1997) (Crys. Structure, Experimental, 

18) 


(1998) (Phase Relations, Thermodyn., 83) 

[1998Tam] Tamiya, T., Shindo, D., Murakami, Y., Bando, Y., Otsuka, K., “In-situ Observations of R-Phase 

Transformation in a Ti 50Ni 48Fe 2 Alloy by Electron Microscopy”, Mater. Trans., 39(7), 714–723 (1998) 


[1999Abr] Abramycheva, N.L., V’yunitskii, I.V, Kalmykov, K.B., Dunaev, S.F., “Isothermal Cross Section of the 

Phase Diagram of the Fe-Ni-Ti System at 1273 K. - I”, Vestn. Mosk. Univ., Ser.2: Khim, 40(2), 139–143 

(1999) (Experimental, Phase Relations, #, *, 4) 

[1999Efi] Efimenko, L.P., Petrova, L.P., Sviridov, S.I., “Interactions in TiFe-Ni System at 1200˚C”, Russ. Metall. 

(Engl. Transl.), (4), 160–165 (1999) (Experimental, 15) 

[1999Lee] Lee, S.M., Perng, T.P., “Correlation of Substitutional Solid Solution with Hydrogenation Properties of 

TiFe 1–xM x (M = Ni, Co, Al) Alloys”, J. Alloys Compd., 291, 254–261 (1999) (Crys. Structure, Experimental, 

18) 

[1999Thi] Thiedemann, U., Rösner-Kuhn, M., Drewes, K., Kuppermann, G., Frohberg, M.G., “Temperature 

Dependence of the Mixing Enthalpy of Liquid Ti-Ni and Fe-Ti-Ni Alloys”, J. Non-Cryst. Solids, 

250–252, 329–335 (1999) (Experimental, Thermodyn., 17) 



MSIT 1


33 

[1999Zha] Zhang, J., Ren, X., Otsuka, K., Tanaka, K., Chumlyakov, Yu.I., Asai, M., “Elastic Constants of Ti-48 

at.%Ni-2 at.%Fe Single Crystal Prior to B2 → R Transformation”, Mater. Trans., JIM, 40(5), 385–388 

(1999) (Crys. Structure, Phys. Prop., Experimental, 21) 

[2000Chu] Chu, J.P., Lai, Y.W., Lin, T.N., Wang, S.F., “Deposition and Characterization of TiNi-Base Thin Films 

by Sputtering”, Mater. Sci. Eng. A, A277, 11–17 (2000) (Crys. Structure, Experimental, Phys. Prop., 20) 

[2000Efi] Efimenko, L.P., Petrova, L.P., Sviridov, S.I., “Interaction of Eutectic Melt Ti 2Ni-Ti and Iron Substrate at 

1100-1250˚C”, Russ. Metall. (Metally), 3, 42–46 (2000), translated from Izv. Ros. Akad. Nauk, Met., (3), 

41–44 (2000) (Experimental, Phase Diagram, Phase Relations, Transport Phenomena, 12) 

[2000Jia] Jiang, C., Xu, H., “Effect of Pre-Deformation on Hysteresis in TiNiFe Shape Memory Alloys”, Mater. 

Sci. Forum, 327–328, 111–114 (2000) (Experimental, 3) 

[2000Lap] Lapshin, V.P., Grishkov, V.N., Lotkov, A.I., “On Certain Anharmonic Characteristics of B2 Phase Ti 

(Ni,Fe) Alloys Under Hydrostatic Pressure”, Russ. Phys. J., 43(12), 999–1002 (2000) (Crys. Structure, 


[2000Vor] Voronin, V.I., Naish, V.E., Novoselova, T.V., Sagaradze, I.V., “Structures of Monoclinic Phases in 

Titanium Nickelide: II. Transformation Cascade B2-R-T”, Phys. Met. Metallogr., 89(1), 19–26 (2000) 


[2000Xu] Xu, H., Jiang, C., Gong, S., Feng, G., “Martensitic Transformation of the Ti 50Ni 48Fe 2 Alloy Deformed 

at Different Temperatures”, Mater. Sci. Eng. A, A281, 234–238 (2000) (Experimental, 11) 

[2001Gup] Gupta, K.P., “The Fe-Ni-Ti System Update (Iron - Nickel - Titanium)”, J. Phase Equilib., 22(2), 

171–175 (2001) (Phase Diagram, Review, #, *, 5) 

[2001Mur] Murakami, Y., Shindo, D., “Changes in Microstructure Near the R-Phase Transformation in 

Ti 50Ni 48Fe 2 Studied by in-situ Electron Microscopy”, Philos. Mag. Lett., 81(9), 631–638 (2001) (Experimental, 

Morphology, Phase Relations, 25) 

[2002Boz] Bozzolo, G.H., Noebe, R.D., Amador, C., “Site Occupancy of Ternary Additions to B2 Alloys”, 

Intermetallics, 10, 149–159 (2002) (Crys. Structure, Review, 27) 

[2002Ish] Ishida, S., Asano, S., “R-Phase and Electronic Structures of TiNi and TiNi 8/9Fe 1/9”, Mater. Trans., 43(5), 


[2002Kuz] Kuznetsov, A.R., Sagaradze, V.V., “On the Possible Mechanism of Low-temperature Strain-induced 

Dissolution of Intermetallic Phases in FCC Fe-Ni-Ti Alloys”, Phys Met Metallogr., 93(5), 404–407 

(2002), translated from Fiz Met. Metalloved., 93(5), 13–16 (2002) (Experimental, 22) 

[2003Miy] Miyamura, H., Takada, M., Hirose, K., Kikuchi, S., “Metal Hydride Electrodes Using Titanium-Iron- 

Based Alloys”, J. Alloys Compd., 356–357, 755–758 (2003) (Electrochemistry, Experimental, Phase 

Diagram, 6) 

[2003Nis] Nishida, M., Tanaka, K., Li, S., Kohshima, M., Miura, S., Asai, M., “Microstructure Modifications by 

Tensile Deformation in Ti-Ni-Fe Alloy”, J. Phys. IV, France, 112(2), 803–806 (2003) (Experimental, 


[2004Jan] Jankowska, E., Jurczyk, M., “Electrochemical Properties of Sealed Ni-MH Batteries Using 

Nanocrystalline TiFe type Anodes”, J. Alloys Compd., 372, L9–L12 (2004) (Crys. Structure, Electrochemistry, 


[2005Cho] Choi, M.-S., Fukuda, T., Kakeshita, T., “Anomalies in Resistivity, Magnetic Susceptibility and Specific 

Heat in Iron-Doped Ti-Ni Shape Memory Alloys”, Scr. Mater., 53(7), 869–873 (2005) (Crys. Structure, 

Electr. Prop., Electronic Structure, Experimental, Phase Relations, Thermodyn., 17) 

[2005Jan] Jankowska, E., Makowiecka, M., Jurczyk, M., “Nickel-Metal Hydride Battery Using Nanocrystalline 

TiFe-Type Hydrogen Storage Alloys”, J. Alloys Compd., 404–406, 691–693 (2005) (Crys. Structure, 

Electrochemistry, Experimental, 11) 

[2005Ste] Sitepu, H., Wright, J.P., Hansen, T., Chateigner, D., Brokmeier, H.-G., Ritter, C., Ohba, T., “Combined 

Synchrotron and Neutron Structural Refinement of R-Phase in Ti 50.75Ni 47.75Fe 1.50 Shape Memory 

Alloy”, Mater. Sci. Forum (Textures of Materials - ICOTOM 14), 495–497, 255–260 (2005) (Crys. 


[2005Wan] Wang, J.J., Omori, T., Sutou, Y., Kainuma, R., Ishida, K., “Two-Way Shape Memory Effect Induced by 

Cold-Rolling in Ti-Ni and Ti-Ni-Fe Alloys”, Scr. Mater., 52(4), 311–316 (2005) (Experimental, 

Kinetics, Phase Relations, Thermodyn., 21) 

[2005Yam] Yamada, Y., Nakamura, K., Kitagawa, K., Obara, G., Nakamura, T., “Magnetic Properties of C14 Laves 

Phase Ti(Fe 1–xT x) 2 with T = Mn, Co and Ni (x < 0.6)”, J. Magn. Magn. Mater., 285(1-2), 28–38 (2005) 

(Crys. Structure, Experimental, Magn. Prop., Optical Prop., Phase Relations, 10) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_14 

ß Springer 2009

34 14 

Fe–Ni–Ti 

[2006Cac] Cacciamani, G., De Keyzer, J., Ferro, R., Klotz, U.E., Lacaze, J., Wollants, P., “Critical Evaluation of the 

Fe-Ni, Fe-Ti and Fe-Ni-Ti Alloy Systems”, Intermetallics, 14, 1312–1325 (2006) (Phase Relations, 

Review, #, *, 161) 

[2006Cho] Choi, M.S., Ogawa, J., Fukuda, T., Kakeshita, T., “Stability of the B2-Type Structure of Ti-Ni-Fe and Ti- 

Ni-Co Shape Memory Alloys”, Mat. Sci. Forum, 512, 233–238 (2006) (Crys. Structure, Experimental, 


[2006Fan] Fan, G., Zhou, Y., Otsuka, K., Ren, X., “Ultrahigh Damping in R-Phase State of Ti-Ni-Fe Alloy”, Appl. 

Phys. Lett., 89, 161902–1–3 (2006) (Experimental, Mechan. Prop., 15) 

[2006Gho] Ghosh, G., “Iron-Nickel-Titanium”, Landolt- Börnstein: Numerical Data and Functional Relationship in 

Science and Technology, New Series, Effenberg, G., Illyenko S., (Eds.), Springer-Verlag, Berlin/Heidelberg, 

Group IV, 11, Subvolume A, Part 4, 299–316 (2005), MSIT Ternary Evaluation Program, in MSIT 


ID: 10.10608.1.20, (1992) (Crys. Structure, Phase Diagram, Assessment, #, *, 44) 

[2006Ria] Riani, P., Cacciamani, G., Thebaut, Y., Lacaze, J., “Phase Equilibria and Phase Transformations in the 

Ti-Rich Corner of the Fe-Ni-Ti System”, Intermetallics, 14, 1226–1230 (2006) (Experimental, Morphology, 


[2006Yam] Yamamoto, T., Fukuda, T., Kakeshita, T., “Electronic Structure of B2-type Ti-Ni-Fe Alloys Exhibiting 

Second-order-like Structural Transformation”, Mater. Trans., 47, 594–598 (2006) (Experimental, Crys. 


[2007Pro] Prokoshkin, S.D., Belousov, M.N., Abramov, V.Ya., Korotitskii, A.V., Makushev, S.Yu., Khmelevskaya, 

I.Yu., Dobatkin, S.V., Stolyarov, V.V., Prokof‘ev, E.A., Zharikov, A.I., Valiev, R.Z., “Creation of 

Submicrocrystalline Structure and Improvement of Functional Properties of Shape Memory Alloys of 

the Ti-Ni-Fe System with the Help of ECAP”, Met. Sci. Heat Treat., 49(1-2), 51–56 (2007) (Crys. 

Structure, Experimental, Morphology, 11) 


G. (Ed.), MSI, Materials Science International Services, GmbH, Stuttgart; to be published, (2008) 

(Crys. Structure, Phase Diagram, Assessment, 41) 

[2008Ted] Tedenac, J.C., Velikanova, T., Turchanin, M., “Ni-Ti (Nickel-Titanium)”, MSIT Binary Evaluation 

Program, in MSIT Workplace, Effenberg, G. (Ed.), Materials Science International Services, GmbH, 

Stuttgart; to be published (2008) (Crys. Structure, Phase Diagram, Assessment, 37) 


(1990) 





MSIT 1

Iron – Nickel – Vanadium 


Andy Watson, Lesley Cornish 

Introduction 

The Fe-Ni-V system is of interest, not only because both Ni and V are components in steels, 

but also because Fe and V are important components of Ni-based superalloys for aerospace 

applications. The VNi 3 phase, which has an ordered tetragonal structure, acts as a strengthening 

phase in Ni-based superalloys [1963Zeg, 1977Bra1, 1977Bra2]. However, a major concern 

with these materials is the precipitation of the σ phase in alloys during service and much 

effort has gone into trying to predict its formation. [1977Bra1, 1977Bra2] attempted to predict 

σ phase formation by calculation of density of states and enthalpies of formation using a tight 

binding Hamiltonian matrix, but more recently it has been the subject of study by Calphad 

techniques [2001Wat]. The other major interest for this system comes from its magnetic 

properties, and Fe-Ni-V Permalloys have superior mechanical properties compared to conventional 

Permalloys. This can give an advantage where abrasion resistance is important, for 

example, [1984Tis], but these materials have a reduced saturation magnetization. Nevertheless, 

there is interest in using these materials as films for magnetic and electronic devices 

[1990Miy]. Considering the level of industrial interest, it is surprising that there has been 

relatively little study of the phase equilibria and thermodynamics of the system. The binary 

systems associated with Fe-Ni-V are well known but there have only been a few studies of 

the ternary system. The earliest record of the phase equilibria and magnetic properties of the 

system were recorded by [1934Kue], and subsequently, the system has been review by [1949Jae, 

1983Ray, 1988Ray, 1994Rag1]. 

Details of experimental studies of the system are summarized in Table 1. 


Fe–Ni–V 15 

1 

The three binary systems, Fe-Ni, Fe-V and Ni-V are well known and appear in [Mas2]. There 

have been a number of attempts at producing thermodynamic descriptions of the systems. The 

earliest thermodynamic description of the Fe-Ni system was produced by [1986Din] and has 

been used on many occasions for the study of ternary and higher order systems. More recently, 

the liquid phase has been remodeled [1993Lee] in order to improve the level of agreement with 

experimental data in the thermodynamic assessment of the Fe-Cr-Ni system. The ordering of 

the fcc phase to FeNi 3 was modeled by [2000Ans]. The Fe-V system was assessed by 

[1991Hua1] but [2006Oka] has reported recent work by [2005Ust] who studied the extent 

of the σ phase in the binary Fe-V system using XRD and electron microscopy. They suggest 

that the σ phase decomposes below about 650˚C accompanied by phase separation of the bcc 

phase. However, in the phase diagram shown by [2006Oka], there would seem to be a narrow 

strip of single phase α between the σ phase and the region of phase separation. As pointed out 

by [2006Oka], this would seem to be unlikely, the σ phase most probably decomposing 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_15 

ß Springer 2009

2 15 

Fe–Ni–V 

eutectoidally to give Fe rich and V rich bcc phases, much like in the Cr-Fe system. As this 

remains uncertain, the feature has been ignored in the present work. The Ni-V system was 

assessed by [1992Luo] and more recently by [2001Wat], who used a variety of different models 

to describe the σ phase. The binary phase diagrams for Fe-V and Ni-V are taken from [Mas2], 

the latter being based on [1982Smi], but a recent review of the Fe-Ni system [2008Kuz], as 

conducted as part of the MSI binary phase evaluation program, is taken as the source for the 

third binary phase diagram. 


No ternary phases have been found in this system. The main feature is the extension of the σ 

phase from the Ni-V to the Fe-V binary system. The σ phase field is quite wide (~28 at.% at 

900˚C) in the Ni-V binary system and is stable below its peritectic formation temperature of 

1280˚C. In the Fe-V system, the congruent transformation temperature of the σ phase field is 

given in [Mas2] as 1252˚C, and at it is reasonable to assume that a single phase field extends 

right across the phase diagram at temperatures below this. Both the Fe-Ni and Fe-V systems 

exhibit large solution phase fields that extend across the binary phase diagrams (γ and α, 

respectively) and these extend well into the ternary system with dissolution of the third 

element. Both the ordered γ’ (FeNi3) and the θ (VNi3) phases dissolve the third element. 

However, it is not known to what level. Both of these phases are different ordered variants of 

fcc (L1 2 and D0 22, respectively) so complete mutual solubility is not likely. 

[1963Zeg] studied the solubility of Fe in the binary V 3Ni compound. Alloys were prepared 

by arc-melting spectroscopically pure V with commercially pure Fe and Ni (99.9+) and 

annealing the cast materials at 800˚C in evacuated quartz ampoules for 3-6 weeks. Optical 

microscopy and powder XRD (Cu kα radiation) were used to study the alloys. They found that 

it was possible to dissolve Fe into the V 3Ni binary compound up to a composition of 

V3(Fe0.7Ni0.3). Crystallographic details of the phases of the system are given in Table 2. 


No invariant equilibria have been detected in this system, but considering the binary invariant 

reactions, it is highly likely that a transition type reaction will be present. The information in 

Table 3 was taken from the review of [1988Ray]. 


No determination of the liquidus surface has been carried out as yet, but the likely form it 

would take was postulated by [1988Ray] based on the liquidus features of the adjoining binary 

systems, Fig. 1. Only three binary invariants are present in the system (Fe-V: peritectic 

L+(δFe)Ð(γFe), Ni-V: peritectic L+(V) Ð σ, eutectic LÐσ+(Ni)) and by considering their 

respective temperatures, they would most likely extend into the ternary system to meet at a 

transition reaction. Thermodynamic calculations conducted by combining the assessed thermodynamic 

descriptions of the binary phases [1986Din, 1991Hua2, 2001Wat] from the 

literature would confirm this hypothesis, although the nature of the invariant was found in 

this case to be eutectic. This was due to the presence of a minimum in the L+(δFe) Ð (γFe) 



MSIT 1

monovariant extending from the Fe-Ni binary edge, however there is no experimental justification 

for this feature and hence it can be ignored at this time. 



3 

Sections at three temperatures have been determined experimentally. [1957Dar] vacuum arcmelted 

electrolytic grade materials to produce alloys that were then sealed in He+8% H2 filled 

quartz ampoules for ‘long time’ annealing at 1200˚C. Following heat treatment, the ampoules 

were broken under water in order to quench the alloys. XRD and microscopic examination 

were used to determine the extent of the σ phase in the ternary system at 1200˚C using the 

disappearing phase technique. They found that the σ phase extended deep into the ternary 

system extending from the Ni-V binary edge, but it stopped short of the Fe-V edge. At that 

time, there was some uncertainty as to the temperature range of the σ phase in the Fe-V 

system, and the results of [1957Dar] seemed to suggest that the σ phase would not be stable in 

the Fe-V binary system at this temperature. Figure 2 shows the isothermal section of the 

system at 1200˚C based on the work of [1957Dar]. In the figure, the σ phase field has been 

extended to meet the Fe-V binary edge and be consistent with the σ phase in that binary 

system. The changes to the phase boundaries are sketched in dashed lines. The extent of the 

two-phase regions was not established by [1957Dar], but their locations were estimated, and 

hence the σ poor phase boundaries are shown dashed. The isothermal section at 1100˚C 

was determined by [1981Zha] using ternary diffusion couples. They were prepared by first 

making a series of binary couples from ground and polished metal blocks, which were then 

heated at high temperature in sealed quartz tubes. A block of the third component metal was 

subsequently welded to the binary couple under flowing argon before heating the assembly at 

1100˚C in a sealed quartz tube for 2 weeks. The materials used were electrolytic Fe, carbonyl Ni 

and V (purity, 99.7% by weight). After quenching, the samples were studied by EMPA and 

hardness measurement in order to determine the phase boundaries of the isothermal section at 

1100˚C. The isothermal section is given in Fig. 3, showing the σ phase extending from the Ni-V 

to the Fe-V binary edge. Small corrections have been made to ensure consistency with the 

accepted binary phase diagrams. 

In their work on the creation of a thermodynamic database for steels, [1998Mie] calculated 

an isothermal section for 1100˚C, using only thermodynamic descriptions for the binary Fe-Ni 

[1987Gab, 1993Lee] and Fe-V [1991Hua2] systems and estimated data for the Ni-V system 

based on [1994Rag2]. Despite using no ternary parameters and performing no formal 

optimization, the calculated γ and α phase boundaries were in reasonable agreement with 

the experimental data from [1981Zha] for Fe rich compositions. 

[1988Ray] reports on work conducted by [1960Arm] who used microstructural analyses to 

derive an isothermal section for the system at 1000˚C. The pure components were melted in 

alumina or zirconia crucibles and chill cast. The alloys were then homogenized at 1300˚C 

before annealing under vacuum at 1000˚C for 2 or 3 d. Following quenching, microscopic 

examination allowed the phase boundaries in the section to be determined to an accuracy 

of ±2 or 3 mass% of any component. Figure 4 shows the isothermal section at 1000˚C, taken 

from [1988Ray], based on the work of [1960Arm]. Alterations have been made where 

necessary to ensure consistency with the binary phase diagrams. The compositions of the 

phases in equilibrium are given in Table 4. These are compared with values for the same 

equilibrium for a temperature of 1200˚C estimated by [1988Ray] based on the work 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_15 

ß Springer 2009

4 15 

Fe–Ni–V 

of [1957Dar]. As can be seen from the figures and the compositions given in the table, the 

size of this three-phase equilibrium increases with decreasing temperature. The only other 

phase found in these sections is the θ phase, which is just stable at 1000˚C. The other 

intermetallic phases in the Ni-V system (Ni 2V and NiV 3) are not stable at these temperatures. 

Neutron diffraction studies of the long range order parameter in the γ’ and θ phases has been 

undertaken by [1970Gom1, 1970Gom2, 1972Gom, 1992Gom] and has suggested that the two 

phases exist in equilibrium with each other in the ternary system (see Temperature-Composition 

Sections section). However, as pointed out by [1988Ray], it would be expected that the 

long range order parameter of the alloys would become constant with varying V content 

within the two-phase region, which is contrary to their findings [1972Gom] (Fig. 5). A more 

plausible analysis of these results is given by [1988Ray] who suggests that the two intermetallic 

phases are in equilibrium with the disordered γ phase at some point along the Ni 3V-FeNi 3 join. 

[1988Ray] produced a room temperature section showing hypothetical phase relationships 

based on this premise, Fig. 6. 


No formal investigation of a vertical section across the phase diagram has been made, however 

of particular interest is how the ordered γ’ phase in the Fe-Ni system and the θ phase in the 

Ni-V system extend into the three component system. A number of studies have been made of 

the phase relationships along the VNi3 - FeNi3 join and how the ordering of the phases change 

with composition. [1970Sar, 1974Sar] used mechanical property studies (Young’s modulus, 

UTS, hardness), resistivity measurement and saturation magnetization measurement to investigate 

the influence of adding V to FeNi 3. Electrolytic Ni, carbonyl Fe and alumothermal V 

were melted under vacuum in alundum crucibles. Alloys were either slowly cooled at 2˚C·h –1 

following annealing at 850˚C for 4h, or after quenching from 1100˚C. Mechanical property 

measurement was carried out during isothermal heat treatments at 440, 500, 550, 610, 670 and 

800˚C. Results suggested that the two ordered phases were in fact in equilibrium with the 

disordered fcc phase in the plane of this section. This is contrary to work conducted by 

[1970Gom1, 1970Gom2, 1972Gom, 1992Gom]. They looked at the influence of substitution 

of the third component on the long range order of VNi 3 and FeNi 3 using neutron diffraction. 

They observed a dramatic decrease in the long range order parameter of FeNi 3 at around 10 

at.% V. Correspondingly, the long range order parameter of the VNi 3 structure was found to 

increase at about 15 at.% V (Fig. 5). This decrease in the long range order parameter for FeNi 3 

was explained by the formation of nuclei of the ordered VNi 3 phase. It would seem that there is 

a two-phase region of FeNi 2 and VNi 3. However, the interpretation of their results is a little 

confusing. As pointed out in [1988Ray], it would be expected that the presence of a two-phase 

field comprising these two phases would result in constant long range order parameter for 

each of the phases rather than them disappearing completely. This section would clearly 

benefit from further investigation. 


The most widely studied properties of alloys of this ternary system are the magnetic properties. 

[1984Gan1, 1984Gan2, 1984Gan3] used both a standard 4 probe dc method and vibrating 



MSIT 1

sample magnetometer to study ferromagnetism in Ni-rich alloys. Alloys were prepared by 

firstly induction melting the component elements and then homogenizing the cast material at 

1100˚C for 48 h before annealing at 900˚C prior to a water quench. Magnetization was studied 

between 77 and 300 K and it was found that the average number of Bohr magnetons per atom 

showed a non-linear variation with V concentration. The magnetization falls with temperature 

much faster than with conventional ferromagnets. There is also a sign reversal in the Hall 

coefficient for the ternary alloy. [1985Laa] studied the magnetic form factors at room 

temperature of alloys of composition (Ni0.6Fe0.4)1–xVx, where x = 0.095-0.159 using polarized 

neutron diffraction. It was found that the addition of V as an impurity affected the magnetic 

structure of the matrix as a whole and the average magnetic moment decreased. The spatial 

distribution, however, remained unaltered. [1986Maj] studied the linear magnetostriction of 

Ni-rich alloys from 10-300 K. Induction melted alloys were homogenized at 1150˚C for 48 h 

followed by an annealing treatment at 900˚C and water quench to retain the high-temperature 

disordered phase. The linear magnetostriction was found to be very small (~4·10 –6 ) and the 

minimum Curie temperature of 147 K was found for an alloy of composition 84Ni-5Fe-11V. 

AMössbauer study at 4.2 K of an alloy of composition (Ni0.594Fe0.406)0.841V0.159 was conducted 

by [1987Sta], and they found a non-zero magnetic moment for Ni. This suggests that the 

electronic structure of this ternary alloy is more complex than the binary Ni-V alloys. 

[1990Miy] studied the magnetoresistivity of an Fe-82Ni thin film with V additions. The 

films were produced by electron-bean evaporation on to crystallized glass in the presence of 

a magnetic field. The saturation magnetization and electrical resistivity of films with a 

thickness of 10μm were measured using the Neugebauer method and a 4-probe technique in 

a magnetic field of 3980 H, respectively. The addition of V increases the electrical resistivity 

only slightly, whereas the anisotropic resistivity decreases. 

The effective permeability μ e and its stress-sensitivity in high frequency fields (H = 

0.4 A·m –1 , f = 1-100 kHz) in Fe-Ni-V alloys were investigated by [1984Tak]. Sheets of Fe- 

Ni-V alloy were cold rolled to a thickness of 0.025 mm and annealed at 873-1473 K in pure 

hydrogen. They were subjected to low temperature heat treatment. The dc magnetic properties, 

saturation magnetostriction, Curie point and electrical resistivity were also measured. It 

was found that the optimum annealing temperature to achieve maximum μ e is shifted to lower 

temperatures with increasing frequency. [1991Yao] studied the mechanical properties of 

γ’ alloys and concluded that they were ductile at room and high temperature. Elongation 

was ~30% at 800˚C. 

A brief listing of the experimental studies associated with materials properties is given in 

Table 5. 

Miscellaneous 


5 

The γ phase in the Fe-Ni-V system undergoes a martensitic transformation and has been the 

subject of particular study. [1981Geo] melted an alloy of Ni-24Fe with 4.5, 5.0, 5.5 and 6.0 

mass% V additions. The alloys were homogenized between 1110 and 1150˚C for 10-21 h. The 

alloys were then heat treated at 1150˚C for 1h before quenching and tempering for 2-30 min in 

liquid Sn before slow cooling for dilatometry. At a cooling rate of 10˚C/min, the M s temperature 

falls from –20˚C at a V content of 4.5 mass% to –45˚C at 6.0 mass% V. The ageing 

of martensite has been studied by [1977Edn, 1978Zai1, 1978Zai2, 1981Zay, 1984Bel]. Hardness 

and electrical resistance measurements, XRD, nuclear gamma-resonance measurements, 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_15 

ß Springer 2009

6 15 

Fe–Ni–V 

and electron microscopy were used by [1977Edn] to investigate the effect of combined 

Ni (0-18 mass%) and V (0-10 mass%) additions in Fe-Ni-V alloys. It was found that alloying 

Fe-V alloys with Ni promoted the formation of martensite after quenching and strengthening 

of the material after heating to 250-550˚C. It was supposed that the strengthening was 

associated with the formation during ageing of disperse precipitates of VNi 3. Subsequent 

work by [1981Zay] indicated that the precipitation of VNi3 is preceded by clustering of 

V atoms or possibly microscopic ordering. This was indicated by an increase in the specific 

electrical resistance of the material. The early stages of precipitation of VNi 3 was studied 

by [1984Bel] using the positron annihilation method. It is the precipitation of VNi 3 that 

was deemed to be responsible for an anomalous increase in the lattice parameter of martensite 

on ageing as the matrix progressively becomes denuded of Ni and V [1978Zai2]. The 

same authors looked at a combined low-temperature and high-temperature ageing of martensite 

and discovered an increase in the degree of hardening over the single heat treatment 

[1978Zai1]. 

[1981Wad] studied nitrogen solubility in Fe-Ni-V alloys with up to 15 mass% V at 

temperatures between 1775 and 2040˚C by the Sievert’s method. The solubility followed 

Sievert’s law for all compositions studied. 

. Table 1 

Investigations of the Fe-Ni-V Phase Relations, Structures and Thermodynamics 




[1957Dar] XRD, microstructural examination Homogeneity range of σ phase at 

1200˚C 

[1960Arm] Microstructural examination Isothermal section at 1000˚C 

[1963Zeg] XRD, microstructural examination Dissolution of Fe in V3Ni [1970Sar] Young’s modulus measurement, 

XRD, potentiometric method 

Compositions along FeNi3-VNi3 

[1970Gom1, 1970Gom2, 

1972Gom, 1992Gom] 

Neutron diffraction Ordering and phase relationships 

in the FeNi3-VNi3 section. 

[1981Zha] Diffusion couples/EPMA Isothermal section at 1100˚C 



MSIT 1

. Table 2 

Crystallographic Data of Solid Phase 


Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 




7 


Fm3m 

(Ni) 

< 1455 

Cu a = 352.4 [V-C2, Mas2] 

(γFe) 

1394 - 912 

a = 364.67 at 915˚C [V-C2, Mas2] 

α, (δαFe,V) cI2 

Im3m 

(δFe) W a = 293.15 1394˚C [Mas2] 

1538 - 1394 dissolves up to 3.8 at.% Ni at 1517˚C 

[2008Kuz] 

(αFe) a = 286.65 at 25˚C [Mas2] 

< 912 dissolves 4.6 at.% Ni at 495˚C [2008Kuz] 

(V) a = 302.40 at 25˚C [Mas2]. Dissolves up to 24 at.% Ni at 

< 1910 

1280˚C. 


P63/mmc Mg 

c = 396.0 

γ’, FeNi3 cP4 a = 355.23 63 to 85 at.% Ni [2008Kuz] 

< 517 Pm3m 

AuCu3 γ’’, FeNi tP4 a = 357.9 ± 0.1 [V-C2] 

metastable P4/mmm c = 357.9 ± 0.1 metastable ordering temperature 

AuCu 320˚C at 51.2 at.% Ni [2008Kuz] 

σ tP30 

P42/mnm σVNi σCrFe a = 895.4 at 57.5 at.% V [1982Smi] 

< 1280 c = 463.5 

a = 899.6 at 63.2 at.% V [1982Smi] 

c = 465.3 contains 73.5 at.% V at 900˚C and 55 at.% V 

at 890˚C [Mas2] 

σVFe a = 896.5 at V0.5Fe0.5 [V-C2] 

< 1252 c = 463.3 29.6-60.1 at.% V [Mas2]. 

θ, VNi3 tI8 a = 354.3 at 23.44 at.% V 

< 1045 I4/mmm 

Ti3Al c = 720.2 

a = 354.2 

c=721.3 

at 24.75 at.% V 

a = 354.1 

c=721.8 

at 25.60 at.% V [Mas2, 1982Smi] 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_15 

ß Springer 2009

8 15 

Fe–Ni–V 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 



VNi2 oI6 a = 255 to 256 at 33.3 at.% V [1982Smi] 

< 922 Immm b = 771 to 764 

MoPt2 c=354 to 355 

V3Ni cP8 

< 900 Pm3n 

V3(FexNi1–x) Cr3Si a = 471.15 ± 0.0007 x=0[1963Zeg] 

a = 469.10 ± 0.0001 x=0.3 [1963Zeg] 

a = 469.45 ± 0.0001 x=0.5 [1963Zeg] 

a = 469.83 ± 0.0001 x=0.7 [1963Zeg] 

VNi8 tI18 a = ~749 [1982Smi] 

< 405 - b=~749 

NbNi8 c=353 

. Table 3 



Fe 


Ni V 

L+α Ð γ + σ ? U - - - - 

. Table 4 

Three-Phase Equilibria 

T [˚C] Phase 

Fe 


Ni V 

1200 α 45.4 22.6 32 

γ 48 20.4 31.6 

σ 44 19.5 36.5 

1000 α 40 32 28 

γ 57 15 28 

σ 48 13 39 



MSIT 1

. Table 5 

Investigations of the Fe-Ni-V Materials Properties 

Reference 



[1981Geo] Neutron diffraction, 

dilatometry 

Martensitic transformation kinetics 

[1984Gan1] 4-probe dc method Hall coefficient 

[1984Gan2] Vibrating sample 

magnetometry 

Ferromagnetism in Ni rich Ni-Fe-V alloys 

[1985Laa] Polarized neutron 

diffraction 


Magnetic form factor in (Fe 0.4Ni 0.6) 1–xV x at RT, 

x = 0.095-0.159 

[1986Maj] Wheatstone bridge Magnetostriction and TC of Fe-Ni-V alloys 

[1987Sta] Mössbauer studies Magnetic moment of Ni in ternary Fe-Ni-V alloys 

[1990Miy] 4-probe technique Electrical resistivity and saturation magnetization of 

82Ni-Fe+V thin film 

[1991Yao] Tensile and fracture test Mechanical properties of alloys with γ’ structure 

[1992Gom] Differential magnetic 

susceptibility 

Variation of Tc from FeNi3 to VNi3 Landolt‐Börnstein 


MSIT 1 

9 

DOI: 10.1007/978-3-540-70890-2_15 

ß Springer 2009

10 15 

Fe–Ni–V 

. Fig. 1 

Fe-Ni-V. Liquidus surface projection 



MSIT 1

. Fig. 2 

Fe-Ni-V. Isothermal section at 1200˚C 



MSIT 1 


11 

DOI: 10.1007/978-3-540-70890-2_15 

ß Springer 2009

12 15 

Fe–Ni–V 

. Fig. 3 




MSIT 1

. Fig. 4 




MSIT 1 


13 

DOI: 10.1007/978-3-540-70890-2_15 

ß Springer 2009

14 15 

Fe–Ni–V 

. Fig. 5 

Fe-Ni-V. Long-range-order parameter S plotted against V content for alloys of the series 

Ni 3Fe 1–xV x 



MSIT 1

. Fig. 6 

Fe-Ni-V. Hypothetical phase relationships at room temperature 



MSIT 1 


15 

DOI: 10.1007/978-3-540-70890-2_15 

ß Springer 2009

16 15 

Fe–Ni–V 

References 

[1934Kue] Kuehlewein, H., Stoermer, R., “The Characteristics of Ferromagnetic Alloys of the Ternary Iron- 

Nickel-Vanadium System” (in German), Z. Anorg. Chem., 218, 65–88 (1934) (Crys. Structure, Kinetics, 

Phase Diagram, Thermodyn., 28) 

[1949Jae] Jaenecke, E., “Fe-Ni-V” (in German) in “Kurzgefasstes Handbuch aller Legierungen”, Winter Verlag, 


[1957Dar] Darby, J.B., Beck, P.A., “σ Phase in Certain Ternary Systems with Vanadium”, Trans. AIME, 209, 69–72 

(1957) (Experimental, Phase Diagram, Phase Relations, #, 8) 

[1960Arm] Armitage, C. H., “The Fe-Ni-V system”, Thesis, Univ. Wisconsin, U.S.A., 21, 579–580 (1960) as quoted 

in [1988Ray] 

[1963Zeg] Zegler, S.T., Downey, J.W., “Ternary Cr 3O-Type Phases with Vanadium”, Trans. Met. Soc. AIME, 227 


[1970Gom1] Goman’kov, V.I., Puzey, I.M., Mal’tsev, E.I., “Effect of Alloying Elements on the Superstructure of 

Ni 3Fe” (in Russian), Dokl. Akad. Nauk SSSR, 194(2), 309–311 (1970) (Crys. Structure, Experimental, 


[1970Gom2] Gomankov, V.I., Puzey, I.M., Maltsev, Ye.I., “Effect of Vanadium, Copper and Germanium on the 

Ni 3Fe Superstructure”, Phys. Met. Metallogr. (Engl. Transl.), 30, 237–240 (1970), translated from Fiz. 

Met. Metalloved., 30(1), 220–222, (1970) (Crys. Structure, Experimental, Phase Diagram, Phase 


[1970Sar] Sarkisyan, R.S., Selissky, Ya.P., Sorokin, M.N., “Study of the Ternary Solid Solutions Ni 3(Fe, V)”, Phys. 

Met. Metallogr.(Engl. Transl.), 30(1), 47–53 (1970), translated from Fiz. Met. Metalloved., 30(1), 47–53 

(1970) (Crys. Structure, Experimental, Kinetics, 17) 

[1972Gom] Gomankov, V.I., Puzey, I.M., Kozis, Ye.V., Maltsev, Ye.I., Sigaev, V.N., “Atomic Ordering in the Ternary 

System Ni-Fe-V”, Phys. Met. Metallogr. (Engl. Transl.), 33(3), 191–194 (1972), translated from Fiz. Met. 

Metalloved., 33(3), 648–651 (1972) (Crys. Structure, Electronic Structure, Experimental, 6) 

[1974Sar] Sarkisyan, R.S., Selisskiy, Ya.P., “Investigation of Ternary Alloys Based on Ni 3Fe with Vanadium”, Phys. 

Met. Metallogr. (Engl. Transl.), 37(4), 137–141 (1974), translated from Fiz. Met. Metalloved., 37(4), 

832–836 (1974) (Crys. Structure, Experimental, Kinetics, 18) 

[1977Bra1] Brauwers, M., “Occurrence of the σ Phase Computed from a Cluster Model”, J. Phys. F: Met. Phys., 

7(6), 921–927 (1977) (Calculation, Phase Diagram, Phase Relations, Theory, 17) 

[1977Bra2] Brauwers, M., Brouers, F., “On the Occurrence of the σ Phase in Transition-Metal Alloys”, Philos. 

Mag., 35, 1105–1109 (1977) (Calculation, Phase Diagram, Phase Relations, Theory, 7) 

[1977Edn] Edneral, A.F., Zaitseva, R.D., Perkas, M.D., Rodionov, Yu.L., Sersenbin, O.S., “Ageing of Martensite in 

Fe-Ni-V Alloys” (in Russian), Fiz. Met. Metalloved., 44(6), 1245–1253 (1977) (Morphology, Mechan. 


[1978Zai1] Zaitseva, R.D., Perkas, M.D., Rodionov, Yu.L., Sarsenbin, O.S., “Influence of Preliminary Low- 

Temperature Ageing of Martensite of Fe-Ni-V Alloys on the Variation of Properties during High- 

Temperature Ageing” (in Russian), Fiz. Met. Metalloved., 45(1), 78–83 (1978) (Morphology, Mechan. 


[1978Zai2] Zaitseva, R.D., Perkas, M.D., “’Anomalous’ Variation in the Lattice Parameter of Martensite during 

the Ageing of Fe-Ni-V and Fe-Ni-Co-V Alloys” (in Russian), Fiz. Met. Metalloved., 45(1), 103–109 

(1978) (Crys. Structure, Morphology, Mechan. Prop., Experimental, 9) 

[1981Wad] Wada,H., Pehlke, R.D., “Nitrogen Solubility in Liquid Fe-V and Fe-Cr-Ni-V Alloys”, Metall. Trans. B, 

12(B), 333–339 (1981) (Experimental, Thermodyn., 10) 

[1981Geo] Georgiyeva, I.Ya., Matyushenko, L.A., Udovenko, V.A., “Investigation of the Martensitic Transformation 

Kinetics and Structural Peculiarities of Ternary Iron-Nickel-Based Alloys”, Phys. Met. Metallogr. 

(Engl. Transl.), 52(3), 111–115 (1981), translated from Fiz. Met. Metalloved., 52(3), 580–584 (1981) 

(Crys. Structure, Experimental, Kinetics, Phase Relations, 2) 

[1981Zay] Zaytseva, R.D., Perkas, M.D., “Investigation of the Maraging Kinetics of Fe-Ni-V and Fe-Ni-Co-V 

Alloys”, Russ. Metall., (2), 106–109 (1981) (Morphology, Kinetics, Mechan. Prop., Experimental, 5) 

[1981Zha] Zhanpeng, J., “A Study of the Range of Stability of σ Phase in some Ternary Systems”, Scand. J. Metall., 

10, 279–287 (1981) (Electronic Structure, Experimental, Phase Diagram, Phase Relations, #, 14) 

[1982Smi] Smith, J.F., Carlson, O.N., Nash, P.G., “The Ni-V (Nickel-Vanadium) System”, Bull. Alloy Phase 

Diagrams, 3(3), 342–348 (1982) (Crys. Structure, Phase Diagram, Review, Thermodyn., 35) 



MSIT 1


17 

[1983Ray] Raynor, G.V., Rivlin, V.G., “Phase Equilibria in Iron Ternary Alloys. XI. Critical Evaluation of 

Constitution of Chromium-Iron-Vanadium and Iron-Nickel-Vanadium Systems”, Int. Met. Rev., 

28(5), 251–270 (1983) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, Review, 44) 

[1984Bel] Belen’kii, A.Ya., Valuev, N.P., Zhikharev, A.N., Zaitseva, R.D., Klimov, A.B., Latyshev, V.K., Moish, Yu. 

V., Perkas, M.D., “Investigation of Ageing of Martensite in Fe-Ni-V and Fe-Ni-V-Mo Alloys by the 

Positron Annihilation Method” (in Russian), Fiz. Met. Metalloved., 57(6), 1128–32 (1984) (Mechan. 


[1984Gan1] Gangopadhyay, A.K., Ray, R.K., Majumdar, A.K., “Sign Reversal of the Extraordinary Hall-Coefficient 

in Ni-Fe-Cr and Ni-Fe-V Alloys”, Phys. Rev. B, 30(4), 1801–1810 (1984) (Experimental, Magn. Prop., 


[1984Gan2] Gangopadhyay, A.K., Ray, R.K., Majumdar, A.K., “Weak Itinerant-Electron Ferromagnetism in 

Ni-Rich Ni-Fe-Cr and Ni-Fe-V Alloys”, Phys. Rev. B, 30(11), 6693–6706 (1984) (Electrical Properties, 

Experimental, Kinetics, Magn. Prop., Thermodyn., 52) 

[1984Gan3] Gangopadhyay, A.K., Majumder, A.K., Ray, R.K., “The Sign Change of the Extra-Ordinary Hall 

Constant R s in Ni-Fe-V and Ni-Fe-Cr Alloys”, Indian J. Cryogenics, 9(4), 294–301, (1984) (Experimental, 

Magn. Prop., Thermodyn., 12) 

[1984Tis] Tischer, Z., “Abrasion Resistant Alloy on the Basis of Ni-Fe-V for Magnetic Head Cores” (in Czech), 

Slaboproudy Obzor, 45(11), 548–50 (1984) (Mechan. Prop., Experimental, 3) 

[1984Tak] Takeyama, T., Sato, Y., “Influence of Heat Treatment and Composition on Effective Permeability and 

its Stress-Sensitivity in thin Sheets of Ni-Fe-V Alloys”, J. Jpn. Inst. Met., 48(7), 754–60 (1984) (Magn. 

Prop., Mechan. Prop., Experimental, 16) 

[1985Laa] van Laar, B., Maniawski, F., Kaprzyk, S., “Neutron Magnetic Form Factors of Ternary Ni-Fe-V Alloys”, 

J. Phys. F: Met. Phys., 15(3), 675–680 (1985) (Experimental, Magn. Prop., 17) 

[1986Din] Dinsdale, A.T., Chart, T.G., MTDS, National Physical Laboratory, Teddington, UK, unpublished work 

(1986) as quoted in [2001Ser] 

[1986Maj] Majumdar, A.K., Greenough, R.D., “Linear Magnetostriction in Polycrystalline Ni-Fe-Cr and Ni-Fe-V 

Alloys”, J. Magn. Magn. Mater., 59(1–2), 57–61 (1986) (Experimental, Magn. Prop., Phase Relations, 


[1987Gab] Gabriel, A., Gustafson, P., Ansara, I., “A Thermodynamic Evaluation of the C-Fe-Ni System”, Calphad, 

11(3), 203–218 (1987) (Phase Diagram, Phase Relations, Thermodyn., Assessment, 41) 

[1987Sta] Stadnik, Z.M., Griesbach, P., Dehe, G., Gutlich, P., Maniawski, F., “Nickel Contribution to the 

Magnetism of the Ni-Fe-V Alloy”, J. Magn. Magn. Mater., 70(1–3), 436–438 (1987) (Electronic 


[1988Ray] Raynor, G.V., Rivlin, V.G., “Fe-Ni-V” in “Phase Equilibria in Iron Ternary Alloys”, Inst. Metals, London, 

433–440 (1988) (Phase Diagram, Phase Relations, Review, 10) 

[1990Miy] Miyazaki, T., Ajima, T., Sato, F., “Magnetoresistance of 82Ni-Fe Based Alloy Films”, J. Magn. Magn. 

Mater., 83(1–3), 111–112 (1990) (Electrical Properties, Experimental, 13) 

[1991Hua1] Huang, W., “A Thermodynamic Evaluation of the Fe-V-C System”, Z. Metallkd., 82(5), 391–401 (1991) 

(Phase Diagram, Phase Relations, Thermodyn., Assessment, 54) 

[1991Hua2] Huang, W., “Thermodynamic Properties of the Fe-Mn-V-C System”, Metall. Trans. A., 22A(9), 

1911–1920 (1991) (Phase Diagram, Phase Relations, Thermodyn., Assessment, 25) 

[1991Yao] Yao, X., Chen, N., “Microstructures and Mechanical Properties of (Fe,Co,Ni) 3V Alloys”, Mater. 

Mechan. Eng., 15(2), 27–31 (1991) (Crys. Structure, Mechan. Prop., Experimental, 10) 

[1992Gom] Gomankov, V.I., Gezalyan, A.D., Tretyakov, B.N., Sumin, V.V., “Structural and Magnetic State of 

Ni 3Fe-Ni 3VAlloys” (in Russian), Russ. Metall. (Engl. Transl.), (2), 195–199 (1992), translated from Izv. 

Ross. Akad. Nauk, Met., (2), 195–199 (1992) (Experimental, Phase Diagram, Phase Relations, Magn. 

Prop., 13) 

[1992Luo] Luoma, R., Report TTK-V-B76, Helsinki University of Technology, Laboratory of Materials Processing 

and Powder Metallurgy, (1992) (Phase Diagram, Phase Relations, Thermodyn., Assessment, 65) 

[1993Lee] Lee, B.-J., “Revision of Thermodynamic Descriptions of the Fe-Cr and Fe-Ni Liquid Phases”, Calphad, 

17(3), 251–268, (1993) (Phase Diagram, Phase Relations, Thermodyn., Assessment, 95) 

[1994Rag1] Raghavan, V., “Fe-Ni-V (Iron-Nickel-Vanadium)”, J. Phase Equilib., 15(6), 630 (1994) (Phase Diagram, 


[1994Rag2] Raghavan, V., Antia, D.P., “The Chromium Equivalents of Selected Elements in Austenitic Stainless 

Steels”, Metall. Mater. Trans. A., 25A(12), 2675–2681, (1994) (Phase Relations, Thermodyn., Calculation, 

32) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_15 

ß Springer 2009

18 15 

Fe–Ni–V 


(1998) (Assessment, Calculation, Phase Diagram, Phase Relations, Thermodyn., 98) 

[2000Ans] Ansara, I., Private Communication, as quoted in [2001Ser] 

[2001Ser] Servant, C., Sundman, B., Lyon, O., “Thermodynamic Assessment of the Cu-Fe-Ni System”, Calphad, 

25(1), 79–95, (2001) (Phase Diagram, Thermodyn., Assessment, 44) 

[2001Wat] Watson, A., Hayes, F.H., “Some Aspects of Modelling the σ Phase in the Ni-V System”, J. Alloys 

Compd, 320(2), 199–206 (2001) (Phase Diagram, Thermodyn., Assessment, 46) 

[2005Ust] Ustinovshikov, Y., Pushkarev, B., Sapegina, I., “Phase Transformations in Alloys of the Fe-V System”, 

J. Alloys Compd., 398, 133–138 (2005) (Crys. Structure, Phase Diagram, Experimental, 9) 

[2006Oka] Okamoto, H., “Fe-V (Iron-Vanadium)”, J. Phase Equilib. Diff., 27(5), 542 (2006) (Review, Phase 

Diagram, 3) 





(1990) 





MSIT 1

Iron – Nickel – Tungsten 


Elena Semenova 

Introduction 

Fe–Ni–W 16 

1 

The Fe-Ni-W system is of great interest in a number of technological fields, such as the 

sintering of hard and refractory W-based alloys. The phase diagram of the Fe-Ni-W system has 

been studied experimentally since 1932. The first work of [1932Win] focused on compositions 

in the region of up to 45 mass% W; eight vertical sections together with the projection of the 

liquidus surface were constructed and later reproduced by [1961Eng, 1949Jae]. The investigation 

was accompanied by the measurement of some magnetic properties. 

Critical assessments of the phase diagram are presented in [1971Win, 1981Ray, 

1988Ray, 1994Rag]. The Ni-rich region of the Fe-Ni-W system was studied in detail between 

1350-800˚C by [1969Aga], for alloys lying on sections with Fe:Ni ratios from 20:80 to 70:30, 

and also isotherms of solubility were constructed. The tungsten solubility in the γ phase was 

presented as isotherms is in agreement with [1932Win]. 

Based mainly on [1932Win] and taking into account the findings of [1969Aga] as well as 

information on the binary systems known at that time, [1971Win] proposed isothermal 

sections of the Fe-Ni-W phase diagram for temperatures between 800 and 1560˚C. The version 

of the liquidus surface projection proposed by [1932Win], as well as the phase diagram at 

1400˚C from [1971Win] was supported in the subsequent work of [1986Fer], which 

incorporated some suggestions of [1981Hen] regarding the existence of a saddle point on 

the surface of the γ primary crystallization field. 

There are, however, a number of discrepancies between the different versions of the phase 

diagram of this system for the solid state. Equilibrium is hard to attain in this system and 

consequently, different phase relations were derived by different researchers depending on 

the annealing time used in their experiments. [1982Ban] studied the phase equilibria in the 

Fe-rich region of the Fe-Ni-W system as a part of the more complex Co-Fe-Ni-W system. 

The latter is of practical interest in relation to the production of martensite-ageing alloys. The 

existence of a three-phase (αFe)+γ+μ domain at 1300, 1200 and 800˚C was suggested. But this 

is in contradiction with most of the other studies of the ternary phase diagram and also with 

the accepted Fe-W binary system [Mas2], where the μ phase decomposes below 1190˚C. The 

Fe 2W phase was not found by [1982Ban] in the alloys investigated as part of their work. 

Moreover, [1972Var] did not see the Laves phase in Fe 2W-Ni 2W alloys at 950˚C, but equilibria 

between the μ and (αFe) phases were observed up to 16.7 at.% Ni in ternary alloys. [1986Zak1, 

1986Zak2, 1991Nik, 1992Nik] studied the phase relationships in the ternary Fe-Ni-W alloys in 

the W rich corner as a part of their study of the Co-Fe-Ni-W system. Isothermal sections for 

1400, 1200, 1050, 950, 800 and 527˚C, as well as vertical sections along 10 and 20 (Fe+Ni) 

(mass%) were constructed. [1979Edm], looking for a cause of embrittlement of Fe-Ni-W 

alloys, found that furnace cooling resulted in the precipitation of the (Fe,Ni)W phase at the 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_16 

ß Springer 2009

2 16 

Fe–Ni–W 

matrix-tungsten interface in (3-5)Fe-(5-7)Ni-W (mass%) alloys. This phase was considered to 

be responsible for embrittlement of the alloys. The distribution of the alloy components 

between the phase constituents on sintering W rich alloys and their redistribution after 

subsequent heat treatment was the subject of investigation by [1965Dzy, 1977Mar, 1980Min, 

1982Buk, 1995Dje]. Diffusion of Ni and Fe in W and of W in Ni and Fe was shown to 

accompany the sintering process. The W solubility was found to be higher in Ni than in Fe and 

to decrease on addition of the latter to an alloy. [1983Du] compared the composition of the γ 

and (W) phases in the as sintered state and after heat treatment. [1981Ahn] calculated the 

solidus and liquidus curves in the Fe-Ni-W system separating at 1540˚C the (W)/(L+(W)) and 

(L+(W))/L regions, respectively. [1986Fer] studied the phase equilibria in the Fe-Ni-W 

system. Their own experimental data presented as a series of tie-lines at temperatures of 

1000, 1100, 1200, 1300 and 1400˚C, as well as data on liquidus surface [1932Win] were used by 

[1986Fer] to evaluate the phase diagram and draw isothermal sections for these respective 

temperatures. The liquidus projection and a number of isopleths were also constructed from 

the data of [1932Win, 1969Aga, 1982Ban]. [1968Ega, 1969Yeg, 1970Gom, 1972Ive,] studied 

the effect of the W substitution for Fe in the FeNi 3 phase and on the degree of the long range 

ordering. [1982Rom] examined the conditions of heat treatment, cooling and ageing at which 

the W phase precipitated from the γ solid solution. The size of W particles was estimated. 

[1986Woo] examined the mechanical properties of a composite formed by a low-tungsten (25 

mass% W) alloy in a W rich (95 mass% W) matrix. 

A number of studies [2000Ryu, 2001Fan, 2001He, 2004Zha1, 2004Zha2, 2006Zha] were 

carried out on Fe-Ni-W alloys produced by mechanical alloying. Their thermal stability, 

microstructure and phase evolution on heating, grain growth, effect of milling time on 

crystallization and mechanical properties were investigated. With a view to using tungsten 

heavy alloys in nuclear fusion facilities, [1990Kra] investigated the radiation induced embrittlement 

of a 1.6Fe-3.4Ni-W (mass%) alloy. With the aim of controlling the formation of the 

Ni 4W phase, which is detrimental to the mechanical properties of the material, [2003Ron] 

examined the ageing mechanism under strain conditions at 800˚C of two Fe-Ni-36W (mass%) 

alloys, with compositions Fe:Ni = 1:9 and 3:7. Fine precipitates of Ni 4W distributed in the γ 

phase were found in the Ni rich sample. 

[2005Mar] produced dense and fine grains in tungsten heavy alloys by reaction synthesis 

combined with a dynamic consolidation process, and the results obtained were compared with 

those observed in conventional material preparation. 

[2006Par] applied a ‘master sintering curve’ to analyze both densification and grain growth 

data obtained by experiment for three Fe-Ni-W compositions. Activation energies of grain 

growth were calculated. 

Investigations of the system related to phase relations, structures and thermodynamic are 

presented in Table 1. 


The Fe-Ni boundary binary system is accepted from the critical assessment of [2008Kuz]. The 

Fe-W system is taken from [Mas2] and Ni-W is from [1991Oka]. It is worth mentioning that 

[Mas2] questioned the stability of the Fe 2W phase and showed it tentatively as metastable. 



MSIT 1



3 

The crystallographic data of the solid phases along with their stability ranges are shown in 

Table 2. No ternary phases are known in the system. The μ (Fe 7W 6) phase was found to be 

stable by [1932Win, 1972Var, 1981Hen, 1982Ban, 1986Fer, 1991Nik, 1992Nik]. The nickel 

solubility of the μ phase was accepted from [1981Hen] (about 10 at.%) as their investigations 

involved annealing alloys for prolonged periods of time in order to reach equilibrium at 

1000˚C (about 8 months). Data from [1972Var] on the phase relationships in Fe2Ni-Ni2W 

alloys at 950˚C indirectly supported this value. In the experimental work of [1932Win, 

1981Hen, 1982Ban, 1972Var] (the last work was carried out specifically to find out if the 

Fe 2W phase exists in the Fe-W binary or Fe-Ni-W ternary systems), the Fe 2W phase was not 

found. It was, however, observed by [1986Fer, 1987Kar]. In both of these last two cases, the 

equilibrium state was evidently not attained in their alloys; by [1986Fer] owing to the nature of 

the method used (diffusion couple technique) and by [1987Kar] because of insufficient heat 

treatment of the compacted powders (an hour at 1150˚C). [2005Mar] showed the presence of 

the phase in a 3Fe-7Ni-W (mass%) alloy that had been consolidated at 1000˚C using a shock 

wave treatment, confirming the metastable character of this phase. Here, according to 

[1972Var, 1981Hen, 1982Ban], the Fe 2W phase is considered to be metastable. [1981Hen] 

found substantial mutual solubility of the FeW and NiW equiatomic binary phases (which 

were assumed to be isomorphic) taking place at 1000˚C and suggested complete mutual 

solubility of them at this temperature and below. The formation of a continuous series of 

solid solutions of (Fe,Ni)W at 950˚C and down to 575˚C was reported by [1991Nik, 1992Nik]. 

[1986Zak1, 1986Zak2] did not observe the FeW phase after annealing at 1200˚C (see Table 1) 

in alloys with 80 and 90 mass% W, but they assumed its appearance after more prolonged 

annealing. The intermetallic precipitates seen in 5Fe-5Ni-90W (mass%) alloys sintered at 

1450˚C were classified as the (Fe,Ni)W phase [1979Edm]. Because of a slowing down of the 

diffusion processes in the solid state, the peritectoid reactions by which the FeW, NiW, NiW 2 

and Ni 4W phases are formed remain incomplete following the heat treatment applied in most 

of the studies. 

Fe-Ni-W powders with 50 and 75 at.% W milled for 40 and 15 h, respectively, and then 

heated to 850˚C, contained as the products of crystallization the NiW and Ni4W phases in 

addition to the W and γ phases that had crystallized in the sample already at 570˚C [2001He]. 

The crystallization of the amorphous phase and the precipitation of the (Fe,Ni)W phase were 

observed by [2006Zha] after prolonged milling of the 6.1Fe-13.2Ni-80.7W (at.%) powders 

(about 60 h) and subsequent annealing. The solubility of W in the γ phase changes slightly 

on decreasing the temperature in the 1350-800˚C range for the Fe-Ni-W alloys lying on the 

20Fe-80Ni section and is of about 33 mass% [1969Aga]. For the 50Fe:50Ni alloy, the value 

of the W solubility at 1350˚C almost coincides with that given by [1932Win] at 1400˚C, at 

about 20 mass%. It decreases with increasing iron content in the alloys. The γ phase in the 

1.5Fe-3.8Ni-W (mass%) alloy has the composition 21.4Fe-55.3Ni-W (mass%) [1986Woo]. 

The amount of W found by [1977Mar] in the last portion of the crystallized liquid of a 

2.4Fe-Ni-93W (at.%) alloy was almost the same. 

[1982Buk] reported the total amounts of Fe and Ni dissolved in the α phase to be about 

0.4-1.3 mass%, depending on the heat treatment conditions. [1990Kra] pointed out that the 

microstructure of a 1.6Fe-3.4Ni-W (mass%) sample exposed to neutron irradiation contained 

two phases, γ+(W). Very small solubility of Fe and Ni in W was also reported by [1977Mar, 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_16 

ß Springer 2009

4 16 

Fe–Ni–W 

1980Min, 1982Rom, 1986Woo, 2001Fan]. [1977Mar] reported 0.28 at.% Ni and 0.13 at.% Fe 

in W. Mechanical alloying of a W heavy alloy (2.1Fe-4.9Ni-93W (mass%)) followed by 

annealing at 1280˚C gives nearly pure W particles embedded in a 63.7W-17.4Ni-19.9Fe 

(mass%) matrix [2004Zha2]. The ball milled mixture (for 60 h) has a melting point 220˚C 

lower than that of the unmilled powdered. According to [1983Du], the composition of the 

phases in the 3Fe-7Ni-W (mass%) alloy changes insignificantly after heat treatment. The 

γ phase had the composition 24Fe-51Ni-W and 26Fe-54Ni-W (mass%), and W grains containing 

less than 0.1 mass% Fe and less than 0.14 mass% Ni were observed after sintering at 

1250˚C. A mixture of the same composition manufactured by [2005Mar] using a shock 

consolidation process had a matrix of approximately the same make-up of about 22Fe- 

53Ni-23W, despite on applying heat, the NiW phase being observed in the specimens 

produced at 1000˚C. On ageing a 6.4Fe-Ni-36W (mass%) alloy at 800˚C, a fine dispersed 

Ni 4W phase precipitates from the γ matrix [2003Ron]. Less than 0.5 mass% Fe dissolves in 

NiW2 at 950˚C [1991Nik]. 

The substitution of W for Fe in the FeNi3 phase leads to a increase in the ordering 

temperature, which reaches a maximum at about 555˚C for an alloy with 2 at.% W 

[1968Ega]. The long-range ordered crystal structure exists up to 3 at.% W [1968Ega, 

1970Gom]. According to [1968Ega, 1969Yeg], the temperature maximum was the result of 

the formation of a three component ordered structure. [1972Ive] considered that the long 

range order started to decrease at a W concentration of 2.05 at.% and the ordered structure 

disappeared in alloys containing about 5 at.% W. 


Details of the invariant equilibria involving the liquid phase are given in Table 3, taken from 

[1932Win]. Amendments have been made to some of the phase compositions. The phase 

labeled as Fe 3W 2 is actually recognized as μ (Fe 7W 6). The available information on the 

invariant reactions proceeding in the solid state is extremely conflicting due to the difficulties 

in obtaining the intermediate phases experimentally, most of which are formed in the solid via 

peritectoid reactions. [1991Nik] assumed that the μ Ð α+γ+(Fe,Ni)W eutectoid decomposition 

took place in the system at about 1130˚C, while [1992Nik] came to the conclusion that it 

should be a peritectoid reaction, μ+α Ð γ+(Fe,Ni)W, taking place in the temperature range 

1200-1050˚C. Attempts to derive a sequence of reactions for the solid state, taking into account 

either of these reactions and the formation of the (Fe,Ni)W solid solution, were not successful. 

Therefore, Fig. 1 gives a partial reaction scheme that reflects only the liquid-solid equilibria in 

the system. 

Liquidus, Solidus Surfaces 

Figure 2 shows the projection of liquidus surface based on that constructed by [1932Win], 

with some modifications relating to the locations of the invariant points in the binary system 

given by [2008Kuz] and the saddle point and homogeneity range of the μ phase given by 

[1981Hen]. Figure 3 gives the solidus surface projection of the system. The solidus temperature 

along the boundary of the γ phase decreases in the ternary system and reaches a minimum 

at about 49 at.% Ni [1932Win]. 



MSIT 1


A series of the isothermal sections at 1560, 1500, 1465, 1455 and 1400˚C were constructed by 

[1971Win] on the basis of experimental data from [1932Win]. The section for 1400˚C agrees 

with that based on experimental data from [1981Hen] and that computed by [1986Fer]. The 

isothermal section at 1400˚C is shown in Fig. 4. On lowering the temperature, the μ phase is 

assumed to decompose to give (W)+FeW below 1190˚C. Fragments of the isothermal sections 

near the W corner at 1050 and 950˚C proposed by [1992Nik] are shown in Figs. 5 and 6, 

respectively. The isothermal section of the whole system at 800˚C according to incomplete 

data given by [1981Hen] is presented in Fig. 7. The composition of the (Fe,Ni)W apex of the 

(Fe,Ni)W + (W) + NiW 2 triangle shown in the partial isothermal section at 950˚C (Fig. 6) is 

richer in Fe than that given for 800˚C shown in Fig. 7. On decreasing the temperature down to 

575˚C, the phase diagram has a similar appearance to that at 950˚C [1992Nik], since among 

the phases taking part in the (W)+NiW 2+(Fe,Ni)W equilibrium at 950˚C, the (W) and NiW 2 

phases do not have any noticeable homogeneity range. The only difference among the sections 

at 950, 800 and 575˚C lies in the location of the (Fe,Ni)W apex of the (W)+NiW2 +(Fe,Ni)W 

triangle. The latter is displaced towards the FeW phase as the temperature decreases. The 

version presented by [1982Ban] for the Fe-rich region at 800˚C can not be used in conjunction 

with the data of [1981Hen] because of the appearance of the μ phase that contradicts the latter 

work. In the isothermal section at 800˚C calculated by [1986Fer], the invariant equilibrium 

(W)+NiW+γ is present while equilibria with NiW 2 phase is omitted. This is in contradiction 

with the accepted Ni-W binary phase diagram [Mas2] where the NiW 2 phase is shown to 

exist at 800˚C, and therefore, must take part in equilibria within the ternary system. This 

section, as well as all of the others computed by [1986Fer] for the temperatures lower than 

1100˚C, are not consistent with the Fe-W binary system either, because both of them show 

equilibria including the μ phase, which does not exist at these temperatures, together with a 

metastable λ phase. 


The first experimental study of the ternary system, by [1932Win], presented 8 vertical sections 

located mainly in the Fe rich corner. None of them can be considered as accurate because of 

differences in the constitution of the binary systems and in the homogeneity range of the μ 

phase. The vertical sections presented by [1986Zak1, 1986Zak2, 1991Nik, 1992Nik] concern 

the W rich corner, at 80 and 90 mass% W. They were deduced from XRD measurements made 

on a great number of annealed alloys and can be taken as tentative. The section at 90 mass% W 

showing an increase in the formation of the (Fe,Ni)W phase and a decrease in the NiW 2 phase 

with increasing Fe content is presented in Fig. 8. The assessed isopleth at 14.3 at.% W is shown 

in Fig. 9. 



5 

[2004Zha1] calculated a positive excess Gibbs energy of mixing, Δ mixG xs , for both the 

amorphous phase and the crystalline solid solution in the Fe-Ni-W system at 300 K. For the 

amorphous Fe6.1Ni17.3W76.6 (at.%) phase, ΔmixG xs is 1.77 kJ·mol –1 . 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_16 

ß Springer 2009

6 16 

Fe–Ni–W 

The apparent activation energy for grain growth in the solid state was estimated by 

[2006Par] to be about 241 kJ·mol –1 , lower than both that for W diffusion in the solid matrix 

(268 to 306 kJ·mol –1 ) and for densification (367 kJ·mol –1 ). The activation energy of grain 

growth during liquid phase sintering is 106 kJ·mol –1 and is comparable with that of densification 

(101 to 136 kJ·mol –1 ). 

[1986Fer] presented an optimization of the thermodynamic description of the liquid, γ 

and μ phases and used it to calculate the phase diagram. The solidus curve separating (W) and 

(W)+L regions calculated by [1981Ahn] at 1540˚C was close to that calculated from the data of 

[1971Win], while the liquidus curve separating the L and L+(W) regions passed at a higher W 

concentration than was shown by experiment. 

The activation energy of the atomic redistribution process determined from data on 

Young’s modulus and resistivity for FeNi 3-Ni 3W alloys containing up to 2 at.% W in the 

temperature range 350-400˚C, is close to that for the FeNi 3 binary alloy and is of about 170 

kJ·mol –1 . For the alloys containing 2-2.5 at.% W, it falls sharply down to 100 kJ·mol –1 

[1968Ega, 1969Yeg]. 


Since tungsten heavy alloys are manufactured conventionally by sintering powder compacts, 

characteristics such as density and hardness are important and are usually reported. The 

density of a 1.5Fe-3.5Ni-95W (mass%) alloy, measuring 18.0 g·cm –3 was compared with that 

of the matrix at 9.2 g·cm –3 in [1986Woo]. The hardness of the matrix was 1.255 GPa (128 HV), 

and was much lower than that of the alloy, which measured 4.609 GPa (470 H V). The strength 

of the matrix was found to be less than half that of the specimen. A 3Fe-7Ni-W (mass%) alloy 

consolidated at 400˚C by shock synthesis had a density of 18.0 g·cm –3 ; that of the tungsten 

particles themselves being of about 29.4 g·cm –3 . The hardness remained consistent throughout 

the specimen [2005Mar]. [1977Mar] found the following characteristics for the 2.4Fe-Ni-93W 

composition: density of 17.4 g·cm –3 , hardness of 3.432 GPa (350 H V), tensile strength of 9 

MPa, elongation of 20%. The highest value of microhardness of the γ phase was reported by 

[1969Aga] in the alloy 10W-54Fe-36Ni (mass%), after sintering at 1350˚C. The (W) phase 

quenched from 800˚C has a hardness of 5.1 GPa [1991Nik]. The hardness of Fe-(5-20)Ni- 

(5-50)W (mass%) alloys increases with the W content; an observation explained by the 

increase in the amount of μ phase present [1982Ban] and the occurrence of a martensitic 

transformation. A maximum hardness, of about 5.384 GPa (540 H V), was found in (W)+γ+μ 

ternary alloys at 1200˚C. The variation in hardness with ageing time at 800˚C of a 36W-6.4Fe- 

57.6Ni and a 36W-19.2Fe-44.8Ni (mass%) alloy was compared by [2003Ron]. The hardness of 

the second alloy decreased monotonically while that of the first one after decreasing to the 

same level, increased, so the hardness gap between these two alloys was enlarged as ageing time 

increased. Fine Ni 4W precipitates strengthened and hardened the first alloy. A 1.4Fe-5.6Ni- 

93W (mass%) specimen sintered at 1300˚C after mechanical alloying exhibited fine tungsten 

particles of about 3 μm, a density higher than 99% of its theoretical value and a high yield 

strength of about 1100 MPa, while its impact energy and elongation characteristics were low 

[2000Ryu]. A large W/W contiguity and a low matrix volume fraction were considered as 

reasons for poor ductility and impact properties. This alloy, being liquid phase sintered in 

addition to being sintered in the solid state, possessed fine tungsten particles of about 6-15 μm 

in size; finer than those obtained through a conventional liquid phase sintering process. 



MSIT 1


7 

An alloy of composition 2.1Fe-4.9Ni-93W sintered at 1150˚C for 0.5 h, contains W particles of 

an average size of 2 μm distributed homogeneously in the γ phase [2004Zha2]. Sintering at 

1280˚C, results in an increase in particle size to 6-8 μm. The density of material sintered at 

1150˚C was above 95% of its theoretical value. A theory of liquid phase sintering is presented 

in [2007Lee] for Fe-Ni-W alloys. 

A number of investigations have been carried out on an alloy of composition 3Fe-7Ni-90W 

(mass%). Fe additions to the Ni-90W (mass%) alloys increase the ductility and elongation of 

the alloy, which may reach 20% [1965Dzy, 1977Mar]. [2002Ekb] found that the microhardness 

of the tungsten particles increases from 3.815 GPa (389 H V) for undeformed specimens to 

4.992 GPa (509 H V) after 57% deformation at 25˚C. The highest value of microhardness 

observed was 5.296 GPa (540±28 H V) following 49% deformation at 800˚C. On increasing 

temperature, this value decreases to a value close to that of an undeformed specimen at 

1100˚C. The dislocation density of the W particle measured for this composite was observed to 

be higher at higher deformation stress. The electrical resistance and hardness increases with 

the amount of deformation of the composite [2000Min]. Impact energy tests show that the 

toughness of heavy alloys is sensitive to the rate of cooling from the sintering temperature; the 

concentration of Ni and Fe in the alloys being a critical factor in the heat treatment process 

[1979Edm]. The ultimate tensile strength of a specimen that had been subjected to heat 

treatment under vacuum at 1500˚C was shown by [1983Du] to increase, depending on the 

applied stress. The ductility of the heat treated specimen increased by about 25 times as 

compared to the as-sintered material, the elongation under tension reaching 26.1-27.2% 

depending on the applied strain. The maximum crack free reduction by cold rolling was 

72% [2000Min]. [1981Hen] showed that the tensile and bending strength of this alloy did not 

depend significantly on the exposure time at 900˚C, but it rather did on the furnace atmosphere. 

On heating a mechanically alloyed specimen, the solubility of W in the γ phase was 

found to decrease on increasing the temperature up to about 1480˚C. The size of W particles 

increased slowly on heating up to about 600˚C, and on heating up to 1200˚C, crystalline 

growth was enhanced [2001Fan]. 

The Young’s modulus of the (Fe,W)Ni 3 ordered phase changes with composition, passing 

through a minimum at 2.2 at.% W [1968Ega, 1969Yeg], which was explained by a decrease in 

the ferromagnetic interaction and an increase in the metallic bond in the ordered alloys on 

substitution of Fe by W atoms. [1969Yeg] found a difference in the Curie point between 

annealed and rapidly cooled specimens, which increases linearly from a composition of FeNi 3 

up to Fe-75Ni-3W (at.%). The Curie temperature of Fe 2W-Ni 2W alloys decreases on increasing 

the Ni content up to 10 at.%, after which the temperature passes through a maximum at 

about 47 at.% Ni [1972Var]. 

The recovery and recrystallization of cold worked tungsten specimens depends on the 

penetration of the Fe-Ni-W liquid, the penetration rate being dependent on microstructure 

and internal stress [2003Ant]. The complete penetration of the Fe-Ni-W melt in deformed 

tungsten was observed after 84 s while for specimens recrystallized before penetration, the rate 

was moderate. 

The experimental techniques used in the investigation of materials properties of Fe-Ni-W 

alloys are listed in Table 4. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_16 

ß Springer 2009

8 16 

Fe–Ni–W 

Miscellaneous 

The addition of 3 at.% W destroys the long range ordering in FeNi 3 owing to the allocation of 

Ni atoms to the second coordination sphere [1970Gom]. 

The fracture surface of an irradiated bend specimen of composition 1.6Fe-3.4Ni-W 

(mass%) showed cleavage fracture in the tungsten grains and simple fracture in the Ni based 

matrix [1990Kra]. The specimen revealed a strong increase in the ductile-brittle transition 

temperature on increasing the neutron flux. 

A small decrease in the lattice parameter of the γ phase was observed towards 47 at.% Ni at 

950˚C from a = 359.9 to 359.3 pm, by [1972Var]. 

The W solubility in the γ solution decreases on increasing the Fe content. The most 

significant change in the W solubility of the γ phase with temperature was observed for the 

alloys lying on the section 50Fe:50Ni [1969Aga]. The solubility of W in the binder phase 

decreases as temperature increases for mechanically alloyed specimens, unlike for those 

obtained by traditional sintering [2001Fan]. 

[1965Dzy] studying the distribution of the alloy components in the phases obtained by 

liquid sintering showed that introducing Fe in a 10Ni-W (mass%) alloy suppressed the process 

of intensive grain boundary diffusion by reducing the Ni solubility in W grains as well as the W 

solubility in the Ni based matrix. The solubility of Fe in Wexceeds that of Ni; the amount of Fe 

in the center of W grain being much greater than that of Ni for alloys with the same 

proportion of elements in the matrix. The low melting binder phase of Fe-Ni-W sintered 

alloys occupies 21-23% of the surface area. 

Depending on cooling conditions, the lattice parameter of the binder phase of a 3Fe-7Ni- 

90W (mass%) alloy determined at RT increases from a = 359.25 pm (annealing at 1200˚C) 

through a = 359.43 pm (slow cooling) to a = 360.20 pm (quenching); the decrease in the W 

content in the binder phase being observed as 2-2.5 mass% on slow cooling and 5 mass% or 

more on annealing [1980Min]. The nickel based solid solution can contain from one to several 

hundred W phase particles. No texture was observed in a 3Fe-7Ni-W (mass%) composite 

quenched from the liquid phase sintering temperature [2000Min]. 

The study of [1983Du] supported the inference of [1979Edm] that the cracking took place 

at the W grain-matrix interface. Hydrogen stored in voids and dissolved in the metals during 

the sintering process causes the interfacial embrittlement. Heat treatment under vacuum was 

shown by [1983Du] to lead to the removal of the embrittlement and to an improvement in the 

tensile properties of the specimens. The different microstructures of two alloys containing the 

same amount of W but different ratios of Ni:Fe (9:1 and 7:3) results, according to [2003Ron], 

in different mechanism of hardening. 

The phase evolution with respect to milling time was determined by [2004Zha2]: the 

supersaturated solid solution forms first followed by a partially amorphous phase and then a 

mixture of amorphous and nanocrystalline phases. It is an example of mechanically induced 

amorphization, the system not having a large negative heat of mixing. During annealing of a 

mechanically alloyed specimen, the following stages were observed: stress relaxation, recovery 

and grain growth of nanocrystalline phases, phase precipitation and amorphous phase crystallization 

[2001Fan]. 

[1995Dje] assumed a statistical distribution of 3 at.% W in the Fe rich alloys of the ternary 

system. 

The distortion on sintering taking place in alloy compacts with W contents of 83, 88 and 

93 (mass%) with Fe:Ni ratio of 3:7, is linked to the underlying microstructure, and for the 



MSIT 1

compositions discussed, the transition from distorting to undistorting compacts occurred at 

compositions between Fe-Ni-88W and Fe-Ni-93W. Heating rates of up to 15˚C/min did not 

have a significant effect on densification or distortion [2004Bol]. 

The study by [2001He] of mechanically alloyed (7 to 19.5)Fe-(5.5 to 18)Ni-75W (at.%) 

material showed that the precipitation of W particles, followed by crystallization of the γ phase 

and formation of the NiW and Ni 4W phases in a glassy matrix, took place under heating. 

[1984Mud] identified the phase forming at the W-matrix interfaces in Fe-Ni-W 

(Fe:Ni=1:1) commercial alloy as (Fe,Ni)6W6C, which seemed to be stabilized by impurities. 

According to the model of liquid phase sintering used by [2007Lee] to simulate coarsening 

kinetics, the average particle volume increases linearly with time and the size of the particles is 

consistent with that obtained experimentally. 

It should be emphasized that the information available for the Fe-Ni-W phase diagram 

that has been considered here concerns only some aspects of the equilibria and thus can not be 

taken as final. The key problem is that it is quite difficult in practice to obtain homogeneous 

specimens owing to the great difference both in the melting points of the components and in 

their densities. Another challenge is to attain equilibrium in the system, as most reactions 

occurring in the solid state are at relatively low temperatures. Similar reservations should be 

made concerning the Ni-W binary system used in the calculations. The lack of reliable versions 

of the Fe-W and Ni-W phase diagrams limits the possibility of deriving an accurate version of 

the Fe-Ni-W phase diagram. 

. Table 1 

Investigations of the Fe-Ni-W Phase Relations, Structures and Thermodynamics 



Range Studied 

[1932Win] Melting, thermal and microscopic analysis Fe-Ni(0-45)W (mass%) 

[1965Dzy] Sintering at 1450˚C, EPMA, optical 

microscopy 

[1968Ega] Induction melting, Young’s modulus, 

electrical resistivity 

[1969Aga] Sintering / melting, microstructure, X-ray 

analysis, microhardness test 

3Fe-7Ni-W, 5Fe-5Ni-W, 7Fe-3Ni-W 

(mass%) 

Fe-75Ni-(0-5.1)W (at.%) 400-560˚C 

Fe-Ni-(0-40)W (mass%) at Fe:Ni = 

20:80, 30:70, 50:50, 60:40, 70:30, 

1350-800˚C 

[1969Yeg] Young’s modulus, saturation magnetization Fe-75Ni-(0.5-5.1)W 

[1970Gom] Neutron diffraction (Ni3Fe) 1–xWx, x = 0.01-0.05 

[1972Ive] X-ray of alloys after heating at 850, 530, 250˚C 

down to RT 

(19.9-24.6)Fe-Ni-(0.5-5.05)W (at.%) 

[1972Var] Sintering then quenching; X-ray analysis, 

optical microscopy, EPMA, magnetic 

properties 


Fe 2W-Ni 2W, at 950˚C 

[1977Mar] Sintering at 1470˚C, EPMA 2.4Fe-Ni-93W (at.%) 



MSIT 1 

9 

DOI: 10.1007/978-3-540-70890-2_16 

ß Springer 2009

10 16 

Fe–Ni–W 



[1979Edm] Sintering, optical microscopy, XRD, TEM, 

EPMA, SEM, AES 

[1980Min] Sintering, X-ray, microstructure, EPMA, 

electron microscopy 

[1981Ahn] Thermodynamic calculation incorporating the 

ternary regular solution model 

[1981Hen] Metallography, X-ray, DTA, tensile strength, 

bending strength tests 

[1982Ban] Arc melting, optical microscopy, XRD, 

microhardness, hardness, dilatometry, 

thermal analysis 


Range Studied 

3Fe-7Ni-W, 5Fe-5Ni-W (mass%) 

10(Fe+Ni)-W (mass%), Fe:Ni = 3:7 

Fe-Ni-W, 1540˚C 

1400˚C, 1000˚C, 850˚C Fe-Ni-(0-75)W 

(mass%) 

Fe-(5-20)Ni-(5-50)W (mass%) at 1300, 

1200, 800˚C 

[1982Buk] EPMA (MS-46 “Cameca”) (3-7)Fe-(7-3)Ni-W (mass%), 

1550-800˚C 

[1982Rom] The two-stage plastic-coal replica extraction 

method, electronic microscopy, XRD, EPMA 

Fe-Ni-90W (mass%) Fe:Ni = 3:7 ageing 

at 1000-800˚C 

[1983Du] EPA, SEM 3Fe-7Ni-W (mass%) sintered and heat 

treated in vacuum at 1500˚C 

[1984Mud] Sintering, TEM, EDX, scanning Auger 

spectrometry 

4.5Fe-4.5Ni-W (mass%) 

[1986Fer] Diffusion couples, optical microscopy, 

microprobe analysis, calculation 

[1986Woo] Optical microscopy, XRD, EMPA, chemical 

analysis 

[1986Zak1] Sintering, X-ray, optical microscopy, EPMA, 

Pirani and Alterthum methods, 

microhardness test 

[1986Zak2] Sintering, X-ray, optical microscopy, EMPA, 



xFe-(100–x)Ni-(0.1-50)W (mass%) 0.2 

≲ x ≲ 98.8, 1000-1400˚C 

1.5Fe-3.5Ni-95W, 21.4Fe-55.3Ni- 

23.4W at 1100˚C 

Fe-(0-10)Ni-W (mass%), stepped 

annealing: 1400˚C for 24 h, 1200 for 

26 h 

20(Fe+Ni)-W (mass%), stepped 

annealing: 1400˚C for 24 h, 1200˚C 

for 26 h 

[1987Kar] Induction melting, XRD, EPMA, metallography Fe-(0-30)Ni-(17-44)W (mass%) 

[1990Kra] Sintering, neutron irradiation, SEM, optical 

metallography, three point bending test 

1.6Fe-3.4Ni-W (mass%) 250˚C 

[1991Nik] Sintering, XRD, optical microscopy, EMPA, 



10 and 20 (Fe+Ni)-W (mass%) at 800 

(720 h), 575˚C (1680 h) 

[1992Nik] Sintering, XRD, optical microscopy 10 and 20 (Fe+Ni)-W (mass%) at 

1050˚C (720 h), 950˚C (1000 h) 

[1995Dje] Sintering, EPMA, Mössbauer spectroscopy, 

TEM, calculation 

Fe-16.3Ni-3W, 450˚C 



MSIT 1



[2001Fan] Mechanical alloying, XRD, optical microscopy, 

EDX, DTA 


Range Studied 

3Fe-7Ni-90W (mass%) 

[2001He] Mechanical alloying XRD, DSC, SEM, TEM (7.9-12.8)Fe-Ni-50W and (7-19.5)Fe- 

Ni-75W (at.%), 570-850˚C 

[2003Ron] Sintering, cold rolling, XRD, TEM, hardness 

test 

Fe-Ni-36W (mass%) Fe:Ni = 9:1; 7:3 at 

800˚C 

[2004Zha1] Mechanical alloying, XRD, TEM 6.1Fe-17.3Ni-76.6W (at.%) 

[2004Zha2] Mechanical alloying, XRD, TEM, DSC, EDX, 

SEM, inert gas fusion infrared analysis 

[2005Mar] Shock wave synthesis and consolidation, SEM, 

XRD, BSE, EPMA 

[2006Par] Solid state and liquid phase sintering, SEM, 

measuring of grain size 

[2006Zha] Mechanical alloying, XRD, TEM, DSC, EDX, 

SEM, an inert gas fusion infrared analysis 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


2.1Fe-4.9Ni-93W (mass%) sintering at 

1150 and 1280˚C 

10(Fe+Ni)-W (mass%) 300, 400, 800 

and 1000˚C 

5.1Fe-11.9Ni-W, 3.6Fe-8.4Ni-W, 2.1Fe- 

4.9Ni-W (mass%), 1200 to 1500˚C 

6.1Fe-13.2Ni-80.7W (at.%) from 200 to 

1400˚C 

Lattice 

Parameters 


γ, Fe1–x–yNixWy cF4 at x =0,0≤ y ≤ 0.146 

Fm3m at y =0,0≤ x ≤ 1 

Cu at y + x =1,y≤ 17.5 at 1495˚C [Mas2] 

a = 358 15Fe-3.5Ni-95W (mass%) [1986Woo] 

a = 359 at x = 4.6, y =93[1977Mar] 

(γFe) 

1394 - 912 

a = 364.67 at 915˚C [Mas2, V-C2] 

(Ni) 

< 1455 

a = 352.40 at 25˚C [Mas2] 

αδ, Fe1–x–yNixWy cI2 at y =0,0≤ x ≤ 0.046 (αFe) 

< 1548 Im3m 

W 

at y =0,0≤ x ≤ 0.038 (δFe) 

(δFe) 

1538 - 1394 

a = 293.15 [Mas2] 

(αFe) 

< 912 

a = 286.65 at 25˚C [Mas2] 



MSIT 1 

11 

DOI: 10.1007/978-3-540-70890-2_16 

ß Springer 2009

12 16 

Fe–Ni–W 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

(εFe) hP2 P63/ 

mmc 

Mg 

Lattice 

Parameters 


a = 246.8 

c = 396.0 

at 25˚C, 13 GPa [2008Kuz] 

(W) cI2 a =316.52 at 25˚C [Mas2] 

< 3422 Im3m dissolves 2.6 at.% Fe and about 

W 0.3 at.% Ni [Mas2, 1991Oka] 

a = 316 in a two-phase alloy of 3Fe-10Ni-90W (mass%) 

[1982Rom] 

γ’, FeNi3 cP4 a = 355.23 63-83 at.% Ni at 347˚C [2008Kuz] 

< 517 Pm3m a = 355.9 ± 0.1 24.6Fe-Ni-0.5W 

AuCu3 a = 356.9 ± 0.1 19.9Fe-Ni-5.05W (at.%) [1972Ive] 

γ’’, FeNi tP4 

P4/mmm 

AuCu 

a = 357.9 Metastable ordering temperature about 320˚C at 

51.2 at.% Ni [2008Kuz] 

λ, Fe2W hP12 - metastable phase at 33.3 at.% W [Mas2] 

≲ 1060 P63/mmc MgZn2 μ, Fe7W6 hR39 from 40.5 to about 42.1 at.% W [Mas2] 

1637 - 1190 R3m a = 475.7 Fe-3.3Ni-33.3W (at.%) 

Fe7W6 c = 258.2 

δ, (Fex Ni 1–x)W oP* 

P212121 0 ≤ x ≤ 1 at 950˚C [1992Nik] 

FeW MoNi from 48.5 to about 50.7 at.% W [Mas2] 

≲ 1215 dissolves about 8.5 mass% Ni at 1050˚C [1992Nik] 

NiW at about 50 at.% W [1991Oka] 

< 1068 a = 776 

b = 1248 

c = 710 

[V-C2] 

Ni4W tI10 at 19.4 at.% W [1991Oka] 

< 1002 I4/m a = 573.0 ± 0.1 [V-C2] 

MoNi4 c = 355.3 ± 0.1 

NiW2 tI96 at 66.7 at.% W [1991Oka] dissolves ≤0.5 mass% Fe 

< 1027 

- 

at 950, 800 and 575˚C [1991Nik, 1992Nik] 

a = 1040 

c = 1090 

[V-C2] 



MSIT 1

. Table 3 



Fe 


Ni W 

L+αδ Ð γ + μ 1465 U1 L 70.7 18.1 11.2 

αδ 75.1 12.8 12.09 

γ 74.5 16.2 9.3 

μ ~48 ~10 ~42 

L+μ Ð γ + (W) 1455 U2 L 54.7 33.6 11.7 

μ ~48 ~10 ~42 

γ 64.1 26.2 9.7 

(W) ~0.5 - ~99.5 

. Table 4 

Investigations of the Fe-Ni-W Materials Properties 


[1965Dzy] EPMA Grain growth 

[1968Ega] Young’s modulus, electrical resistivity Fe-75Ni-(0-5.1)W (at.%) alloys 

[1969Yeg] Young’s modulus, saturation 

magnetization 

Fe-75Ni-(0.5-5.1)W (at.%) alloys 

[1969Aga] Microhardness of γ phase measured using 

a PMT-3 instrument 

[1972Var] Curie temperature measured on alloys 

water quenched from 950˚C 

[1977Mar] Mechanical properties of the alloy 

sintered at 1470˚C 


10 and 20 mass% W with Ni:Fe = 40:60; 

30:70, after sintering at 1350˚C 

Change in Curie temperature of Fe 2W- 

Ni 2W alloy as a function of Ni content 

Ductility, hardness, fracture toughness 

Fe 2.4Ni 4.6W 93 alloy 

13 

[1979Edm] Un-notched Charpy test, AES The variations in toughness of the 3(5)Fe- 

7(5)Ni-W (mass%) alloys 

[1981Hen] Bend test Tensile and bending strength at 900˚C 

[1982Ban] Hardness Change in the alloy hardness with respect 

to W content at 1200˚C 

[1983Du] EPMA, SEM, microhardness tensile test Variation of ultimate tensile and yield 

strength with strain rate of 3Fe-7Ni-W 

(mass%) alloy 

[1986Woo] Sintering, optical microscopy, XRD, EMPA, 

uniaxial compression test 

Density, hardness, stress/strain curves 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_16 

ß Springer 2009

14 16 

Fe–Ni–W 



[1990Kra] Neutron irradiation test at 250-300˚C in 

the reactors FRJ2 and HFR fluxes of up to 

56·10 24 neutrons μ –2 . SEM, metallography 

analysis 

[1991Nik] Microhardness of (W) phase of the 

Fe-Ni-W alloys quenched from 800˚C 

[2000Ryu] Density, yield strength, elongation impact 

energy, size of W particles, matrix volume 

fraction, W/W contiguity. Tensile test 

[2000Min] Tensile test, microhardness, electrical 

resistance, SEM, microstructure, X-ray 

[2001Fan] Mechanical alloying of the 3Fe-7Ni-90W 

(mass%) mixture, XRD, optical 

microscopy, EDX, DTA 

[2002Ekb] Deformation by elongation in a tensile 

testing machine and by isostatic 

extrusion, XRD, microhardness, HVEM, 

stereographic photography 

[2003Ron] Hardness (Rockwell A) measured at 

different ageing times at 800˚C 

[2003Ant] Melt penetration test, SEM, TEM, hardness 

measurement 

[2004Bol] Dilatometry, density, solid volume 

fraction and contiguity measured with 

image analysis software 

[2004Zha2] Mechanical alloying, XRD, TEM, DSC, EDX, 

SEM, Archimedes water immersion 

method 

[2005Mar] SEM, EDS, X-ray, quantitative image 

analysis, microhardness, density, grain 

size 

Ductile-brittle transition temperature of 

1.63Fe-3.52Ni-W (mass%) alloy 

Variation of microhardness of (W) phase 

of the alloys along the 90 mass% W 

section 

of 1.4Fe-5.6Ni-93W (mass%) alloy 

mechanically alloyed, sintered at 1300˚C 

and subsequently liquid phase sintered at 

1470˚C and water quenched 

Effect of deformation by rolling on 

hardness and electrical resistance of the 

3Fe-7Ni-90W (mass%) composite slowly 

and rapidly cooled 

W particle size 

Variation of W in γ phase with 

temperature 

Dislocation density, microhardness 

The variation of hardness of the Fe-Ni- 

36W (mass%) alloys where Fe:Ni = 1:9 

and 3:7 

Penetration rate, W solid exposed to 

24Fe-43Ni-33W (mass%) melt 

Distortion, grain size, grain growth rate 

of (Fe,Ni)1–xWx, x = 83, 88, 93 mass%; 

Fe:Ni = 3:7 

Density, W grain size in 2.1Fe-4.9Ni-93W 

(mass%) composition after sintering at 


Grain size, density, consolidation of 

compacts by shock synthesis 



MSIT 1

. Fig. 1 

Fe-Ni-W. Reaction scheme 



MSIT 1 


15 

DOI: 10.1007/978-3-540-70890-2_16 

ß Springer 2009

16 16 

Fe–Ni–W 

. Fig. 2 

Fe-Ni-W. Liquidus surface projection 



MSIT 1

. Fig. 3 

Fe-Ni-W. Solidus surface projection 



MSIT 1 


17 

DOI: 10.1007/978-3-540-70890-2_16 

ß Springer 2009

18 16 

Fe–Ni–W 

. Fig. 4 

Fe-Ni-W. Isothermal section at 1400˚C 



MSIT 1

. Fig. 5 

Fe-Ni-W. Fragment of the isothermal section at 1050˚C 



MSIT 1 


19 

DOI: 10.1007/978-3-540-70890-2_16 

ß Springer 2009

20 16 

Fe–Ni–W 

. Fig. 6 

Fe-Ni-W. Fragment of the isothermal section at 950˚C 



MSIT 1

. Fig. 7 

Fe-Ni-W. Isothermal section at 800˚C 



MSIT 1 


21 

DOI: 10.1007/978-3-540-70890-2_16 

ß Springer 2009

22 16 

Fe–Ni–W 

. Fig. 8 

Fe-Ni-W. Isopleth at 90 mass% W, plotted in at.% 



MSIT 1

. Fig. 9 

Fe-Ni-W. Isopleth at 14.3 at.% W 



MSIT 1 


23 

DOI: 10.1007/978-3-540-70890-2_16 

ß Springer 2009

24 16 

Fe–Ni–W 

References 

[1932Win] Winkler, K., Vogel, R., “The Ternary System of the Iron-Nickel-Tungsten” (in German), Arch. 

Eisenhuettenwes., 6, 165–172 (1932) (Experimental, Morphology, Phase Diagram, Phase Relations, 


[1949Jae] Jaenecke, E., “Fe-Ni-W” (in German) in “Kurzgefasstes Handbuch aller Legierungen”, Winter Verlag, 

Heidelberg, 635–636 (1949) (Review, Phase Diagram, Phase Relations, 2) 

[1961Eng] English, J.J., “Binary and Ternary Phase Diagrams of Columbium, Molybdenum, Tantalum and Tungsten”, 

Defense Metals Information Center, Batelle Memorial Institute, Columbus 1, Ohio, 152, 204–206 (1961) 


[1965Dzy] Dzykovich, I.Ya., Makarova, R.V., Teodorovich, O.K., Frantsevich, I.N., “Distribution of Elements 

During the Formation of Sintered Alloys of the System W-Ni-Fe”, Sov. Powder Metall. Met. Ceram., 8, 

655–660 (1965), translated from Poroshk. Metall., (8), 62–69, (1965) (Experimental, Phase Relations, 


[1968Ega] Eganyan, I.L., Selissky, Y.P., “Investigation of the Effects of Atomic Ordering in Ternary Solid Solutions 

on the Basis of Ni 3Fe Alloyed by VI Group Elements - Chromium, Molybdenum, Tungsten” (in 

Russian), Izv. Akad. Nauk Ukr. SSR, Metallofizika, (20), 100–104 (1968) (Crys. Structure, Experimental, 

Phase Relations, Mechan. Prop., Thermodyn., 3) 

[1969Aga] Agababova, V.M., Chaporova, I.N., “Boundary of the Monophasic γ-Solid Solution Region in the 

Ternary System W-Ni-Fe”, Sov. Powder Metall. Met. Ceram., (7), 571–576 (1969), translated from 

Poroshk. Metallurg., (7), 65–72, (1969) (Experimental, Phase Relations, Mechan. Prop., 2) 

[1969Yeg] Yeganyan, I.L., Selisskiy, Ya.P., “A Study of the Effects of Atomic Ordering in Ternary Solid So1utions of 

Cr, Mo, and W in Ni 3Fe.”, Phys. Met. Metallogr., 27(2), 18–25 (1969), translated from Fizika Metallov i 

Metalloved., 27(2), 210–218 (1969) (Experimental, Thermodyn., 8) 

[1970Gom] Goman’kov, V.I., Puzey, I.M., Mal’tsev, E.I., “Effect of Alloying Elements on the Superstructure of 

Ni 3Fe” (in Russian), Dokl. Akad. Nauk SSSR, 194(2), 309–311 (1970) (Crys. Structure, Experimental, 6) 

[1971Win] Winslow, F.R., “The Iron-Nickel-Tungsten Phase Diagram”, U.S. At. Energy Comm. Pubn, Y-1758 (1971) 

(Phase Diagram, Phase Relations, Review) as quoted in [1988Ray] 

[1972Ive] Iveronova, V.I., Katsnelson, A.A., Silonov, V.M., “On Atomic Ordering in the System Nickel-Iron- 

Tungsten”, Phys. Met. Metallogr., (3), 77–81 (1972), translated from Fiz. Met. Metalloved., (3), 535–539 


[1972Var] Varli, K.V., Dyakonova, N.P., Korneva, O.S., Umansky, Ya.S., “Investigation of Some Alloys of the 

System Fe-Ni-W” (in Russian), Izv. Vyssh. Ucheb. Zaved., Chern. Met., (1), 120–123 (1972) (Experimental, 

Phase Relations, Crys. Structure, Morphology, Mechan. Prop., Magn. Prop., 5) 

[1977Mar] Margaria, T., Allibert, C., Driole, J., “Structural Characterisation of W-Base Sintered Alloys: W-Ni -Fe, 

W-Ni-Co and W-Ni-Cr” (in French), J. Less-Common Met., 53, 85–95 (1977) (Crys. Structure, Experimental, 

Mechan. Prop., Morphology, Phase Relations, 6) 

[1979Edm] Edmonds, D.V., Jones, P.N., “Interfacial Embrittlement in Liquid-Phase Sintered Tungsten Heavy 

Alloys”, Metall. Trans. A, 10A, 289–295 (1979) (Crys. Structure, Experimental, Mechan. Prop., Morphology, 


[1980Min] Minakova, R.V., Storchak, N.A., Verkhovodov, P.A., Bazhenova, L.G., Poltoratskaya, V.L., “Some 

Structural Characteristics of the Binder Phase of W-Ni-Fe Alloys”, Sov. Powder Metall. Met. Ceram., 

(12), 842–846 (1980), translated from Poroshk. Metall., (12), 45–50 (1980) (Experimental, Crys. 

Structure, Morphology, Phase Relations, 16) 

[1981Ahn] Ahn, S.T., “Thermodynamic Calculation of W-Ni-Fe Ternary Phase Diagram at 1540˚C”, J. Korean Inst. 

Met., 19(11), 947–951 (1981) (Calculation, Phase Diagram, Phase Relations, Thermodyn., 12) 

[1981Hen] Henig, E.T., Hofman, H., Petzow, G., “The Constitution of W-Fe-Ni alloys and its Influence on 

its Mechanical Properties” (in German) in “Plansee Seminar”, Ortner, H.M., (Ed.), Reutte, Austria, 

Metallwerk Plansee, 335–359 (1981) (Experimental, Phase Diagram, Phase Relations, Mechan. 

Prop., 63) 

[1981Ray] Raynor, G.V., Rivlin, V.G., “Critical Evaluation of Constitutions of Certain Ternary Alloys Containing 

Iron, Tungsten and a Third Metal”, Int. Met. Rev., 26, 213–249 (1981) (Crys. Structure, Phase Diagram, 


[1982Ban] Bannykh, O.A., Kurbatkina, O., Prokofiev, D.J., “Phase Diagram for Fe-Ni-W System”, Izv. Akad. Nauk 

SSSR, Met., (6), 197–203 (1982) (Experimental, Phase Diagram, Phase Relations, Mechan. Prop., 5) 



MSIT 1


25 

[1982Buk] Bukatov, V.G., Romashov, V.M., Gostev, Yu.V., “Effect of Heat Treatment on the Distribution of 

Elements in the Phase Components of W-Ni-Fe Alloys” (in Russian), Poroshk. Metall., (10), 38–41 

(1982) (Experimental, Crys. Structure, Phase Relations, 6) 

[1982Rom] Romashov, V.M., Kurganov, G.V., Vlasov, E.E., “Precipitated Particles in the Binder Phase of W-Ni-Fe 

Alloys”, Sov. Powder Metall. Met. Ceram., (12), 952–953 (1982), translated from Poroshk. Metall., (12), 

55–56 (1982) (Experimental, Crys. Structure, Morphology, Phase Relations, 5) 

[1983Du] Du, J., “Strain and Fracture of Liquid Phase Sintered Alloy 90W-7Ni-3Fe”, Acta Metall. Sin. (China), 19 

(4), A354-A358 (1983) (Experimental, Phase Relations, Morphology, Mechan. Prop., 11) 

[1984Mud] Muddle, B.C., “Interphase Boundary Precipitation in Liquid Phase Sintered W-Ni-Fe and W-Ni-Cu 

Alloys”, Metall. Trans. A, 15A, 1089–1098 (1984) (Crys. Structure, Morphology, Experimental, 34) 

[1986Fer] Fernandez-Guillermet, A., Ostlund, L., “Experimental and Theoretical Study of the Phase Equilibria in 

the Fe-Ni-W System”, Metall. Trans. A, 17A, 1809–1823 (1986) (Experimental, Calculation, Thermodyn., 


[1986Woo] Woodward, R.L., McDonald, I.G., Gunner, A., “Comparative Structure and Physical Properties of 

W-Ni-Fe Alloys Containing 95 and 25 wt.% Tungsten”, J. Mater. Sci. Lett., 5(4), 413–414 (1986) 

(Experimental, Phase Relations, Morphology, Crys. Structure, Mechan. Prop., 3) 

[1986Zak1] Zakharov, A.M., Parshikov, V.G., Vodop’yanova, L.S., Novozhonova, V.A., “Phase Equilibria in Alloys 

of the W-Fe-Co-Ni System. I. Alloys Containing 10% (Fe+Co+Ni) at 1400-1200˚C”, Sov. Powder Metall. 

Met. Ceram., (4), 313–316 (1986), translated from Poroshk. Metall., (4), 60–64 (1986) (Experimental, 


[1986Zak2] Zakharov, A.M., Parshikov, V.G., Vodopyanova, L.S., Godovannaya, E.B., “Phase Equilibria In 

Tungsten-Iron-Cobalt-Nickel Alloys Containing 20% Iron + Cobalt + Nickel at 1400-1200˚C” (in 

Russian), Izv. Vyss. Uchebn. Zaved., Tsvetn. Metall., (5), 75–79 (1986) (Assessment, Crys. Structure, 

Phase Diagram, Mechan. Prop., Experimental, 9) 

[1987Kar] Kardonskii, V.M., “Effect of Ni on the Structure and Phase Composition of Fe-W Alloys” (in Russian), 

Fiz. Met. Metalloved., 63(1), 133–136 (1987) (Experimental, Crys. Structure, Phase Relations, Morphology, 

4) 

[1988Ray] Raynor, G.V., Rivlin, V.G., “Fe-Ni-W” in “Phase Equilibria in Iron Ternary Alloys”, Inst. Metals, London, 

4, 441–452 (1988) (Crys. Structure, Phase Diagram, Phase Relations, Review, 7) 

[1990Kra] Krautwasser, P., Derz, H., Kny, E., “Influence of Fast Neutron Fluence on the Ductile-Brittle Transition 

Temperature of Tungsten, W-10Re, and W-3.4Ni-1.6Fe”, High Temp.-High Pressures, 22(1), 25–32 

(1990) (Experimental, Morphology, Mechan. Prop., 8) 

[1991Nik] Nikol’skii, A.V., Zakharov, A.M., Parshikov, V.G., Vodop’yanova, L.S., “Phase Equilibria in the 

Tungsten-rich Field of the W-Fe-Ni System in the 800-575˚C”, Sov. Powder Metall. Met. Ceram., (8), 

675–680 (1991), translated from Poroshk. Metall., (8), 61–67 (1991) (Crys. Structure, Experimental, 

Phase Diagram, Phys. Prop., Phase Relations, 11) 

[1991Oka] Okamoto, H., “Ni-W (Nickel-Tungsten)”, J. Phase Equilib., 12(6), (1991) (Phase Diagram, Phase 


[1992Nik] Nikosky, A.V., Zakharov, A.M., “The W-Fe-Ni Systems at 1050-950˚C and 10-20% (Fe + Ni)”, Russ. 

Metall., (5), 213–217 (1992) translated from Izv. Akad. Nauk, Met., (5), 220–223 (1992) (Crys. Structure, 

Experimental, Phase Diagram, Phys. Prop., 15) 

[1994Rag] Raghavan, V., “Fe-Ni-W (Iron-Nickel-Tungsten)”, J. Phase Equilib., 15(6), 631–632 (1994) (Phase 


[1995Dje] Djega-Mariadassou, C., Bessais, L., Servant, C., “Nanocrystalline Precipitates Formed by Aging of BCC 

Disordered Fe-Ni-Mo Alloys”, Phys. Rev. B: Condens. Matter, 51(14), 8830–8840 (1995) (Crys. Structure, 

Experimental, Phys. Prop., 16) 

[2000Min] Minakova, R.V., Pachek, A.P., Kryachko, L.A., Kresanova, A.P., Zatovskii, V.G., “Texture Formation in 

the Cold Rolling of Pseudo-Alloys”, Powder Metall., Met. Ceram., 39, 78–84 (2000) (Crys. Structure, 

Phase Relations, Electr. Prop., Experimental, Mechan. Prop., 5) 

[2000Ryu] Ryu, H.J., Hohg, S.H., “Effects of Sintering Conditions on Mechanical Properties of Mechanically 

Alloyed Tungsten Heavy Alloys”, Key Eng. Mater., 183–187, 1291–1296 (2000) (Experimental, Morphology, 

Kinetics, Mechan. Prop., 15) 

[2001Fan] Fan, J., Huang, B., Qu, X., Zou, Zh., “Thermal Stability, Grain Growth and Structure Changes of 

Mechanically Alloyed W-Ni-Fe Composite During Annealing”, Inter. J. Ref. Met. Hard Mater., 19(2), 

73–77 (2001) (Experimental, Phase Relations, Morphology, 17) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_16 

ß Springer 2009

26 16 

Fe–Ni–W 

[2001He] He, Z., Courtney, T.H., “Crystallization and Thermal Stability of Mechanically Alloyed W-Ni-Fe 

Noncrystalline Materials”, Mater. Sci. Eng. A, 315(1-2), 166–173 (2001) (Experimental, Phys. Prop., 


[2002Ekb] Ekbom, L., Antonsson, T., “Tungsten Heavy Alloy: Deformation Texture and Recrystallization of 

Tungsten Particles”, Inter. J. Refract. Met. Hard Mater., 20, 375–379 (2002) (Experimental, Morphology, 


[2003Ant] Antonsson, T., Ekbom, L., Eliasson, A., Fredriksson, H., “Liquid Ni-Fe Penetration and Recrystallisation 

in Tungsten”, Int. J. Refract. Met. Hard Mater., 21, 159–170 (2003) (Experimental, Kinetics, 

Transport Phenomena, 30) 

[2003Ron] Ronghua, L., Jihua, H., Sheng, Y., Jun, Zh., “Strain Aging Precipitation Behavior of β Phase in W-Ni-Fe 

Ternary System”, J. Mater. Sci. Lett., 22(5), 397–398 (2003) (Experimental, Phase Relations, Mechan. 

Prop., Morphology, 7) 

[2004Bol] Bollina, R., German, R.M., “Heating Rate Effects on Microstructural Properties of Liquid Phase 

Sintered Tungsten Heavy Alloys”, Int. J. Refract. Met. Hard Mater., 22, 117–127 (2004) (Experimental, 


[2004Zha1] Zhang, Zh-W., Zhou, J.-E., Xi, Sh-Q., Ran, G., Li, P.-L., Zhang, W.-X., “Formation of Crystalline and 

Amorphous Solid Solutions of W-Ni-Fe Powder During Mechanical Alloying”, J. Alloys Compd., 370, 

186–191 (2004) (Experimental, Morphology, Phase Relations, Calculation, Thermodyn., Kinetics, 35) 

[2004Zha2] Zhang, Z.-W., Zhou, J.-E., Xi, S.-Q., Ran, G., Li, P.-L., “Phase Transformation and Thermal Stability of 

Mechanically Alloyed W-Ni-Fe Composite Materials”, Mater. Sci. Eng. A, 379A, 148–153 (2004) (Crys. 

Structure, Experimental, Kinetics, Morphology, 21) 

[2005Mar] Marquis, F.D.S., Mahajan, A., Mamalis, A.G., “Shock Synthesis and Densification of Tungsten Based 

Heavy Alloys”, J. Mat. Proc. Tech., 161, 113–120 (2005) (Crys. Structure, Experimental, Mechan. Prop., 

Morphology, Phase Relations, Phys. Prop., 14) 

[2006Par] Park, S.J., Martin, J.M., Guo, J.F., Jonson, J.L., German, R.M., “Grain Growth Behaviour of Tungsten 

Heavy Alloys Based on the Master Sintering Curve Concept”, Metall. Mater. Trans. A, 37A, 3337–3346 

(2006) (Experimental, Calculation, Thermodyn., 63) 

[2006Zha] Zhang, Z.W., Chen, G.L., Chen, G., Zhou, J.E., “Amorphization and Thermal Stability of Mechanical 

Alloyed W-Ni-Fe”, Mater. Sci. Eng. A, 417A, 34–39 (2006) (Experimental, Phys. Prop., 28) 

[2007Lee] Lee, S.-B., Rickman, J.M., Rollett, A.D., “Three-Dimensional Simulation of Isotropic Coarsening in 

Liquid Phase Sintering I: A Model”, Acta Mater., 55(2), 615–626 (2007) (Crys. Structure, Experimental, 

Kinetics, Mechan. Prop., Thermodyn., 36) 





(1990) 





MSIT 1

Iron – Nickel – Zinc 


Nataliya Bochvar, Lazar Rokhlin 

Introduction 

The Fe-Ni-Zn phase diagram is of a great importance for galvanizing steels containing Si. The 

various alloying elements are added into the molten Zn bath in hot galvanizing. The technology 

of the hot bath galvanizing is widely used for handling most steels. But galvanizing the Si 

containing steels remains a technical problem. In general, galvanizing Si in steel gives rise to a 

thin, dull grey coating with poor adhesion to the steel substrate. The use of Ni as additive in Zn 

bath may decrease the detrimental effects of the silicon. However, the Ni addition to a 

galvanizing bath frequently introduces a new type of defect, the entrapment of so-called 

“floating dross” particles in the coating. A galvanizing bath is always saturated with Fe, as Fe 

constantly dissolves from the galvanized steel articles, and bath essentially becomes a Fe-Ni-Zn 

ternary system. Simultaneously, the intermetallic compounds forming in the bath, commonly 

referred to as dross particles. Therefore, the study of the Fe-Ni-Zn phase diagram represents a 

practical interest. 

The Fe-Ni-Zn phase diagram was investigated in a number of works and summarized in 

[1987Bha, 2003Rag, 2007Rag] reviews. 

A ternary phase of the assumed formula Fe 6Ni 5Zn 89 was reported by [1957Ray]. 

However, the ternary phase was shown by the later works [1989Per, 1992Reu, 1994Per, 

1999Reu] to be an extensive solid solution of the cubic structure closely related to that of 

Fe 11Zn 40. 

The nature of phases and phase relations were studied experimentally in the Zn rich part of 

the Fe-Ni-Zn system at various temperatures at 700˚C [1940Glu], 370˚C [1957Ray], 450˚C 

[1993Che, 1989Per, 1992Reu, 1994Per, 1999Reu, 2000Tan] and 560˚C [2005Pen]. Using the 

Calphad method, [2001Tan] calculated the phase boundaries in the Zn rich corner of the 

system at 450, 465 and 480˚C, as [1994Per] calculated those at 450 and 480˚C. The experimental 

studies are summarized in Table 1. 

The phase equilibria close to the Zn corner which depict the liquid phase boundary 

in equilibrium with solid phases are of importance for galvanizing process. They allow 

determining the constitution of floating dross particles at the galvanizing temperatures. 

However, there is difference in the description of the equilibria close to the Zn corner 

[1994Per, 1995Per, 1995Tan, 1996Tan] which will be debated below in the section “Isothermal 

Sections”. 


Fe–Ni–Zn 17 

1 

The Fe-Zn, Fe-Ni and Ni-Zn binary phase diagrams are accepted from [2008Per], [2008Kuz] 

and [2008Leb], respectively. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_17 

ß Springer 2009

2 17 

Fe–Ni–Zn 


A ternary phase of the approximate “formula” of Fe 6Ni 5Zn 89 has been reported by [1957Ray] 

to exist in the Zn rich corner of the Fe-Ni-Zn phase diagram. Using microprobe analysis, 

[1994Lid] gave an approximate composition as FeNiZn 18 and its formula as (Fe,Ni)Zn 6.5. 

However, no evidence showing conclusively structurally different τ from the Γ2 phase does 

exist. On the other hand, [1989Per, 1992Reu, 1994Per, 1999Reu] established the existence of a 

continuous series of solid solution between Γ 2 phase and Zn 89Fe 6Ni 5 -dross composition at 

450˚C. This conclusion was made after examination of the isolated ternary phase annealed 

under vacuum at 450˚C by X-ray diffraction method. Its pattern was the same as that of the Γ 2 

compound and could be indexed into the same fcc crystal lattice system [1989Per]. Comparing 

X-ray diffraction results with Mössbauer data, [1999Reu] supposed that Ni atoms occupied Zn 

position in the Fe 6Ni 5Zn 89 phase. Also, [1994Lid] proposed that the crystal structure of (Fe, 

Ni)Zn6.5 single crystal examined by X-ray analysis is closely related to the Γ2 phase with 

the small difference in site occupation. Both structures may be considered as superstructures 

of γ-brass. Although [2001Tan, 2005Pen] called it a true ternary phase, all their results show 

only that this is an extended solid solution based on the Γ 2 phase. Structural investigations of 

[2005Pen] did not confirm difference of crystal structures of Γ 2 and (Fe,Ni)Zn 6.5. The fact that 

at 560˚C [2005Pen] observed it only in the ternary system, while it does not exist in the binary 

is no evidence for being a true ternary phase. An appearance of a binary phase in the ternary 

region at a temperature where the binary phase does not exist itself is quite common case in 

ternary systems. 

In the present evaluation the “(Fe,Ni)Zn6.5 phase” is accepted to be a part of an extended 

solid solution based on the Γ 2 phase. 

The solubility of Ni in the δ 1 and ζ phases of the Fe-Zn system amounts up to 2 and 1 at.%, 

respectively, and the Fe solubility in the δ phase of the Ni-Zn system is less than 0.5 at.% at 

450˚C [1989Per]. The solid phases of the Fe-Ni-Zn system are listed in Table 2. 

The phases Fe 3Zn 10 and γ of the Ni-Zn system form a continuous solid solution (Γ 1). 


Based on the metallographic examination of the annealed at 370˚C Zn rich alloys with 0.5Fe- 

1.5Ni and 0.75Fe-1.25Ni (mass%), [1957Ray] proposed the ternary compound Fe 6Ni 5Zn 89 (in 

fact Γ 2) to be formed by a peritectic reaction from the liquid and ζ phases. However, such a 

peritectic reaction is not possible because according to [2005Pen] Γ 2 is stable at the temperature 

of 560˚C that is higher than that of the ζ phase formation. Taking into account the phase 

equilibria at 560˚C and a schematic liquidus surface (Fig. 1), an invariant four-phase reaction 

of the Γ2 formation L + δ1 + Γ1 Ð Γ2 (560


[1957Ray] presented a schematic surface of the primary crystallization fields in the Zn rich 

corner up to 3 mass% Fe and 3 mass% Ni with the wide surface of Γ 2 and five narrow surfaces 

of (Zn), ζ, δ 1, δ, γ. The schematic surface of the primary crystallization was presented without 

possible directions of the monovariant lines (Fig. 1 is redrawn in at.% and adjusted to the 

accepted binary systems). 



3 

There are two discrepancies in the description of the liquid phase boundaries and phases in 

equilibrium with liquid in the Zn rich alloys at the ordinary temperature of the galvanizing 

process 450˚C. [1995Per] believed for the liquid in equilibrium with ζ a constant solubility of 

Fe (0.039 mass%) which was independent from the Ni content in the liquid. On the other 

hand, [1995Tan, 1996Tan] based on the [1993Che] results and own experiments indicated the 

Fe solubility to decrease from 0.029 mass% at 0% Ni to 0.021 mass% at 0.061 mass% Ni for the 

equilibrium of the liquid and ζ phases. A further increase in Ni to 0.10 mass% lowered the Fe 

solubility limit to 0.016 mass%. These results are confirmed by [2000Tan] and are accepted in 

the [2003Rag] review and in this assessment. 

The other difference concerns the equilibrium of δ 1 with liquid at 450˚C. Interpreting the 

[1993Che]’s results, [1995Tan, 1996Tan] proposed an equilibrium of the δ 1 phase with the 

molten Zn, whereas [1993Che] gave the equilibria only between L and ζ;L,ζ and Γ2; L and Γ2. 

On the other hand, [1995Per] indicated that no experimental evidence existed for the 

equilibrium of the δ 1 phase with the liquid in the Zn rich corner. Only one layer (ζ) ortwo 

layers (ζ + Γ 2) were found between the δ 1 phase and the Zn rich liquid in the galvanizing bath. 

The ζ - Γ 2 equilibrium prohibited any tie line between δ and the liquid phase. These data 

agreed with the phase equilibria at 370˚C [1957Ray]. New results of [2001Tan] also are in line 

with those of [1994Per]. 

The isothermal sections at 450˚C shown in Figs. 2 and 3 after [2003Rag] who redrawn 

them from [1989Per, 1994Per] (Fig. 2) and from [2001Tan] (Fig. 3). Here they are slightly 

modified to correspond with the accepted binary systems. The difference between the two 

sections is that in Fig. 2 a continuous solid solution Γ 2 exists, whereas in Fig. 3 the solution is 

broken and Γ 2 appears ones again (Γ 2’) in the ternary region. [2003Rag] proposes that this 

result could be interpreted as a miscibility gap existing at 450˚C rather than the existence of a 

true ternary compound. The continuous solid solution is apparently metastable (Fig. 2) and 

breaks up into two phases of different compositions (Fig. 3) with the much-longer annealing 

times (15 days) used by [2001Tan], as compared with 30 min used by [1989Per, 1995Per]. 

However, [2001Tan] believes that in the Zn rich corner the ternary phase with a not fixed 

stoichiometry exists indeed and has an appreciable homogeneity range. The limits of its 

homogeneity range at 450˚C change from 2.1 to 8.7 at.% Ni and from 14.1 to 4.1 at.% Fe, 

respectively. The phases being in equilibrium with molten Zn are identical in [1989Per] and 

[2001Tan]: ζ, Γ 2 (or T) and δ. 

Figure 4 shows a partial isothermal section at 560˚C based on [2005Pen] and adjusted to 

the accepted binary diagrams. The Γ 2 phase has a homogeneity range from 3.2 to 9.1 at.% Ni 

and from 10.8 to 4.1 at.% Fe, respectively. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_17 

ß Springer 2009

4 17 

Fe–Ni–Zn 

The Fe solubility in the liquid Zn phase is much higher at 560˚C then at 450˚C, and 

decreases substantially with increasing Ni content in the liquid. In contrast, the reduction of 

the Fe solubility in the liquid Zn with Ni addition is relatively insignificant at 450˚C. 

[2000Tan] constructed experimentally the liquid-phase boundaries of the Fe solubility 

at 450, 465 and 480˚C and [1993Che] constructed those at 450˚C. [1993Che] found that for 

Ni 0.06 mass% in the bath a second phase Γ 2, containing ~3 mass% Ni, started to appear. 

For Ni ≈ (0.06 to 0.09) mass% in the bath the ζ and Γ 2 phases could co-exist. 

[2001Tan] presented a thermodynamic assessment of the Zn rich corner of the Fe-Ni-Zn 

phase diagram, deriving the ternary interaction parameters and calculated isothermal sections 

at 450, 465 and 480˚C. They are presented in Fig. 5. The experimental results of [1993Che, 

2000Tan] agreed with the calculation very good. The tie triangles (broken lines in Fig. 5) were 

added by [2003Rag] approximately and did not take into account the possible presence of the 

δ phase in equilibrium with liquid above 450˚C. 


A thermodynamic description of dross formation in the Ni-Zn bath with galvanizing steel was 

made by [1994Per]. The Gibbs energies of the alloy Fe 0.06Ni 0.89Zn 0.05 was Δ fG = –6638 J·mol –1 

at 450˚ and ΔfG= –6329 J·mol –1 at 480˚C. The change of the Gibbs energies with the 

temperature could be calculated by the equation: ΔfG = –1036 – 8.5407 T J·mol –1 . 


Using the Mössbauer effect, [1991Doo] studied the microscopic magnetic properties of cubic 

microwave ferrite (Zn 0.41Ni 0.59)Fe 2O 4. 

Miscellaneous 

[1997Ana] investigated the stability of the Fe-Ni-Zn coatings during heat treatments up to 

400˚C, using microscopic studies. They established the electrocatalytic activity of Fe-Ni-Zn codeposits 

to depend on electrodeposition and surface topography parameters. 

Studying the X-ray magnetic circular dichroism, the Fe-ion distribution in crystal lattice of 

the spinel ferrite Fe2.01Ni0.48Zn0.51 was established [2002Pat]. 

[2005Hwa] synthesized the ferrite with the chemical formula of Fe2Ni0.5Zn0.5O4 and 

investigated the homogeneity range of the precursor and reproducibility of the as-synthesized 

product by elementary analysis and other analyses. The reaction mechanism was also studied 

using thermal and escaping gas analyses. 



MSIT 1

. Table 1 

Investigations of the Fe-Ni-Zn Phase Relations, Structures and Thermodynamics 


[1940Glu] Diffusion experiment, Fe-Ni alloys 

dissolved in liquid Zn bath. 

X-ray and chemical analyses, 

microstructure examination, hardness 

measurement 

[1957Ray] Annealing of cast alloys at 370˚C for 85 

days followed by quenching or cooling 

slowly. 

Metallographic examination, X-ray 

diffraction, chemical analysis 

[1989Per] Diffusion couples obtained with Fe-Ni 

alloys at galvanizing in (Zn+0.1 at.% Ni) 

bath at 450˚C. 

Electron microprobe analysis, X-ray 

diffraction 

[1992Reu] Diffusion layers after Fe galvanized in Ni- 

Zn bath at 450˚C for 8 min. 

SEM, determination of the fractal 

dimension 

[1993Che] Ni was dissolved in Zn molten in low 

carbon steel bath at 450˚C for 270 h. Dross 

was periodically removed from coating of 

bath and then remelted in a graphite 

crucible in electrical furnace at 450˚C for 

5 h and quenched in water. 

Microstructure examination, XRD and EDS 

analyses 

[1994Lid] The mixture from Fe and Zn was heated in 

stainless steel ampoules, sealed under Ar, 

heated to 1300 K in 2 h and cooled to 

room temperature at a rate of 30 K/h. 

X-ray and electron microprobe analyses 

[1994Per] Fe was galvanized in a (Zn-0.1 mass% Ni) 

bath at 450 and 480˚C for 30 min. 

Electron microprobe analysis, 

thermodynamic calculation 

[1999Reu] δ 1(FeZn 10) phase was obtained by 

mechanical alloying and phase Zn 89Fe 6Ni 5 

was obtained in galvanizing bath. XRD 

method, Mössbauer spectra 



MSIT 1 



Studied 

Composition of Fe-Ni alloys changing 

across 10 mass%. Phase composition of 

diffusion layers. 

Zn rich alloys with Fe and Ni up to 3 mass%. 

Isothermal section at 370˚C and surface of 

primary separation. 

Zn rich alloys (Zn>80 at.%). Crystal 

structure and lattice parameter of the Γ 2 

phase, isothermal section at 450˚C 

Ni content in Ni-Zn bath from 0 to 0.13 

mass%. Determination of phases in 

equilibrium with liquid in diffusion layers 

in dependence from Ni content 

Ni content from 0.024 to 0.102 mass% and 

Fe content from 0.024 to 0.016 mass%. 

Structure and composition of dross 

phases. Isothermal section of the Zncorner 

at 450˚C 

Crystal structure and lattice parameter of 

Zn6.5(FeNi) single crystal 

Zn rich corner. Determination of phases in 

equilibrium with liquid. Calculation of 

liquidus at 450 and 480˚C 

Crystal structures of δ 1(FeZn 10) and 

Fe 6Ni 5Zn 89 

5 

DOI: 10.1007/978-3-540-70890-2_17 

ß Springer 2009

6 17 

Fe–Ni–Zn 



[2000Tan] Zn bath with the submerged samples was 

heated at 600˚C for 3 h, then at 450, 465 

and 480˚C for 40h and quenched in water. 

Microstructure examination, atomic 

absorption spectrophotometry 

[2001Tan] The powder of pure Fe, Ni, Zn were sealed 

in an evacuated quartz tube, heated to 

above its estimated liquidus temperature, 

kept for 2 days and quenched in water. 

Optical and scanning electron 

microscopes and SEM-EDS analysis. 

Thermodynamic calculation 

[2005Pen] The powders of pure Fe, Ni, Zn were 

sealed in an evacuated quartz tube, 

heated to above its estimated liquidus 

temperature, kept for 2 days and 

quenched in water. Then the annealing at 

560˚C for 21 days and quenching in water. 

SEM, EDS, X-ray diffraction 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Studied 

Liquid phase boundaries in the Zn rich 

region at 450, 465 and 480˚C 

Zn rich alloys from 2 to 16 at.% Fe and 

from 2 to 11 at.% Ni. Calculation of the 

isothermal sections at 450 and 480˚C and 

liquidus at 450˚C 

Zn rich alloys from 2 to 16 at.% Fe and 

from 2 to 11 at.% Ni. Isothermal section at 

560˚C 

Lattice 

Parameters 


γ, (γFe,Ni) cF4 continuous solid solution in Fe-Ni. 

Fm3m 

(Ni) Cu a = 352.4 pure Ni at 25˚C [V-C2, Mas2] 

< 1455 Dissolves up to 39.4 at.% Zn at 1040˚C in Ni-Zn 

[2008Leb]. 

(γFe) a = 364.67 pure Fe at 915˚C [V-C2, Mas2] 

1394 - 912 Dissolves up to 6 at.% Zn in Fe-Zn [2008Per] 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Lattice 

Parameters 


7 

α, (αδFe) cI2 

Im3m 

(δFe) W a = 293.15 pure Fe at 1390˚C [V-C2, Mas2]. 

1538 - 1394 Dissolves up to 42 at.% Zn at 782˚C in Fe-Zn, 

[2008Per] 

Dissolves up to 3.8 at.% Ni at 1517˚C in Fe-Ni 

[2008Kuz]. 

(αFe) a = 286.65 pure Fe at 25˚C [Mas2]. Dissolves 4.6 at.% Ni at 

< 912 

495˚C [2008Kuz] 

(Zn) hP2 a = 266.50 pure Zn at 25˚C [Mas2] 

< 419.58 P63/mmc Mg 

c = 494.70 

γ’, FeNi cP4 63 to 85 at.% Ni [2008Kuz] 

< 517 Pm3m 

AuCu3 a = 355.23 

Γ1 cI52 

Im3m 

continuous solid solution. 

Fe3Zn10 

< 782 

Cu5Zn8 a = 899 ~75.5 to 79 at.% Zn [2008Per] 

γ, Ni-Zn 

< 881 

a = 893.57 70 to 77 at.% Zn [2008Leb] 

Γ2,Fe1–xNixZny cF408 at 450˚C [1994Per]: 

F43m at y ≈ 0.93 0.023 < x ≈ 0.045 

Fe11Zn40 at x ≈ 0.103 y ≈ 0.87 

at 560˚C [2005Pen]: 

at x ≈ 0.09 y ≈ 0.87 

at x ≈ 0.036 y ≈ 0.906 

at x ≈ 0.03 y ≈ 0.863 

a = 1808.38 [1994Lid] 

a = 1800 [1989Per] 

a = 1801.7 [1999Reu] 

Fe11Zn40 a = 1796.3 at x = 0 ~0.658 < y < 0.81 [2008Per] 

< 550 a = 1798.6 

δ1, FeZn10 hP550 86 to 92.5 at.% Zn, [2008Per] 

< 672 P63mc a = 1283 

FeZn10 c = 5770 

ζ, FeZn13 mC28 a = 1342.4 ~93 to 94 at.% Zn, [2008Per] 

< 530 C2/m b = 760.8 

CoZn13 c = 506.1 

β = 127.3˚ 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_17 

ß Springer 2009

8 17 

Fe–Ni–Zn 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


β, NiZn cP2 47.3 to 58.3 at.% Zn 

1040 - 675 Pm3m 

CsCl 

a = 290.83 [2008Leb] 

β1, NiZn tP4 a = 389.5 45.3 to 58.3 at.% Zn 

< 818 P4/mmm 

AuCu 

c = 321.4 [2008Leb] 

δ, Ni-Zn mC28 a = 1337.6 89 to 90 at.% Zn 

< 490 C2/m b = 751.1 [2008Leb] 

CoZn13 c = 762.7 



MSIT 1


. Fig. 1 

Fe-Ni-Zn. Schematic partial surface of the primary phase separation in the Zn corner 



MSIT 1 

9 

DOI: 10.1007/978-3-540-70890-2_17 

ß Springer 2009

10 17 

Fe–Ni–Zn 

. Fig. 2 

Fe-Ni-Zn. Partial isothermal section at 450˚C 



MSIT 1

. Fig. 3 




MSIT 1 


11 

DOI: 10.1007/978-3-540-70890-2_17 

ß Springer 2009

12 17 

Fe–Ni–Zn 

. Fig. 4 




MSIT 1

. Fig. 5 

Fe-Ni-Zn. Calculated liquid phase boundaries at 450, 465, 480˚C 



MSIT 1 


13 

DOI: 10.1007/978-3-540-70890-2_17 

ß Springer 2009

14 17 

Fe–Ni–Zn 

References 

[1940Glu] Gluskin, D.Ya., “Phases, Formed by Interaction of Refractory Metals with Light-Melts Metals”, Zh. Tekh. 

Fiz., 10(18), 1486–1501 (1940) (Crys. Structure, Experimental, 15) 

[1957Ray] Raynor, G.V., Noden, J.D., “A Note on the Zn-Rich Alloys of the System Zn-Fe-Ni”, J. Inst. Met., 86, 

269–271 (1957) (Experimental, Crys. Structure, 5) 

[1987Bha] Bhan, S., Jain, K.C., Singh, M., “The Iron-Nickel-Zinc System”, J. Alloy Phase Diagrams, 3(1), 31–37 

(1987) (Review, Phase Diagram, Crys. Structure, 39) 

[1989Per] Perrot, P., In-Wha, C., Reumont, G., Dauphin, J.-Y., “Phase Equilibria in the Zinc Rich Corner of the 

Iron-Nickel- Zinc Ternary System”(in French), Compt. Rend. Acad. Sci. Paris, Ser. II, 308, 1413–1417 

(1989) (Phase Diagram, Phase Relations, Crys. Structure, 7) 

[1991Doo] Dooling, T.A., Cook, D.C., “Magnetic-Field Distributions in Zinc-Nickel Ferrite”, J. Appl. Phys., 69(8), 

5352–5354 (1991) (Experimental, Magn. Prop., 4) 

[1992Reu] Reumont, G., Perrot, P., Foct, J., “Fractal Evaluation of Liquidus in the Fe-Zn-Ni System at 450˚C”, 

J. Mater. Sci. Lett., 11, 1611–1613 (1992) (Experimental, Morphology, Phase Diagram, Phase Relations, 

9) 

[1993Che] Chen, Z.W., See, J.B., “Dross Phases Formed in Galvanizing Baths Containing (0-0,1) wt% Nickel 

at 450˚C”, ISIJ Int., 33(2), 307–312 (1993) (Experimental, Phase Diagram, Phase Relations, Crys. 


[1994Lid] Lidin, S., Jacob, M., Larsson A.-K., “(Fe, Ni)Zn 6.5, a Superstructure of γ-Brass”, Acta Crys., Sect. C: Cryst. 

Struct. Commun., 50C(3), 340–342 (1994) (Crys. Structure, Experimental, 7) 

[1994Per] Perrot, P., Reumont, G., “Thermodynamic Description of Dross Formation When Galvanizing Silicon 

Steels in Zinc-Nickel Baths”, J. Phase Equilib., 15(5), 479–482 (1994) (Phase Diagram, Phase Relations, 

Morphology, Thermodyn., 15) 

[1995Per] Perrot, P., Reumont, G., “Authors Reply to- An Alternative Description of Dross Formation When 

Galvanizing Silicon Steels in Zinc-Nickel Baths”, J. Phase Equilib., 16(3), 207 (1995) (Abstract, Phase 

Relations, 6) 

[1995Tan] Tang, N.-Y., “An Alternative Description of Dross Formation When Galvanizing Silicon Steels in Zinc- 

Nickel Baths”, J. Phase Equilib., 16(2), 110–112 (1995) (Review, Phase Diagram, Phase Relations, 14) 

[1996Tan] Tang, N.-Y., “Accurate Description of Liquid Boundary -A Reply to the Reply by Professors Perrot and 

Reumont”, J. Phase Equilib., 17(2), 89–91 (1996) (Review, Phase Relations, 20) 

[1997Ana] Ananth, M.V., Parthasaradhy, N.V., “Hydrogen Evolution Characteristics of Electrodeposited Ni-Zn-Fe 

Coatings in Alkaline Solutions”, Int. J. Hydrogen Energy, 22(8), 747–751 (1997) (Experimental, Morphology, 


[1999Reu] Reumont, G., de Figueiredo, R.S., Fost, J., “Structural Comparison between the γ 2-FeZn 4 Compound 

Obtained by Mechanical Alloying and the γ 2-Fe 6Ni 5Zn 89 Galvanizing Dross”, J. Mater. Sci. Lett., 18, 

1879–1882 (1999) (Crys. Structure, Experimental, Phase Relations, 15) 

[2000Tan] Tang, N-Y., “Determination of Liquid-Phase Boundaries in Zn-Fe-Mx Systems”, J. Phase Equilib., 21(1), 


[2001Tan] Tang, N.Y., Su, X., Toguri, J.M., “Experimental Study and Thermodynamic Assessment of the Zn-Fe-Ni 

System”, Calphad, 25(2), 267–277 (2001) (Assessment, Experimental, Phase Relations, Thermodyn., 16) 

[2002Pat] Pattrick, R.A.D., van der Laan, G., Henderson, C.M.D., Kuiper, P., Dudzik, E., Vaughan, D.J., “Cation 

Site Occupancy in Spinel Ferrites Studied ba X-Ray Magnetic Circular Dichroism: Developing a 

Method for Mineralogists”, Eur. J. Mineral, 14(6), 1095–1102 (2002) (Crys. Structure, Experimental, 34) 

[2003Rag] Raghavan, V., “Fe-Ni-Zn (Iron-Nickel-Zinc)”, J. Phase Equilib., 24(6), 558–560 (2003) (Review, Phase 


[2005Hwa] Hwang, C.-C., Tsai, J.-S., Huang, T.-H., “Combustion Synthesis of Ni-Zn Ferrite by Using Glycine and 

Metal Nitrates-Investigations of Precursor Homogeneity, Product Reproducibility, and Reaction 

Mechanism”, Mater. Chem. Phys., 93, 330–336 (2005) (Experimental, 28) 

[2005Pen] Peng, F., Yin, F., Su, X., Zhi, L., Zhao, M., “560˚C Isothermal Section of Zn-Fe-Ni System at the Zn-rich 

Corner”, J. Alloys Compd., 402(1-2), 124–129 (2005) (Experimental, Morphology, Phase Diagram, Phase 


[2007Rag] Raghavan, V., “Fe-Ni-Zn (Iron-Nickel-Zinc)”, J. Phase Equilib. Diffus., 28(4), 394–394 (2007) (Review, 

Phase Diagram, 5) 



MSIT 1


15 

[2008Kuz] Kuznetsov, V., “Fe-Ni (Iron-Nickel)”, MSIT Binary Evaluation Program, in MSIT Workplace, 

Effenberg, G. (Ed.), MSI, Materials Science International Services, GmbH, Stuttgart; to be published 

(2008) (Crys. Structure, Phase Diagram, Phase Realtions, Assessment, #, 41) 

[2008Leb] Lebrun, N., “Ni-Zn (Nickel-Zinc)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg, G. 

(Ed.), MSI, Materials Science International Services, GmbH, Stuttgart; to be published (2008) (Crys. 

Structure, Phase Diagram, Phase Realtions, Assessment, 9) 

[2008Per] Perrot, P., “Fe-Zn (Iron-Zinc)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg, G. 

(Ed.), MSI, Materials Science International Services, GmbH, Stuttgart; to be published (2008) (Crys. 

Structure, Phase Diagram, Phase Realtions, Assessment, 5) 


(1990) 





MSIT 1 

DOI: 10.1007/978-3-540-70890-2_17 

ß Springer 2009

Iron – Nickel – Zirconium 


Viktor Kuznetsov 

Introduction 

The system itself had not attracted much attention, and proper phase equilibria are known 

rather poorly. [1968Tar1, 1973Tar] studied phase equilibria in the Zr corner; unfortunately, 

these results seem to suffer from oxygen contamination. The review [1992Rag] contains 

virtually only three hypothetical sections and data for the solubility of Fe and Ni in Zr. 

Recently [1999Vju] has constructed a partial isothermal section at 1000˚C for the Fe-ZrFe 2- 

Zr 2Ni 7-Ni region, combining diffusion couple technique and study of equilibrated alloys by 

EPMA, XRD and scanning electron microscopy. 

On the other hand, the amorphous alloys of the system, which are formed moderately 

easily, are considered promising as high-permeability and resistive alloys [1990Sid]. So there 

exist a number of studies of their properties [1983Shi, 1983Ino, 1984Shi, 1984Kri, 1987Puz, 

1987Sta, 1988Vio1, 1988Vio2, 1993Noh, 1994Zat, 1999Dik, 2005Ham]. 

Thermodynamic data exist only for the enthalpies of formation of the liquid phase. Those 

were measured by [1989Sid, 1993Wan, 1999Thi] along three composition sections. Calculations 

of the enthalpy of formation, based on the extrapolation of descriptions of bounding 

binaries, were performed by [1990Sid, 1995Tom, 1996Tom] with generally good results. 

[1993Wan] tested systematically a number of extrapolation models which all also gave nearly 

equally good results. [1985Col] suggested a simple electronic model for the enthalpies of 

formation of liquid alloys of transition metals. 

The studies of phase equilibria, crystal structures and thermodynamic properties are 

summarized in Table 1. 


The Fe-Ni system is accepted from the MSIT evaluation [2008Kuz]. The accepted version of 

the Fe-Zr edge, taken from the recent experimental revision of the system [2002Ste], is 

presented in Fig. 1. The phase diagram of the Ni-Zr binary is given in Fig. 2. It is based on 

[2007Oka], but the temperature of the eutectic L Ð ZrNi + Zr 2Ni was changed to 1022˚C, 

measured by [2007Wan]. 


Fe–Ni–Zr 18 

1 

No ternary compounds were reported. The absence of a mutual solubility of Zr2Fe and Zr2Ni, 

claimed by [1968Tar1, 1973Tar], is most probably due to the contamination of their samples 

by O and/or N, which leads to the appearance of a phase with the Fe 3W 3C(cF112) structure 

instead of the binary Zr 2Fe phase [1972Hav, 1992Rag]. Under oxygen free conditions at 850˚C, 

where both Zr 2Fe and Zr 2Ni are stable, those do form a continuous solid solution [1972Hav]. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_18 

ß Springer 2009

2 18 

Fe–Ni–Zr 

The solid solubility of Ni in ZrFe 2 at 800 and 1200˚C is about 80 mol% “ZrNi 2”[1958Ell]. 

The smaller value, presented by [1999Vju] in their figure 1a, seems to be inferred by analogy 

with the investigated simultaneously Hf-Fe-Ni system, as no experimental data for that region 

are provided. Some physical properties of Zr(Fe 1–xNi x) 2 were studied by [1977Mur] (lattice 

spaces, Curie temperatures, Mössbauer data) and [1982Osi] (Curie temperature), both for 0 ≤ 

x ≲ 0.4. Contrary to the statement of [1992Rag], neither [1977Mur] nor [1982Osi] measured 

the solubility limit; both found their samples to retain the Laves phase structure for the whole 

concentration range studied. 

The solubility of Ni and Fe in Zr at 700 and 600˚C is below 0.1 at.% [1973Tar]. 

The metastable icosahedral quasicrystalline phase was found as a primary precipitation 

phase from the supercooled liquid, obtained by heating of an amorphous phase of the 

Zr 70Fe 20Ni 10 composition above the glass transition temperature [2000Sai]. At the heating 

rate of 0.67 K·s –1 a clear crystallization temperature of 400˚C was observed. It decomposes at 

further heating at about 627˚C, giving a mixture of Zr2Fe and Zr2Ni. 

Crystallographic data for the stable phases are presented in Table 2. 


All the invariant equilibria suggested by [1973Tar] include the “Fe 2Zr” phase, which nearly 

definitely is oxygen-stabilized [1972Hav, 1992Rag]. Therefore they cannot be accepted here. 


A partial isothermal section (solubility of Fe and Ni in the (βZr) phase) at 1100˚C is given in 

Fig. 3, based on the results of [1968Tar1]. The authors claim that partial sections obtained for 

1200, 1100 and 1000˚C proved to be identical. 

Figure 4 presents a partial isothermal section at 1000˚C, based on the results of [1999Vju] 

with slight modifications necessary to bring it into agreement with the accepted versions of the 

binary systems. In particular, the uncertain equilibria with the Fe 3Zr phase, which is not stable 

at this temperature, were removed. The solubility of Ni in the ZrFe 2(h 1) Laves phase is 

accepted from [1958Ell]. 

Figure 5 presents a partial isothermal section (solubility of Fe and Ni in the (βZr) phase) 

at 900˚C. It is based on the results of [1973Tar] with the following modifications. Though 

EPMA of all their two-phase samples gave only Zr 2(Fe,Ni) as the second phase, which 

indeed is in agreement with [1972Hav], they arbitrarily inserted a three-phase field (βZr)+ 

Zr 2(Ni,Fe)+Zr 2(Fe,Ni). This field, as well as the corresponding kink on the solubility line, were 

removed here. 

A partial section at 820˚C, presented by [1973Tar], can not be accepted, as it contradicts to 

the accepted versions of both Fe-Zr and Ni-Zr binary systems. 


The vertical sections presented in [1968Tar1] and [1973Tar] include equilibria with the 

“Fe 2Zr” phase (different from the Laves phase), which in agreement with [1992Rag] are 

considered to be oxygen stabilized. Therefore these sections are not accepted here. 



MSIT 1


The measured values of the enthalpies of formation of liquid are summarized in Table 3. For 

[1989Sid] the approximating equation is given (the table provided in the original work is 

indeed calculated from that). For [1993Wan] data from their table 2 are reproduced, and data 

of [1999Thi] are presented in Fig. 6, as no tabular data are provided in the original work. There 

are several attempts to generalize these fragmentary data and obtain a description for the 

whole concentration range using both the polynomial description [1995Tom, 1996Tom] and 

the regular associate model [1999Thi], but those seem to be too model-dependent. 


[1968Tar2] studied the influence of small (up to ~2 mass%) additions of Fe and Ni on 

mechanical and corrosion (in superheated water, CO2 and air) properties of Zr. Corrosivity 

in water and CO2 remained essentially the same, whereas the influence on the oxidation 

behavior as well as on the strength at room temperature and at 400˚C was favorable. 

[1983Ino] and [1992Zhi] studied mechanical properties of partially crystallized amorphous 

alloys. 

[1993Pec] investigated stability of precipitates of Zr 2(Fe,Ni) in the commercial alloy 

Zircaloy-2 under irradiation. 

[2005Ham] found nonlinear I-V characteristics of a nanocrystalline mixture of Zr 2Ni and 

Zr2Fe obtained by annealing of an initially amorphous alloy Fe0.27Ni0.11Zr0.62 at 973K. 

Miscellaneous 


3 

The concentration dependence of the lattice spaces of the Zr 2(Fe,Ni) phase is presented in 

Fig. 7 [1972Hav, 1992Rag]. 

As was noted in the Introduction, amorphous alloys of the system attracted rather much 

attention, and a number of their physical properties was measured. [1983Shi, 1984Shi] 

measured resistivity in a wide interval of temperatures and pressures. Various magnetic 

properties were studied by [1984Kri, 1987Puz, 1987Sta, 1994Zat]. [1988Vio1, 1988Vio2] 

studied the relaxation of magnetic properties after irradiation. [1993Noh] investigated relaxation 

of the structure during cyclic heat treatment within a stability range of amorphous 

alloys (“enthalpy relaxation”). [1999Dik] searched for a correlation between the local structure 

of amorphous alloys as determined from Mössbauer data and the products of their crystallization. 

[2001Abr] studied alloys of Zr with stainless steel. They determined phase composition 

and stability of alloys during annealing. 

[2004Bio] measured structural and magnetic properties of Ni 81Fe 19/Zr multilayers. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_18 

ß Springer 2009

4 18 

Fe–Ni–Zr 

. Table 1 

Investigations of the Fe-Ni-Zr Phase Relations, Structures and Thermodynamics 


Temperature / Composition / 


[1958Ell] XRD Section ZrFe 2-“ZrNi 2”, 800 and 

1200˚C 

[1968Tar1] Metallography, hardness and microhardness 

measurement 

[1973Tar] Metallography, XRD, DTA, EPMA, hardness and 

microhardness measurement 

[1977Mur] XRD, Curie temperature and magnetization 

measurements, Mössbauer study 

0.25 to 25 mass% (Fe + Ni), 1200 

to 700˚C 

Zr-Zr 2Ni-ZrFe 2, 900 to 600˚C 

Zr(Fe1–xNix)2, 0≤ x ≲ 0.4 

[1982Osi] XRD, Curie temperature measurement Zr(Fe1–xNix) 2,0≤ x ≲ 0.44 

[1989Sid] High-temperature isoperibolic calorimetry Ni1–x(Fe0.67Zr0.33) x,0≤ x ≲ 0.15, 

1600˚C, liquid 

[1993Wan] High-temperature calorimetry (Fe0.86Ni0.14)-Zr (0 to 0.14 Zr), 

1600˚C, liquid 

[1999Thi] Levitation alloying calorimetry (NiZr)-Fe, 0 to 0.35Fe, 1619˚C, 

liquid 

[2000Sai] DSC, TEM, electron microdiffraction, XRD Fe20Ni10Zr70 (initially amorphous), 

327˚C to 727˚C 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 



1538 - 1394 Im3m 

W 


< 912 Im3m 

W 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Lattice 

Parameters 


5 


(γFe) Fm3m a = 364.67 pure Fe at 915˚C [V-C2, Mas2] 

< 1517 Cu 

(Ni) 

< 1455 

a = 352.40 pure Ni at 25˚C [Mas2] 

(βZr) cI2 a = 360.90 pure Zr at T > 863˚C [Mas2, V-C2] 

1855 - 863 Im3m 

W 

(αZr) hP2 a = 323.16 pure Zr at 25˚C [Mas2] 

< 863 P63/mmc Mg 

c = 514.75 

λ1,Zr cF24 0 < x < 0.8 [1958Ell] 

(Fe1–xNix) 2 Fd3m C15 structure 

MgCu2 a = 705.4 x = 0.1 [1977Mur] 

a = 704.2 x = 0.2 [1977Mur] 

a = 702.3 x = 0.3 [1977Mur] 

a = 700.9 x = 0.4 [1977Mur] 

ZrFe2(h1) at x =0 

< 1673 a = 702 to 709 ~27.5 to 34.4 at.% Zr [2002Ste] 

λ2, ZrFe2(h2) hP24 

a = 701.67 ± 0.06 x = 0; 27.6 at.% Zr [2002Ste] 

a = 705.24 ± 0.05 x = 0; 30.8 at.% Zr [2002Ste] 

a = 708.75 ± 0.05 x = 0; 34.6 at.% Zr [2002Ste] 

26.5 to ~27 at.% Zr [2002Ste] 

1345 - ~1240 P63/mmc C36 structure 

MgNi2 a = 495.34 ± 0.07 in the alloy Zr25Fe75 (at.%) annealed at 1290˚C for 

c = 1614.3 ± 0.3 7.5 h, together with (αFe) and Zr6Fe23 phases 

[2002Ste] 

a = 498.8 

c = 1632 

at 1100˚C [V-C2] 

Zr3Fe oC16 74.8 to 75.4 at.% Zr 

< 851 Cmcm a = 332 [2002Ste] 

Re3B b = 1100 in the alloy Zr60Fe40 (at.%) annealed at 700˚C for 

c = 882 1000 h, together with the λ1 phase and traces of 

the Zr2Fe phase 

a = 333 [2002Ste] 

b = 1095 

c = 882 

at 75 at.% Zr [1991Ard] 

ZrNi5 < 1300 cF24 

F4m 

a = 670.64 ± 0.06 at 14.85 at.% Zr [1991Nas] 

AuBe5 a = 670.72 ± 0.06 at 18.40 at.% Zr 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_18 

ß Springer 2009

6 18 

Fe–Ni–Zr 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


Zr2Ni7 mC36 a = 469.8 ± 0.9 [1991Nas] 

< 1440 C2/m b = 823.5 ± 1.3 dissolves Fe up to gross composition 

Ni7Zr2 c = 1219.3 ± 1.6 

β = 95.83˚ 

Zr0.219Fe0.423Ni0.358 [1999Vju] 

ZrNi3 hP8 a = 530.9 [1991Nas] 

< 920 P63/mmc Ni3Sn 

c = 430.3 

Zr8Ni21 aP29 a = 647.21 [1991Nas] 

< 1180 P1 b = 806.45 

Ni21Hf8 c = 858.75 

α = 75.18˚ 

β = 68.00˚ 

γ = 75.20˚ 

Zr7Ni10 oC68 a = 1238.6 ± 0.6 at 41.07 at.% Zr [1991Nas] 

< 1160 Aba2 b = 915.6 ± 0.5 

Ni10Zr7 c = 921.1 ± 0.5 

a = 1249.7 ± 0.4 

b = 921.0 ± 0.5 

c = 932.5 ± 0.2 

at 43.54 at.% Zr [1991Nas] 

Zr9Ni11 tI40 a = 988.0 ± 0.1 [1991Nas] 

1170 - 978 I4/m 

Pt11Zr9 c = 661 ± 1 

Zr oC8 a = 326.8 [1991Nas] 

Ni Cmcm b = 993.7 

< 1280 CrB c = 410.2 

Zr2(Fe1–xNix) tI12, 

I4/mmc complete solid solution at 850˚C [1972Hav] C16 

CuAl2 structure 

Zr2Fe a = 637.3 ± 0.1 at x = 0 in the alloy Zr40Fe60 (at.%) annealed at 800˚ 

951 - 780 c = 560.4 ± 0.1 C for 500 h, together with the λ2 and Zr3Fe phases 

[2002Ste] 

Zr 2Ni a = 648.3 at x =1[1991Nas] 

< 1120 c = 526.7 see Fig. 7 for dependence on x 



MSIT 1



Temperature 

Range [˚C] 

Zr 6Fe 23 

(metastable) 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


cF116 20.6 to 21.6 at.% Zr; metastable; 

Fm3m an oxygen-stabilized phase [2002Ste] 

Th6Mn23 a = 1172 in the alloy Zr30Fe70 (at.%) annealed at 1000˚C for 

200 h, together with the ZrFe2(h2) phase [2002Ste] 

a = 1169 [V-C2] 

. Table 3 



(1–x) Ni(L) + 0.67x Fe(L) + 0.33x 

Zr(L) = Ni 1–xFe 0.67xZr 0.33x(L) 

0.67(1–x) Fe(L) + 0.14(1–x) 

Ni(L) + x Zr(L) = 

Fe 0.67(1–x)Ni 0.14(1–x)Zr x(L) 



Temperature 

[˚C] 

1600 ΔH = x(1–x) 

(–96.17–52.86x 

+233.42x 2 ) 

Quantity, per 

mole of atoms 

[kJ, mol, K] Comments 

1600 ΔH = 1.521 x =0 


7 

0 ≤ x ≤ 0.15 high-temperature 

isoperibolic calorimetry 

[1989Sid] 

ΔH = 2.716 x = 0.013 

ΔH = 4.975 x = 0.037 

ΔH = 7.252 x = 0.061 

ΔH = 9.937 x = 0.092 

ΔH = 12.46 x = 0.122 

ΔH = 14.60 x = 0.151 

ΔH = 16.52 x = 0.178 

ΔH = 17.87 x = 0.194 

ΔH ± 5% high-temperature calorimetry 

[1993Wan] 

MSIT 1 

DOI: 10.1007/978-3-540-70890-2_18 

ß Springer 2009

8 18 

Fe–Ni–Zr 

. Fig. 1 

Fe-Ni-Zr. The Fe-Zr system 



MSIT 1

. Fig. 2 

Fe-Ni-Zr. The Ni-Zr system 



MSIT 1 


9 

DOI: 10.1007/978-3-540-70890-2_18 

ß Springer 2009

10 18 

Fe–Ni–Zr 

. Fig. 3 

Fe-Ni-Zr. Solubility of Fe and Ni in (βZr) at 1100˚C 



MSIT 1


11 

. Fig. 4 

Fe-Ni-Zr. Partial isothermal section at 1000˚C. Dashed lines in two-phase regions are tie lines 

determined by EPMA 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_18 

ß Springer 2009

12 18 

Fe–Ni–Zr 

. Fig. 5 

Fe-Ni-Zr. Solubility of Fe and Ni in (βZr) at 900˚C 



MSIT 1


13 

. Fig. 6 

Fe-Ni-Zr. Enthalpies of formation of the liquid phase from liquid components at 1600˚C on the 

section ZrNi-Fe 

1 - experimental points, 

2 - calculated using regular associated model, 

3 - point from [1993Wan] falling to the section 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_18 

ß Springer 2009

14 18 

Fe–Ni–Zr 

. Fig. 7 

Fe-Ni-Zr. Lattice parameters of the Zr 2(Fe 1–xNi x) solid solution (metastable at room temperature) 



MSIT 1

References 


15 

[1958Ell] Elliott, R.P., Rostoker, W., “The Occurrence of Laves-Type Phase Among Transition Elements”, Trans. 

Am. Soc. Met., 50, 617–632 (1958) (Crys. Structure, Experimental, 27) 

[1968Tar1] Tararaeva, E.M., Grigor’ev, A.T., “The Zr corner of the Zr-Fe-Ni System” (in Russian), Fiz.-Khim. 

Splavov Tsirkoniya, 107–113 (1968) (Phase Diagram, Experimental, *, #, 7) 

[1968Tar2] Tararaeva, E.M., Grigor’ev, A.T., “Corrosional and Mechanical Properties of the Alloys Zirconium- 

Iron-Nickel” (in Russian), Fiz.-Khim. Splavov Tsirkoniya, 113–117 (1968) (Experimental, Interface 

Phenomena, Mechan. Prop., 7) 

[1972Hav] Havinga, E.E., Damsma, H., Hokkeling, P., “Compounds and Pseudo-Binary Alloys with the CuAl 2 

(C16)-Type Structure”, J. Less-Common Met., 27, 169–186 (1972) (Crys. Structure, Phase Relations, 


[1973Tar] Tararaeva, E.M., Ivanov, O.S., “The Zr-Fe-Ni Diagram” (in Russian), Stroenie i Svoistva Splavov dlya 

Atom. Energ., 131–138 (1973) (Phase Diagram, Phase Relations, Phase Relations, Experimental, *, #, 3) 

[1977Mur] Muraoka, Y., Shiga, M., Nakamura, Y., “Magnetic Properties and Mössbauer Effects of A(Fe 1–xB x) 2 

(A = Y or Zr, B = Al or Ni) Laves Phase Inter-Metallic Compounds”, Phys. Status Solidi, 42A, 369–374 

(1977) (Crys. Structure, Experimental, Magn. Prop., 15) 

[1982Osi] Osipova, L.V., Panteleymonov, L.A., “Magnetic Properties of Fe-Ni-Zr and Fe-Ni-Nb Alloys”, Russ. 

Metall., (3), 183–185 (1982), translated from Izv. Akad. Nauk, Met., (3), 205–207 (1982) (Experimental, 


[1983Ino] Inoue, A., Tomioka, H., Masumoto, T., “Mechanical Properties of Ductile Fe-Ni-Zr and Fe-Ni-Zr (Nb 

or Ta) Amorphous Alloys Containing Fine Crystalline Particles”, J. Mater. Sci., 18, 153–160 (1983) 

(Crys. Structure, Experimental, Mechan. Prop., Morphology, 5) 

[1983Shi] Shirakawa, K., Fukamichi, K., Kaneko, T., Masumoto, T., “Electrical Resistance of Fe-Zr and Fe-Ni-Zr 

Amorphous Alloys Under Hydrostatic Pressure”, Phys. Lett. A, 97, 213–216 (1983) (Experimental, 

Electr. Prop., 28) 

[1984Kri] Krishnan, R., Rao, K.V., Liebermann, H.H., “Magnetization and FMR Studies in Amorphous Fe 90Zr 10 

and Fe 70Ni 20Zr 10 Ribbons”, J. Appl. Phys., 55, 1823–1825 (1984) (Experimental, Magn. Prop., 16) 

[1984Shi] Shirakawa, K., Fukamichi, K., Kaneko, T., Masumoto, T., “Electrical Resistivity Minima of Fe-(Ni, Co)- 

Zr Amorphous Alloys”, J. Phys. F: Met. Phys., 14, 1491–1499 (1984) (Electr. Prop., Experimental, 36) 

[1985Col] Colinet, C., Pasturel, A., Hicter, P., “A d Band Bonding Model of the Enthalpy of Formation of Ternary 

Transition Metal Alloys”, Z. Metallkd., 76, 542–545 (1985) (Calculation, Thermodyn., 33) 

[1987Puz] Puzniak, R., Rao, K.V., “Anomalous Temperature Dependence of the Effective Susceptibility Exponent 

in Amorphous Fe-Ni-Zr Alloys (Abstract)”, J. Appl. Phys., 61, 4428–4428 (1987) (Abstract, Magn. 

Prop., 1) 

[1987Sta] Stadnik, Z., Griesbach, P., Dehe, G., Guetlich, P., Miyazaki, T., “Nickel Contribution to the Magnetism 

of Fe-Ni-Zr Metallic Glasses”, Phys. Rev. B, 35, 430–432 (1987) (Electr. Prop., Experimental, Magn. 

Prop., 27) 

[1988Vio1] Violet, C.E., Borg, R.J., Rao, K.V., Noques, J., Taylor, R.D., Batra, A.P., “Temperature Hysteresis and 

Relaxation Effects in Amorphous Fe-Ni-Zr Alloys (Abstract)”, J. Appl. Phys., 63, 3398–3398 (1988) 

(Abstract, Magn. Prop., 0) 

[1988Vio2] Violet, C.E., Borg, R.J., May, L., Rao, K.V., Nogues, J., Taylor, R.D., Batra, A.P., “Magnetic Behavior of 

Amorphous Fe-Ni-Zr Alloys and Their Response to Radiation Damage”, Hyperfine Interact., 42, 

963–966 (1988) (Electrical Prop., Experimental, 4) 

[1989Sid] Sidorov, O.Yu., Esin, Yu.O., Geld, P.V., “Enthalpies of Formation of Zirconium Alloys with Iron, 

Cobalt, Nickel, and Copper” (in Russian), Rasplavy, (3), 28–33 (1989) (Calculation, Experimental, 

Thermodyn., *, 22) 

[1990Sid] Sidorov, O.Yu., Valishev, M.G., Pletneva, E.D., Esin, Yu.D., Geld, P.V., “Enthalpies of Formation of 

Nickel-based Ternary Liquid Alloys”, J. Appl. Chem. USSR, 63, 1497–1501 (1990), transl. from Zh. Prikl. 

Khim., 63, 1371–1374, (1990) (Experimental, Calculation, Thermodyn., 27) 

[1991Ard] Ardisson, J.D., Mansur, R.A., da Silva, E.G., “A Study of Structural and Electronic Properties of the 

Alloy Systems (Zr 1–xTi x) 2Fe and (Zr 1–xTi x) 3Fe in the Range 0 ≤ x ≤ 0.2”, Scr. Met. Mater., 25(6), 

1327–1331 (1991) (Crys. Structure, Experimental, Electronic Structure, Magn. Prop., 6) cited from 

abstract 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_18 

ß Springer 2009

16 18 

Fe–Ni–Zr 

[1991Nas] Nash, P., Zayanth C.S., “Ni-Zr (Nickel-Zirconium)” in “Phase Diagrams of Binary Nickel Alloys”, 

Nash, P., (Ed.), ASM Intl., Materials Park, OH, 390–394 (1991) (Phase Relations, Crys. Structure, 

Assessment, 38) 

[1992Rag] Raghavan, V., “The Fe-Ni-Zr (Iron-Nickel-Zirconium) System” in “Phase Diagrams of Ternary Iron 

Alloys”, Indian Institut of Metals, Calcutta, 6B, 1094–1098 (1992) (Crys. Structure, Phase Diagram, 


[1992Zhi] Zhigalina, O.M., Sosnin, V.V., Glezer, A.M., “Structure and Mechanical Properties of Microcrystalline 

Alloys of the System Ni-Fe-Zr”, Met. Sci. Heat Treat., 34, 263–268 (1992), translated from Metallov. 

Termich. Obrab. Met., 34, 25–28 (1992) (Crys. Structure, Experimental, Mechan. Prop., Morphology, 7) 

[1993Noh] Noh, T.-H., Inoue, A., Fujimori, H., Masumoto, T., “Enthalpy Relaxation and Curie Temperature 

Behavior in Fe-(Ni,Co)-Zr Amorphous Alloys”, J. Non-Cryst. Solids, 152, 212–218 (1993) (Experimental, 


[1993Pec] Pecheur, D., Lefebvre, F., Motta, A.T., Lemaignan, C., Charquet, D., “Effect of Irradiation on 

the Precipitate Stability in Zr Alloys”, J. Non-Cryst. Solids, 205, 445–451 (1993) (Experimental, 


[1993Wan] Wang, H., Lueck, R., Predel, B., “Thermodynamic Investigation on Liquid Iron-Nickel-Zirconium 

Alloys”, J. Phase Equilib., 14, 48–53 (1993) (Experimental, Calculation, Thermodyn., *, 15) 

[1994Zat] Zatroch, M., Kovac, J., Rohr, L., Aubertin, F., Gonser, U., “Moessbauer and Magnetic Investigations of 

Iron-rich Fe-Ni-Zr Amorphous Alloys”, Phys. Status Solidi B, 184, 499–508 (1994) (Electr. Prop., 

Experimental, Magn. Prop., Thermodyn., 23) 

[1995Tom] Tomiska, J., Wang, H., “On the Algebraic Evaluation of the Ternary Molar Heat of Mixing HE from 

Calorimetric Investigations”, Ber. Bunsen-Ges. Phys. Chem., 99, 633–640 (1995) (Calculation, Thermodyn., 

27) 

[1996Tom] Tomiska, J., Neckel, A., “The Margules Concept: The Basis of Modern Algebraic Representations of 

Thermodynamic Excess Properties”, J. Phase Equilib., 17, 11–20 (1996) (Calculation, Thermodyn., 23) 

[1999Dik] Dikeakos, M., Altounian, Z., Ryan, D.H., Kwon, S.J., “Local Structure in Amorphous Fe-TM-Zr (TM = 

Co, Ni, Cu) Studied by Moessbauer Spectroscopy”, J. Non-Cryst. Solids, 250–252, 637–641 (1999) (Crys. 

Structure, Electr. Prop., Experimental, 17) 

[1999Thi] Thiedemann, U., Roesner-Kuhn, M., Drewes, K., Kuppermann, G., Frohberg, M.G., “Mixing Enthalpy 

Measurements of Liquid Ti-Zr, Fe-Ti-Zr and Fe-Ni-Zr Alloys”, Steel Res., 70, 3–8 (1999) (Experimental, 

Calculation, Thermodyn., *, 20) 

[1999Vju] Vjunitsky, I.V., Abramycheva, N.L., Kalmykov, K.B., Dunayev, S.F., “II. Solid Phase Interaction of 

Elements in the Fe-Ni-Zr and Fe-Ni-Nb Systems at 1273 K” (in Russian), Vestn. Mosk. Univ., Ser. 2, 

Khim., 40, 179–182 (1999) (Experimental, Phase Relations, *, #, 4) 

[2000Sai] Saida, J., Li, Ch., Matsushita, M., Inoue, A., “Nano-Icosahedral Quasicrystalline Phase Formation from 

a Supercooled Liquid State in Zr-Fe-Ni Ternary Metallic Glass”, Appl. Phys. Lett., 76, 3037–3039 (2000) 

(Crys. Structure, Experimental, Phase Relations, 12) 

[2001Abr] Abraham, D.P., Richardson, J.W., McDeavitt, S.M., “Microscopy and Neutron Diffraction Study of a 

Zirconium-8 mass% Stainless Steel Alloy”, J. Mater. Sci., 36, 5143–5154 (2001) (Crys. Structure, 

Experimental, Morphology, Phase Diagram, Phase Relations, 32) 



(2002) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 88) 

[2004Bio] Biondo, A., Nascimento, V.P., Lassri, H., Passamani, E.C., Morales, M.A., Mello, A., Biasi, R.S., Baggio- 

Saitovitch, E., “Structural and Magnetic Properties of Ni 81Fe 19/Zr Multilayers”, J. Magn. Magn. Mater., 

277, 144–152 (2004) (Crys. Structure, Experimental, Magn. Prop., Morphology, 22) 

[2005Ham] Hamed, F., “Nonlinear I-V Characteristics Observed in Annealed Ni-Fe-Zr Metallic Glass”, Physica B, 


[2007Oka] Okamoto, H., “Ni-Zr (Nickel-Zirconium)”, J. Phase Equilib. Diff., 28, 409 (2007) (Phase Relations, 

Phase Diagram, Review, *, #, 3) 

[2007Wan] Wang, N., Li, Ch., Du, Z., Wang, F., “Experimental Study and Thermodynamic Re-assessment of the 

Ni-Zr System”, Calphad, 31, 413–421 (2007) (Experimental, Assessment, Calculation, Phase Relations, 

Phase Diagram, Thermodyn., *, 30) 



Structure, Phase Diagram, Phase Realtions, Assessment, #, 41) 



MSIT 1


17 


(1990) 





MSIT 1 

DOI: 10.1007/978-3-540-70890-2_18 

ß Springer 2009

Iron – Oxygen – Lead 



Introduction 

Ferrites, non-metallic solid magnetic materials, are the complex compounds of the iron oxide 

Fe 2O 3 with oxides of other metals by their chemical compositions. By their magnetic properties 

the ferrites are the analogues of ferromagnetics but they possess lower densities and lesser 

losses on the eddy currents. That’s why ferrites are widely used in radio engineering, electronics 

and super high frequent technology productions. With a view to optimization of alloys 

compositions selection for preparation of ferrites information about phase relations in the 

corresponding ternary and multicomponent systems is of a great importance. Among these 

systems the Fe-O-Pb system plays a considerable role, but information concerning phase 

relations is quite scanty. It is presented in literature by a partial isobaric section in air 

[1984Sha], the solubility of lead in liquid iron in the presence of oxygen [1995Li] and the 

constitution of the PbO-Fe 2O 3 temperature-composition section [1955Coc, 1957Ber, 

1960Mar, 1962Mou, 1978Mex, 1984Sha, 1986Nev]. Phase contents of the alloys and crystal 

structures of the identified intermediate phases were studied by [1928Joh, 1938Ade, 1955Coc, 

1957Ber, 1960Mar, 1962Mou, 1978Mex, 1984Sha, 1986Nev, 1988Ara, 1997Dor, 1998Cla, 

1998Hua, 2000Dia, 2001Dia, 2002Car, 2002Mar, 2003Cas, 2004Dia, 2005Pal]. Data on thermodynamic 

properties were experimentally obtained by [1986Nev] and [1995Li]. The applied 

experimental methods as well as the studied temperature and composition ranges are presented 

in Table 1. Literature information concerning the Fe-O-Pb system was reviewed in 

[1989Rag]. Further determination of the phase equilibria character is necessary, in particular, 

on the constitution of the temperature-composition sections formed by Fe 2O 3 with lead 

oxides Pb 3O 4,Pb 12O 17, Pb 12O 19 and PbO 2. 


Phase diagrams of the Fe-O and Fe-Pb systems are accepted from [Mas2]. The constitution of 

the O-Pb system is accepted on the basis of [1998Ris] assessment (Fig. 1). 


Fe–O–Pb 19 

1 

Crystallographic data about known unary, binary and ternary phases are compiled in Table 2. 

Compositions of the all reported ternary phases lie along the PbO-Fe 2O 3 section. Existence 

of the τ 1, τ 2 and τ 3 phases was established certainly during both crystal structures and 

phase relations studies. In particular, data about the τ 1 phase were reported by [1955Coc, 

1957Ber, 1962Mou, 1978Mex, 1984Sha, 1986Nev], about the τ 2 phase - by [1928Joh, 1957Ber, 

1960Mar, 1962Mou, 1984Sha, 1986Nev], as well as concerned the τ 3 phase - by [1938Ade, 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_19 

ß Springer 2009

2 19 

Fe–O–Pb 

1957Ber, 1960Mar, 1962Mou, 1978Mex, 1984Sha, 1986Nev, 1997Dor, 1998Cla, 2000Dia, 

2001Dia, 2002Mar, 2003Cas, 2004Dia, 2005Pal]. Also information about the τ 4 and τ 5 existence 

was presented by [1955Coc], but later it was shown by [1962Mou] that the τ 2 and τ 3 

phases possess homogeneity ranges covering the compositions of the τ 4 and τ 5 phases. 

Data about the existence of the τ 6 and τ 7 phases ([1960Mar] and [1978Mex, 1999Hsu], 

respectively) were not confirmed by investigations of phase relations along the PbO-Fe2O3 

temperature-composition section [1984Sha, 1986Nev]. 


On the basis of a dissociation process studies it was established by [1984Sha] that equilibria 

with the participation of the following phases take place: L + τ 2 + τ 3 + β at 1315˚C, 

L+βPb3O4 + αPbO + τ1 at 455˚C, L + βPb3O4 + τ1 + τ2 at 430˚C and L + βPb3O4 + τ3 + β 

at 410˚C. Also equilibria with the participation of the PbOx-based phase with inexact stoichiometry 

were reported. The character of all the respective invariant reactions is not established. 


Phase relations at subsolidus temperatures in the range of compositions adjacent to the PbO- 

Fe2O3 section were schematically shown by [1984Sha]. It was established that the βPb3O4 

phase takes part in equilibria with the τ1, τ2 and τ3 phases and with the β phase. 


The solubility of lead in the liquid iron in the presence of oxygen was studied by [1995Li] at the 

temperatures of 1550, 1600 and 1650˚C and various oxygen contents. The obtained dependences 

are shown in Fig. 2. A rise in lead solubility with increasing oxygen content and 

temperature was observed. Using the method of linear regression, the following functions 

lg(at.%){Pb} were evaluated as –0.51 + 0.50·{at.% O} ± 0.025 at 1550˚C, –0.43 + 0.67·{at.% O} 

± 0.089 at 1600˚C and –0.36 + 0.76· {at.% O} ± 0.038 at 1650˚C. 


The PbO-Fe2O3 temperature - composition section being named as quasibinary in many 

publications, does not possess quasibinary character on the Fe2O3 side because this phase 

melts incongruently in the boundary binary Fe-O system. The section shown in Fig. 3 after 

[1989Rag] is based on the data of [1986Nev] in the PbO rich part and [1962Mou] in the Fe 2O 3 

rich side. Another version of the PbO-Fe 2O 3 phase diagram was constructed by [1984Sha] 

on the basis of dissociation curves projections. The character of the phase relations at 

low temperatures needs further verification using different physico-chemical experimental 

techniques. 



MSIT 1


Enthalpies of melting ΔH S melt of the τ 1, τ 2 and τ 3 phases were calculated by [1986Nev] using 

the solution of equations following from the equilibrium conditions of coexisting phases. 

These values were obtained as 22.24 kJ·mol –1 , 49.92 kJ·mol –1 and 61.67 kJ·mol –1 , respectively. 

The enthalpies of formation of the τ 3 phase from oxides (Δ fH) or from simple substances 

(ΔfH298) were calculated by [1992Rez] by approximate methods using the enthalpies of the 

change of cation coordination in the formation of the compounds from simple oxides. The 

reported values are 37 kJ·mol –1 and –5115 kJ·mol –1 , respectively. In the study of lead solubility 

in liquid iron, [1995Li] have calculated the activity coefficient f o Pb and the interaction 

parameter e o Pb at the temperatures of 1550, 1600 and 1650˚C (Table 3). 



3 

In case Pb is used as heat exchanger liquid in steel tubes of a nuclear reactor, the system is 

interesting in case of oxygen contamination of the cooling system producing oxide compounds 

which are radioactive and may be deposited in cool parts of the tubing system causing 

unwanted levels of radiation in the outer parts of the reactor system. 

Because of their particular magnetic properties, ferrites, in particular, lead-containing, 

find many industrial applications, in the first instance as magneto-electric materials. Information 

concerning investigations of the Fe-O-Pb materials properties is collected in Table 4. 

[1957Ber] studied dependence of magnetic energy on the temperature of sintering for alloys 

with different PbO:Fe2O3 ratios [1957Ber] and observed a maximum energy values at the 

composition PbO-4Fe 2O 3. The corresponding dependences of the residual magnetic induction 

and the coercive force were also constructed by [1957Ber]. Magnetic measurements on 

the epitaxial films with the composition Fe 12.9PbO 22.9 were carried out by [1997Dor]. These 

objects exhibit magnetically isotropic behavior in the film plane with magnetic remanence to 

saturation magnetization divided by 4π ratio M(r)/M(s) = 88 ± 2.9% and coercive field H c = 

198.94 ± 7.72 kA·m –1 . However, the films were anisotropic with respect to the film normal 

such that the c crystallographic axis is a magnetically hard direction and all directions 

normal to the c axis are magnetically easy. The saturation magnetization (4πM (s)) value for 

the films is 0.063 T at room temperature. Magnetic properties of thin films with the composition 

of Fe 12PbO 19 prepared by deposition on Si\SiO 2 and sapphire substrates were 

studied by [2000Dia] and [2001Dia], respectively. The influence of the substrate temperature 

(550-775˚C) and the oxygen pressure (1-3 mbar) on the magnetic properties during the 

deposition was reported by [2000Dia]. The χ type lead hexaferrite films with high saturation 

magnetization and high coercive field (302.39 kA·m –1 ) were grown using a substrate temperature 

of 700˚C and a pressure of 3.0 mbar of oxygen, while moderate value of coercive field of 

the thin films deposited on sapphire substrate at 700˚C under 3.0 mbar partial pressure of high 

purity oxygen was 198,94 kA·m –1 [2001Dia]. The optimum value of coercive field of the 

Fe 12PbO 19 powder obtained by [2004Dia] using modifications to the traditional ceramic route 

was 318.31 kA·m –1 at 900˚C. It was concluded that at temperatures higher than 900˚C 

the magnetic properties are drastically affected as a consequence of the volatility of PbO. 

Phase formation during self-propagating high-temperature synthesis of ferrites was studied 

by [2002Mar]. The combustion temperature was 1267˚C, the average front velocity was 

9·10 –4 m·s –1 , the obtained intermediate phases were FeO, Fe3O4 and Fe4PbO7. The value 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_19 

ß Springer 2009

4 19 

Fe–O–Pb 

of coercivity was 48 kA·m –1 . Results of tunneling magnetoresistance effect studies in the Fe-O- 

Pb granular films were presented by [1998Cla, 1999Hsu, 2000Hsu]. The dynamics of the 2b 

site in the Fe 12PbO 19 compound was investigated by [1998Cla] on polycrystalline and oriented 

single-crystal samples above the Curie temperature. 

. Table 1 

Investigations of the Fe-O-Pb Phase Relations, Structures and Thermodynamics 


[1928Joh] as quoted 

by [1962Mou] 

X-ray diffraction Fe 4PbO 7 

[1938Ade] X-ray Laue and rotation techniques Fe 12PbO 19 

[1955Coc] as quoted 

by [1960Mar] and 

[1989Rag] 

Temperature/ 

Composition/Phase 

Range Studied 

optical microscopy The PbO-Fe 2O 3 section 

[1957Ber] X-ray Debye-Scherrer studies, thermal analysis, 

magnetic steel tester measurements 

[1960Mar] Thermal analysis, metallography, powder X-ray 

diffraction 

875-1275˚C, the PbO- 

Fe 2O 3 section 

The PbO-Fe 2O 3 section 

[1962Mou] X-ray diffraction (Norelco diffractometer), DTA 600-1400˚C, the PbO- 

Fe2O3 section 

[1978Mex] Solid state reactions studying, 

thermogravimetry, X-ray diffraction 

The PbO-Fe2O3 section 

[1984Sha] Thermobalance, X-ray diffraction The PbO-Fe2O3 section 

[1986Nev] DTA, X-ray diffraction, crystal growth studying The PbO-Fe2O3 section 

[1995Li] Gas-light Tammann furnace measurements of 1550, 1600, 1650˚C, the 

solubility 

Fe rich corner 

[1997Dor] X-ray diffraction (standard and grazing 600˚C, room 

incidence), Rutherford back-scattering temperature, the 

spectrometry 

Fe12.9PbO22.9 thin films 

[1998Cla] Comparative Fe-57 Mössbauer spectroscopy 

(polycrystalline and oriented single-crystal 

samples) 

477-707˚C, Fe12PbO19 [1998Hua] Method of manufacturing granular films whole range of 

compositions 

[2000Dia] Pulsed laser ablation deposition 550-775˚C, Fe12PbO19 [2001Dia] Pulsed laser ablation deposition, X-ray 

diffraction 

700˚C, Fe 12PbO 19 



MSIT 1



[2002Car] Optical microscopy, scanning electron 

microscopy, electron probe microanalysis, Xray 

diffraction, Mössbauer spectroscopy 

[2002Mar] Self-propagating high-temperature synthesis, 

X-ray diffraction, thermal analysis, chemical 

analysis, magnetic properties determination, 

density measurements, arrested front method 

Temperature/ 

Composition/Phase 

Range Studied 

476˚C, Fe-O-Pb thin 

layers 

Fe 12PbO 19 

[2003Cas] Laser ablation deposition 700˚C, Fe12PbO19 thin 

films 

[2004Dia] Mössbauer spectroscopy, X-ray diffraction > 800˚C, Fe12PbO19 [2005Pal] Ceramic method, Rietveld refinement X-ray 

diffraction 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Fe 12PbO 19 

Lattice 

Parameters 


(δFe) (h2) cI2 a = 293.15 [Mas2] 

1538 - 1394 Im3m 

Fe1–x–yPbxOy W x =0,0

6 19 

Fe–O–Pb 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


(αPb) hP2 a = 326.5 at 25˚C [Mas2] 

> 1.03·10 5 bar P6 3/mmc c = 538.7 

Mg 

α, Fe1–xOx cF8 x = 0.5126 to 0.5457 [Mas2] 

(wüstite) Fm3m 

1424 - 570 NaCl a = 430.88 in the alloy Fe48.5O51.5, T = 20˚C [E] 

a = 428.00 in the alloy Fe47.2O52.8, T = 20˚C [E] 

γFe3O4 (h) cF56 57.1 to 58.02 at.% O [Mas2] 

1596 - 580 Fd3m 

MgAl2O4 a = 840 [E] 

βFe3O4 (r) mC224 - ~57.1 at.% O [Mas2] 

< 580 Cc 

βFe3O4 

αFe3O4 (hp) 

> 2.5·10 

m*14 - ~57.1 at.% O [Mas2] 

–5 bar 

β, Fe2O3 hR30 59.82 to ~60 at.% O [Mas2] 

< 1457 R3c a = 503.42 at 600˚C [Mas2, V-C2] 

Al2O3 c = 1374.83 

ε (Fe-O) c** - metastable; ~51.3 to ~53.5 at.% O [Mas2]; labelled as 

“P’ (wüstite)” [Mas2] 

η (Fe-O) mP500? - metastable; ~52 to ~54 at.% O [Mas2]; labelled as “P” 

P21/m 

(wüstite)” [Mas2] 

κ (Fe-O) hR6 - metastable; 51.3 to 53.2 at.% O [Mas2]; labelled as 

R3 

NiO (l) 

“wüstite (low-tempe-rature)” [Mas2] 

λ (Fe-O) cI80 

Ia3 

Mn2O3 

- metastable; ~60 at.% O; labelled as “βFe2O3”[Mas2] μ (Fe-O) tP60 

P43212 - metastable; ~60 at.% O; labelled as “γFe2O3”[Mas2] ν (Fe-O) m*100 metastable; ~60 at.% O; labelled as “εFe2O3” a = 1299 

b = 1021 

c = 844 

β = 95.33˚ 

[Mas2] [S] 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Lattice 

Parameters 


βPbO (h) oP8 50 at.% O, labelled as “PbO-M” [Mas2, 1998Ris] 

~887 - ~489 Pbma 

or a = 547.6 [1961Lec1] 

Pbcm b = 474.3 

βPbO c = 587.6 

a = 548.9 

b = 475.5 

c = 589.1 

at T = 27˚C [H] 

αPbO (r) tP4 50 at.% O, labelled as “PbO-L” [Mas2, 1998Ris] 

≲ 489 P4/nmm 

αPbO a = 396 

c = 501 

[1961Lec2] 

a = 397.59 

c = 502.3 

at T = 27˚C [H] 

a = 397.2 

c = 501.8 

[1989Rag] 

βPb3O4 (r) tP28 57.1 at.% O, labelled as “Pb3O4-T” [Mas2, 1998Ris] 

595 - (–103) P42/mbc βPb3O4 (r) a = 881.5 

c = 656.5 

at T = 25˚C [S] 

a = 880.6 

c=656.4 

[1989Rag] 

αPb3O4 (l) oP28 57.1 at.% O, labelled as “Pb3O4-R” < –103 Pbam [Mas2] 

a = 912.4 

b = 846.7 

c = 656.7 

at T = – 268˚C [1988Wri, 2001Guz] 

a = 881.89 

b = 880.68 

c = 656.36 

[1989Rag] 

γ, Pb12O17 oP28 58.6 at.% O [Mas2, 1998Ris] 

361 - < 0 Pmc21? a = 778 

b = 1098 

c = 1148 

[1988Wri, 2001Guz] 



MSIT 1 

7 

DOI: 10.1007/978-3-540-70890-2_19 

ß Springer 2009

8 19 

Fe–O–Pb 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


δ, Pb12O19 mP62 61.3 at.% O [Mas2, 1998Ris] 

335 - 54 Pc? orP21/c a = 773 

b = 1083 

c = 1147 

β = 88.77˚ 

in the alloy PbO1.57 [E] 

a = 775.3 

b = 1084.8 

c = 1150.2 

β = 88.93˚ 

[S] 

a = 1150 

b = 1084.3 

c = 777.3 

β = 91.08˚ 

[1988Wri, 2001Guz] 

βPbO2 tP6 66.1 to 66.7 at.% O, with a small amount of hydrogen; 

251 - < 0 P42/mnm TiO2 (rutile) 

labelled as “PbO2-I” [Mas2, 1998Ris] 

a = 491 

c = 336 

[E] 

a = 495.5 

c = 338.3 

[S] 

a = 495.56 

c = 338.67 

1988Wri, 2001Guz] 

a = 495.78 

c = 338.78 

[1989Rag] 

αPbO2 (hp) cF12 - metastable; 

Fm3m about 66.7 at.% O; contains a small amount of 

CaF2 hydrogen; labelled as “PbO2-III” [Mas2] 

θ (Pb-O) m** - metastable; 

P21 or 21/m 50 at.% O [Mas2] 

ρ (Pb-O) o** - metastable; 

50 at.% O; labelled as “PbOα” [Mas2] 

σ (Pb-O) o** - metastable; 

57.1 at.% O [Mas2] 

ξ (Pb-O) o** - metastable; 

57.1 to 61.1 at.% O; labelled as “PbOn”[Mas2] ζ (Pb-O) pseudocubic - metastable; 

58.6 at.% O [Mas2] 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Δ, Pb 2O 3, mP20 metastable; 

1 bar 

hydrostatic 

pressure 

Lattice 

Parameters 


P2 1/a 60 at.% O [1961Whi] 

a = 781.4 [1988Wri, 2001Guz] 

b = 562.5 

c = 846.6 


R (Pb-O) pseudocubic - metastable; 

61.3 at.% O [Mas2] 

R’ (Pb-O) m** - metastable; 

61.3 at.% O [Mas2] 

f (Pb-O) oP12 - metastable; 

Pbcn about 66.7 at.% O; contains a small amount of 

Nb2FeO6 hydrogen; labelled as “PbO2-II” [Mas2] 

* τ1,Fe2Pb2O5 t** a = 779 [1957Ber, 1962Mou] 

870 - ~650 c = 1585 

a = 780 

c = 1582 

[1978Mex] 

labelled as “δ” [1962Mou] 

* τ2,Fe4PbO7 h** a = 1186 [1928Joh, 1962Mou] 

880 - 750 c = 4714 

labelled as “γ” [1962Mou] 

* τ3,Fe12PbO19 hP64 [1938Ade] 

~1315 - ~760 P63/mmc a = 588 

c = 2302 

in the Fe12.9PbO22.9 epitaxial films 

a = 512 

c = 2367 

deposited at T = 600˚C [1997Dor] 

a = 588.5 in the Fe12PbO19 thin films deposited at T = 700˚C 

c = 2306.6 [2001Dia] 

a = 592 

c = 2322 

[2002Mar] 

a = 587 

c = 2312 

[2002Mar] 

labelled as “β” [1962Mou] 

* τ4, Fe10Pb2O17 - - [1955Coc] 



MSIT 1 

9 

DOI: 10.1007/978-3-540-70890-2_19 

ß Springer 2009

10 19 

Fe–O–Pb 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

* τ5, Fe10PbO16 - - [1955Coc] 

* τ6,Fe8PbO13 h** a = 662 

c = 1019 

[1960Mar] 

* τ7,Fe6PbO10 h** a = 591 

c = 2352 

[1978Mex] 

Lattice 

Parameters 


. Table 3 

Values of Activity Coefficient and Interaction Parameters Referring to O [1995Li] 

T [˚C] % {Pb} Fe-Pb f ˚ Pb e˚ Pb 

1550 0.31 3.23 – 0.50 

1600 0.38 2.66 – 0.67 

1650 0.43 2.31 – 0.76 

. Table 4 

Investigations of the Fe-O-Pb Materials Properties 


[1957Ber] Magnet steel tester measurements Residual magnetic induction, coercive 

force, magnetic energy 

[1997Dor] Vibrating sample magnetometer, SQUID 

magnetometer static magnetic 

techniques 

[1998Cla] Comparative Fe-57 Mössbauer 

spectroscopy 

Magnetic anisotropy, magnetic 

remanence, coercive field, saturation 

magnetization 

Dynamics of the 2b site 

[1998Hua] Magnetic resistivity measurements Magnetic resistivity 

[1999Hsu] Magnetic resistivity measurements Magnetic resistivity 

[2000Dia] Saturation magnetization and coercive 

field measurements 

Saturation magnetization, coercive field 

[2000Hsu] Tunneling magnetoresistance 

measurements 

Tunneling magnetoresistance 



MSIT 1







[2002Mar] Coercive field measurements Coercive field 






MSIT 1 

11 

DOI: 10.1007/978-3-540-70890-2_19 

ß Springer 2009

12 19 

Fe–O–Pb 

. Fig. 1 

Fe-O-Pb. The O-Pb phase diagram 



MSIT 1


13 

. Fig. 2 

Fe-O-Pb. Lead solubility as a function of oxygen content in liquid iron at 1550, 1600 and 1650˚C 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_19 

ß Springer 2009

14 19 

Fe–O–Pb 

. Fig. 3 

Fe-O-Pb. Temperature - composition section PbO-Fe 2O 3 



MSIT 1

References 


15 

[1928Joh] Johansson, K., “Mineralogical Communications” (in German), Z. Kristallogr., 68, 87–118 (1928) (Crys. 

Structure, Experimental) as quoted by [1962Mou] 

[1938Ade] Adelskoeld, V., “X-Ray Studies on Magnetoplumbite, Pb 0.6Fe 2O 3 and other Substances Resembling 

“β-Alumina”, Na 2O·11Al 2O 3”, Arkiv Kemi, Mineral. Geol., 12A(29), 1–9 (1938) (Crys. Structure, Experimental, 

12) 

[1955Coc] Cocco, A., “The Binary System PbO-Fe 2O 3” (in Italian), Ann. Chim. (Rome), 45, 737–753 (1955) (Crys. 

Structure, Phase Relations, Experimental, 4) as quoted by [1960Mar] and [1989Rag] 

[1957Ber] Berger, W., Pawlek, F., “Crystallographic and Magnetic Studies of the PbO-Fe 2O 3 System” (in German), 

Arch. Eisenhuettenwes., 28(2), 101–108 (1957) (Crys. Structure, Phase Diagram, Experimental, Magn. 

Prop., 10) 

[1960Mar] Margulis, E.V., Kopylov, N.I., “The Lead Monoxide-Ferric Oxide System”, Russ. J. Inorg. Chem. (Engl. 

Transl.), 5(11), 1196–1199 (1960), translated from Zh. Neorg. Khim., 5(11), 2474–2479 (Crys. Structure, 

Morphology, Phase Diagram, Experimental, *, 11) 

[1961Lec1] Leciejewicz, J., “Neutron-Diffraction Study of Orthorhombic Lead Monoxide”, Acta Crystallogr., 14(1), 


[1961Lec2] Leciejewicz, J., “On the Crystal Structure of Tetragonal (Red) PbO”, Acta Crystallogr., 14(12), 1304 


[1961Whi] White, W.B., Dachille, F., Roy, R., “High-Pressure-High Temperature Polymorphism of the Oxides of 

Lead”, J. Am. Ceram. Soc., 44(4), 170–174 (1961) (Crys. Structure, Phase Relations, Experimental, 16) 

[1962Mou] Mountvala, A.J., Ravitz, S.F., “Phase Relations and Structures in the System PbO-Fe 2O 3”, J. Am. Ceram. 

Soc., 45(6), 285–288 (1962) (Crys. Structure, Phase Diagram, Experimental, #, 11) 

[1978Mex] Mexmain, J., Hivert, S.L., “Preparation and Characterization of Lead Ferrites” (in French), Ann. Chim. 

(Paris), 3(2), 91–97 (1978) (Crys. Structure, Experimental, Phase Diagram, *, 5) 

[1984Sha] Shaaban, S.A., Abadir, M.F., Mahdy, A.N., “The System Pb-Fe-O in Air”, British Ceram. Transact. J., 

83(4), 102–105 (1984) (Crys. Structure, Phase Diagram, Phase Relations, Experimental, *, 7) 

[1986Nev] Neviva, M., Fischer, K., “Contribution to the Binary Phase Diagram of the System PbO-Fe 2O 3”, Mater. 

Res. Bull., 21(11), 1285–1290 (1986) (Crys. Structure, Phase Diagram, Thermodyn., Calculation, 

Experimental, #, 11) 

[1988Ara] Arakcheeva, A.V., Karpinskii, O.G., “Polytypic Relations in the Structures of the Group of Hexagonal 

Ferrites. II. Ferrites of Ba, Pb, Sr, K”, Sov. Phys.-Crystallogr. (Engl. Transl.), 33, 381–383 (1988), 

translated from Kristallografiya, 33, 646–649 (1988) (Crys. Structure, Theory, 7) 

[1988Wri] Wriedt, H.A., “O-Pb (Oxygen-Lead)”, Bull. Alloy Phase Diagrams, 9(2), 106–127 (1988) (Crys. Structure, 

Phase Diagram, Review, 174) as quoted by [2001Guz] 

[1989Rag] Raghavan, V., “The Fe-O-Pb System”, Ternary Systems Containing Iron and Oxygen, 5, 242–244 (1989) 

(Phase Diagram, Review, #, 9) 

[1992Rez] Reznitskii, L.A., “Estimate of the Enthalpies of Formation of Compounds with the Magnetoplumbite 

Structure MFe 12O 19 (M = Pb, Sr, Ba) and of Barium Ferrites”, Russ. J. Phys. Chem. (Engl. Transl.), 66(7), 

1027–1028 (1992), translated from Zh. Fiz. Khim., 66, 1931–1932 (1992) (Thermodyn., Calculation, 8) 

[1995Li] Li, L., Weyl, A., Janke, D., “Solubility of Zn and Pb in Liquid Iron and their Partition Between Liquid 

Iron and Selected Steelmaking Slag Systems”, Steel Research, 66(4), 154–160 (1995) (Phase Diagram, 

Phase Relations, Thermodyn., Experimental, Kinetics, 19) 

[1997Dor] Dorsey, P.C., Qadri, S.B., Grabowski, K.S., Knies, D.L., Lubitz, P., Chrisey, D.B., Horwitz, J.S., “Epitaxial 

Pb-Fe-O Film with Large Planar Magnetic Anisotropy on (0 0 0 1) Sapphire”, Appl. Phys. Lett., 70(9), 

1173–1175 (1997) (Crys. Structure, Experimental, Magn. Prop.) cited from abstract 

[1998Cla] Clark, T.M., Evans, B.J., “Mössbauer Investigation of M-Type Hexaferrites Above Their Curie 

Temperatures”, J. Magn. Magn. Mater., 177, 237–238 (1998) (Crys. Structure, Experimental, Magn. 

Prop, 5) 

[1998Hua] Huang, Y.H., Hsu, J.H., Chen, J.W., Chang, C.R., “Granular Fe-Pb-O Films with Large Tunneling 

Magnetoresistance”, Appl. Phys. Lett., 72(17), 2171–2173 (1998) (Crys. Structure, Experimental, Magn. 


[1998Ris] Risold, D., Nagata, J.-I., Suzuki, R.O., “Thermodynamic Description of the Pb-O System”, J. Phase 

Equilib., 19(3), 213–233 (1998) (Crys. Structure, Phase Relations, Thermodyn., Experimental, 19) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_19 

ß Springer 2009

16 19 

Fe–O–Pb 

[1999Hsu] Hsu, J.H., Huang, Y.H., “Tunneling Magnetoresistance Effect in Fe-Pb-O and Fe-PbO Granular Films: a 

Comparison”, J. Magn. Magn. Mater., 203, 94–96 (1999) (Morphology, Experimental, Magn. Prop.) 


[2000Dia] Diaz-Castanon, S., Leccabue, F., Watts, B.E., Yapp, R., “PbFe 12O 19 Thin Films Prepared by Pulsed Laser 

Deposition on Si/SiO 2 Substrates”, J. Magn. Magn. Mater., 220(1), 79–84 (2000) (Crys. Structure, 

Experimental, Magn. Prop.) cited from abstract 

[2000Hsu] Hsu, J.H., Chang, C.R., Huang, Y.H., “Enhancement of Tunneling Magnetoresistance through a 

Magnetic Barrier of Granular Fe-Pb-O System”, IEEE Trans. Magn., 36(5), 2815–2817 (2000) (Morphology, 

Experimental, Magn. Prop.) cited from abstract 

[2001Dia] Diaz-Castanon, S., Leccabue, F., Watts, B.E., Yapp, R., Asenjo, A., Vasquez, M., “Oriented PbFe 12O 19 

Thin Films Prepared by Pulsed Laser Deposition on Sapphire Substrate”, Mater. Lett., 47(6), 356–361 

(2001) (Crys. Structure, Experimental, Magn. Prop.) cited from abstract 

[2001Guz] Guzei, L.S., “O-Pb. Oxygen-Lead” in “Phase Diagrams of Binary Metallic Systems” (in Russian), Lyakishev, 

N.P. (Ed.), Vol. 3, Chapter 1, Mashinostroenie, Moscow, 768–769 (2001) (Crys. Structure, Phase 

Diagram, Review, 1) 

[2002Car] Carbucicchio, M., Rateo, M., Martini, C., Palombarini, G., Benamati, G., Fazio, C., “Phase 

Composition of the Oxidised Layers Grown on Steel Exposed to Liquid Lead at 749 K”, Hyperfine 

Interactions, 141(1-4), 403–408 (2002) (Crys. Structure, Phase Relations, Experimental, Transport 

Phenomena) cited from abstract 

[2002Mar] Martirosyan, K.S., Avakyan, P.B., Nersesyan, M.D., “Phase Formation during Self-Propagation High- 

Tempetature Synthesis of Ferrites”, Inorg. Mater. (Engl. Trans.), 38, 400–403 (2002) (Crys. Structure, 

Magn. Prop., Phys. Prop., Experimental, 11) 

[2003Cas] Castro-Rodriguez, R., Palomares-Sanchez, S., Leccabue, F., Arisi, E., Watts, B.E., “Optimal Target- 

Substrate Distance in the Growth of Oxides Thin Films by Pulsed Laser Deposition”, Mater. Lett., 57 

(22-23), 3320–3324 (2003) (Crys Structure, Phase Relations, Experimental, Theory, Transport Phenomena) 


[2004Dia] Dias-Castanon, S., Faloh-Gandarilla, J.C., Leccabue, F., Albanese, G., “The Optimum Synthesis of High 

Coercivity Pb-M Hexaferrite Powders Using Modifications to the Traditional Ceramic Route”, J. Magn. 

Magn. Mater., 272, 2221–2223 (2004) (Crys. Structure, Experimental, Magn. Prop.) cited from abstract 

[2005Pal] Palomares-Sanchez, S.A., Diaz-Castanon, S., Ponce-Castaneda, S., Mirabal-Garcia, M., Leccabue, F., 

Watts, B.E., “Use of the Rietveld Refinement Method for the Preparation of Pure Lead Hexaferrite”, 

Mater. Lett., 59(5), 591–594 (2005) (Crys. Structure, Experimental, 17) 


[H] Hansen, M. and Anderko, K., Constitution of Binary Alloys, McGraw-Hill, New York (1958) 

[Mas2] Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, 

Ohio (1990) 


[V-C2] Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, 

2nd edition, ASM, Metals Park, Ohio (1991) 



MSIT 1

Iron – Oxygen – Silicon 


Olga Fabrichnaya 

Introduction 

Fe–O–Si 20 

1 

The Fe-O-Si system has several applications in materials sciences and geology. Silicon is most 

commonly used as deoxidizer for molten steel [1952Gok, 1957Fit]. Silicon is also an important 

residual alloying element in steels. The extensively studied FeO-Fe 2O 3-SiO 2 system is part of a 

slag system [1943Whi] and it is important in silica-brick technology [1989Rag]. Iron silicates 

are end members of solid solutions important for understanding of mantle mineralogy and 

seismic structure of the Earth. Therefore, elastic properties, thermal expansion and seismic 

wave velocities of these minerals were extensively studied by different techniques [2004Fab]. 

The phase transformations in the FeO-SiO2 system were experimentally studied at high 

pressures and temperatures [1967Lin, 1967Aki, 1977Aki, 1980Boh, 1987Yag]. Si, S and O 

are possible light elements, which dissolve in Fe-Ni alloys composing the outer core of the 

Earth [1989And, 1989Sve, 1991Ito]. Iron alloys and silicates were studied under extreme 

pressure and temperature conditions to understand the processes in the mantle and core of 

the Earth [1991Ito, 1996Boe]. Experiments in diamond anvil cells and shock-wave studies 

enable to study materials at the p, T conditions of the Earth interior and to interpret results of 

seismic studies [1989And, 1989Sve, 1991Ito, 2002Che]. 

In the experimental study of the iron saturated FeO-SiO2 system by [1932Bow, 1939Cro, 

1951Sch, 1952Mic, 1955All] the phase diagram was constructed and liquid compositions 

(content of FeO, Fe 2O 3, SiO 2) were determined. The silica rich part of this diagram is 

characterized by the presence of a miscibility gap in liquid. The invariant equilibrium between 

two liquids of different composition and silica was investigated by [1927Gre1, 1927Gre2]. 

[1939Cro] experimentally studied melting in the FeO-SiO 2 system in presence of Fe as well as 

in SiO 2 crucibles without Fe and demonstrated that in the later case melt consists mainly of 

Fe 3O 4 and SiO 2 forming a different series than in presence of Fe. The temperature dependence 

of solid phase buffers (univariant equilibria providing constant activity of O) was measured 

by different techniques. An electrochemical method (emf) was used by [1981Jac, 1981Sch, 

1985Jac, 1987One, 1988One, 1989Jac]. Equilibration with CO/CO 2 gas mixtures was performed 

by [1932Sch, 1946Cir, 1966Sch2], a H 2 membrane method was applied by [1978Hew] 

and a thermogravimetric method by [1965Val, 1983Mye]. [1948Dar] investigated SiO 2 + 

Fe 3O 4+slag and SiO 2+Fe 2SiO 4+slag equilibria at different CO 2/CO gas mixtures to determine 

melting temperatures. Using data from an earlier study [1932Sch] the phase diagram 

log 10(p CO2/p CO) vs temperature was constructed by [1948Dar]. An investigation of [1952Mic] 

provides information on SiO2+slag and SiO2+Fe3O4+slag equilibria at different oxygen partial 

pressures and temperatures. Schühmann and Esio [1951Sch] determined the oxygen 

partial pressure by recording the CO 2/CO ratio in gas phase bubbled through slag in Fe 

crucibles. The composition of slag was also analyzed. Distin et al. [1971Dis] carried out oxygen 

content measurements in liquid Fe for calculation of the FeO activity in FeO-SiO 2 liquid 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

2 20 

Fe–O–Si 

equilibrated with liquid iron. Bodsworth [1959Bod] used Fe crucibles and H 2/H 2O mixtures 

to determine the oxygen partial pressure of FeO-SiO 2 liquid in equilibrium with metallic Fe. 

Schühmann et al. [1953Sch] used a quenching technique to study the liquidus surface in 

the FeO-Fe 2O 3-SiO 2 region between 1250 and 1450˚C. Muan [1955Mua] presented liquidus 

data at oxygen partial pressures ranging from 10 –11 to 1 bar. Turkogan and Bill [1957Tur] 

equilibrated melt with CO2/CO gas mixtures at 1550˚C. Their values were used by [1962Tur] 

to calculate SiO2, FeO and Fe2O3 activities in melt. Oishi et al. [1982Ois] performed electromotive 

force measurements of slag at 1300˚C. Their data for SiO 2+Fe+slag equilibria deviate 

from [1951Sch, 1952Mic]. 

Silicon is the most commonly used deoxidizer for steel. Therefore the equilibrium between 

silicon and oxygen in molten iron was studied in many works [1950Hil, 1952Gok, 1961Hsi, 

1967Buz, 1969Nov, 1970For, 1974Ark, 1977She, 1981Ave, 2005Shi]. Solubility of oxygen in 

Fe-Si melt was recently studied by [2005Shi] in inert atmosphere at 1600˚C. A minimum of the 

oxygen solubility at 20 mass% Si was indicated by [2005Shi]. At the same temperature of 

1600˚C, [1961Hsi], [1967Buz], [1969Nov] and [1977She] indicated minima at 5-6, 6.8, 3.6 or 

3.89 mass% Si, respectively, while [1950Hil, 1952Gok] studied compositions up to 10 and 

15 mass% Si, respectively and in both works no minimum was found. [1974Ark] indicated the 

presence of a minimum in the solubility curves at 1600-1700˚C. A maximum of the oxygen 

solubility at 85 mass% Si mentioned by [2005Shi] is based on thermodynamic calculations. 

There is no experimental confirmation of this maximum. An isothermal section at 1600˚C 

showing details of the Si and O solubility in the Fe rich corner was constructed in the works 

[1952Gok, 1970For]. An assessment of interaction parameters is presented by [1966Sch1, 

1974Sig]. 

The equilibrium between silicon and oxygen in (δFe) in contact with liquid iron has been 

studied by [1970Nis] and [1981Fuj]. [1981Fuj] calculated a first-order interaction coefficient 

in the δ phase for compositions up to 0.1 mass% Si. 

The activities of Si and O in liquid iron alloys were studied by [1967Sch, 1973Vla, 

1986Zin] using the emf technique. [1964Tay, 1981Lev] applied the emf method to derive 

the Gibbs energy of the Fe 2SiO 4 (fayalite) phase. Activity of FeO in the FeO-SiO 2 system was 

measured by a gas equilibration technique [2004Fre]. Ban-ya et al. measured the activity of 

FeO at 1400˚C [1980Ban] and the enthalpy of mixing of FeO-SiO2 melts at 1420˚C in Fe 

crucibles [1982Ban]. 

A review of thermodynamic data (enthalpy of formation, entropy and C p) of the phases in 

the FeO-Fe 2O 3-SiO 2 system is presented by [2004Fab]. There are calorimetric data available 

for fayalite [1952Kin, 1953Orr, 1982Wat, 1982Rob] and for the high-pressure phases γ-spinel 

Fe 2SiO 4 [1982Wat, 1979Nav, 1989Aka, 2007Yon] and FeSiO 3 [1982Wat, 1979Nav]. Thermodynamic 

data for high-pressure phases were also calculated from phase equilibria for ferrosilite 

[1980Boh] and for γFe2SiO4 [1965Aki, 1977Aki, 1979Oht, 1987Yag]. 

Reviews of experimental data available for the Fe-O-Si system were presented by 

[1937Wen, 1943Whi, 1957Fit, 1965Mua, 1989Rag, 2004Fab]. 

There are several thermodynamic assessments of the Fe-O-Si system [1979Kau, 1980Goe, 

1985Bjo, 1993Wu, 1996Sax, 1997Fab, 1997Sel, 1999Rom, 2004Jun1, 2007Jak]. [1979Kau] used 

the substitutional solution model for the liquid phase and calculated phase diagrams. 

[1997Sel] and [1997Fab] used the ionic liquid model to describe the liquid phase and obtained 

very similar results. The difference between these two assessments is in the thermodynamic 

parameters selected for the phases and in the additional consideration of high pressure 

phases by [1997Fab]. [1980Goe] used the associate model to describe the liquid phase. 



MSIT 1

[1985Bjo] described liquid as an ideal solution of three silicate complexes. [1985Sas] used the 

model of central atom to calculate activity, enthalpy of mixing and enthalpy of formation of 

fayalite. [2002Dav] also assessed this system using the associate model. [1993Wu, 1999Rom] 

assessed the FeO-SiO 2 system using the quasichemical model. The modified quasichemical 

model was also used by [2004Jun1, 2007Jak] to assess thermodynamic parameters in the FeO- 

Fe 2O 3-SiO 2 system and to calculate phase diagrams. Jung et al. [2004Jun2] used a modified 

Wagner model to calculate deoxidation equilibria in liquid iron for 15 elements including Si. 

Experimental and theoretical studies of the Fe-O-Si system are summarized in Table 1. 


The Fe-Si binary system is accepted from [1982Kub]. Si-O is accepted from [1992Hal] based 

on an evaluation of [1990Wri]. Polymorphic transformations in SiO 2 at high pressures 

and temperatures are accepted from [2004Fab]. The phase diagram of the Fe-O system is 

accepted from [1991Sun]. The thermodynamic assessment of [1991Sun] gives results very 

close to [Mas2]. 



3 

The crystallographic data for solid phases are listed in Table 2. Fe and Si have very low 

solubility for oxygen, Si has practically no solubility for Fe, while Fe can dissolve up to 25 

at.% of Si. The SiO2 binary compound undergoes polymorphic transformations, the order 

with increasing temperature is α-quartz, β-quartz, tridymite, crystobalite. Two high pressure 

modifications of SiO 2 were found experimentally with coesite and stishovite structure. Coesite 

forms at a pressure of 3-4 GPa. With the pressure increasing above 9 GPa it transforms to the 

more dense stishovite phase with rutile structure. At atmospheric pressure only one ternary 

phase Fe 2SiO 4 (fayalite) is stable, having the olivine structure. However, at pressures of 

5-8 GPa fayalite transforms to the spinel structure (γ-spinel), which decomposes to a mixture 

of FexO (wüstite) and SiO2 (stishovite) at pressures of about 18 GPa. A crystal structure 

investigation of spinel Fe2SiO4, performed by [1990Din], indicates that it has mixed normalinverse 

structure - 37.9% of Si occupy octahedral sites and 18.9% of Fe occupy tetrahedral 

sites. A FeSiO 3 ferrosilite ternary phase with pyroxene structure forms at 1-3 GPa from 

fayalite and SiO 2 (β-quartz) [1980Boh]. At high pressures and temperatures an ortho modification 

and two clino modifications of pyroxene were found [1984Sue, 1997Hug, 1997Woo] 

(see Fig. 1). According to the phase diagram presented by [1994Hug] a triple point for 

ferrosilite composition is placed at 4.6 GPa and a temperature of about 800˚C. [1997Woo] 

studied the equilibrium between ortho- and high-clinoferrosilite at 800-1300˚C. [1983Web] 

reported high-temperature pyroxenoid FeSiO3 with triclinic structure, synthesized at 2 GPa 

and 1250˚C. Ferrosilite decomposes in the range 8-10 GPa to a mixture of γ spinel Fe 2SiO 4 and 

SiO 2 (Stishovite). Calculated p-T phase diagrams of SiO 2 and FeO-SiO 2 systems at high 

pressures are presented in [2004Fab] (see Fig. 2 and 3). Transformations between the ortho 

and clino modifications of FeSiO 3 are not shown in Fig 3, because these two phases were 

described as a single phase by [2004Fab] due to lack of thermodynamic data. Several experimental 

studies [1992Ros, 1997Oht, 1998Ang, 1998Woo, 2000Haz] indicated stability of 

spinelloid solid solutions of composition Fe3–xSixO4 (x = 0.28-0.75), which form in the 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

4 20 

Fe–O–Si 

Fe 3O 4-Fe 2SiO 4 system at pressures of 3-8 GPa. A complete solid solution with γ-spinel 

structure is stable in this system above 9 GPa. In this work γ-spinel and Fe 3O 4 are presented 

as different phases because at normal pressure Fe 3O 4 does not dissolve any Fe 2SiO 4. According 

to [2000Woo] there are three spinelloid polytypes II, III and V (spd II, spd III, spd V) which 

differ in the b unit cell parameter. The phase diagram of [2000Woo] at 1100˚C is presented in 

Fig. 4. It was also shown by [2000Woo] that a phase Fe7SiO10, previously reported as 

metastable [1985Mod], appears in phase assemblages at 5-6 GPa and therefore it is a stable 

phase at moderate pressures. The crystal structure of Fe 7SiO 10 was investigated by [2005Ake] 

using TEM and, combining the obtained results with XRD data of [1985Mod], a space group 

different from that given by [1985Mod] was determined for this compound. 


The isobaric section of the FeO-Fe2O3-SiO2 system at the oxygen partial pressure of air 

approximately is a quasibinary system Fe 3O 4-SiO 2 [1965Mua], because magnetite is stable 

phase at this condition. Strictly speaking this diagram is not exactly quasibinary, because the 

Fe +2 /Fe +3 ratio of Fe 3O 4 in air slightly changes with temperature. Experimentally this system 

was studied by [1927Gre2, 1955Mua]. The results of these experimental studies are summarized 

in [1959Phi, 1965Mua]. The calculated diagram at oxygen partial pressure of air agrees 

well with data of [1965Mua], it is presented in Fig. 5. 

A calculated phase diagram of the Fe2O3-SiO2 system [1997Sel] is presented in Fig. 6. In 

this calculation the gas phase is suppressed and thus it is hypothetical, as at elevated temperatures 

all Fe-containing phases decompose into O 2 gas and phases with lower O-content. 

The miscibility gap in the iron-saturated FeO-SiO 2 system was studied by [1927Gre1]. The 

phase diagram of the FeO-SiO 2 system at iron saturation was experimentally studied by 

[1932Bow]. The corresponding calculated phase diagram from [1997Fab] is presented in 

Fig. 7a. The Fe 2O 3 content in the liquid phase is presented in Fig. 7b. Strictly speaking this 

diagram is not exactly quasibinary, because metallic Fe is present at some amount. 

Kato et al. [1984Kat] investigated melting relations in the Fe2SiO4-FeSiO3 quasibinary part 

of the FeO-SiO2 system at pressures of 5, 6 and 9 GPa. Between the fayalite and ferrosilite 

compositions a eutectic melting occurs. Ferrosilite was observed to melt incongruently forming 

liquid and coesite. Phase diagrams at 6 and 9 GPa from [1984Kat] are presented in Figs. 8a 

and 8b. 


A reaction scheme of the Fe-Fe2O3-SiO2-Si partial system is presented in Figs. 9a to 9c. Itis 

based on the review of [1989Rag] with some corrections according to [1997Fab]. This scheme 

does not include equilibria with the gas phase. Details (temperatures and phase compositions) 

of the invariant reactions in the FeO-Fe 2O 3-SiO 2 system calculated by [1997Fab] are presented 

in Table 3. 

Invariant equilibria at high pressures were determined by [1984Kat]. A eutectic point 

L Fe Ð Fe 2SiO 4+FeSiO 3 was indicated at an Fe 2SiO 4 content of 74 mol% and a temperature of 

1335˚C at 6 GPa. A eutectic point L Ð γFe2SiO4+FeSiO3 was indicated at 55 mol% Fe2SiO4, 

1530˚C and 9 GPa. A peritectic formation of FeSiO3 from liquid and SiO2(Coes) was 



MSIT 1

determined at 35 mol% of Fe 2SiO 4 at 1435˚C at 6 GPa and 15 mol% Fe 2SiO 4 at 1610˚C and 

9 GPa. According to [1967Aki] an invariant point αFe 2SiO 4-γFe 2SiO 4-liquid was indicated at 

1520˚C and 6.2 GPa, while [1979Oht] placed this point at the same temperature but at a 

pressure of 7 GPa. 


The liquidus surface projection of the FeO-Fe 2O 3-SiO 2 partial system, calculated by 

[1997Fab], is presented in Fig. 10. It agrees well with the experimental data of [1953Sch, 

1955Mua]. A schematic liquidus surface of the larger region Fe-Fe 3O 4-SiO 2-Si from [1989Rag] 

is presented in Fig. 11 based on calculations performed by [1973Iye]. 

The Tr = Cr transformation in SiO 2 was not taken into account by [1989Rag] and the 

corresponding degenerated reactions D 1 and D 2 at 1471˚C are not shown in the reaction 

scheme. 

Liquidus phase relations at high pressures were established in the works of Lindsley 

[1964Lin, 1967Lin], Alimoto et al. [1967Aki], Ohtani [1979Oht] and Kato et al. [1984Kat]. 

The schematic liquidus relations of the FeO-SiO 2 system at high pressures are presented in 

Fig. 12, taken from [1984Kat]. [1967Aki] found that both αFe 2SiO 4 and γFe 2SiO 4 melt 

congruently at pressures up to ~7 GPa. [1979Oht] confirmed congruent melting of 

γFe 2SiO 4 up to 13 GPa, while at pressures above 13 GPa it melts incongruently decomposing 

to liquid and stishovite. The phase diagram from [1979Oht] is presented in Fig. 13. 


In the work of Schuhmann et al. [1953Sch] isothermal sections of the FeO-Fe 2O 3-SiO 2 partial 

system were constructed based on experimental phase equilibrium studies at 1250, 1300, 1350, 

1400, 1450˚C. Isothermal sections at lower temperatures (1000˚C and 25˚C) are constructed by 

extrapolations. [1982Ois] constructed a partial isothermal section at 1300˚C from emf measurements. 

[1997Sel] and [1997Fab] calculated isothermal sections at 1300 and 1450˚C, which 

are in reasonable agreement with data of [1953Sch, 1982Ois], although the experimental 

solubilities of FeO and Fe 2O 3 in liquid at 1300˚C are slightly higher than the calculated 

ones. The isothermal sections at 1300 and 1450˚C from [1997Fab] are presented in Figs. 14a 

and 14b. 

The isothermal section of the iron rich corner of the Fe-O-Si system at 1600˚C showing 

details of solubilities at SiO 2 saturation is shown in Fig. 15 according to [1989Rag]. 

Potential Diagrams 


5 

The potential diagram log 10(p CO2/p CO) vs temperature was constructed by Darken [1948Dar] 

including his own experimental results and results from other studies. The value of log 10(p CO2/ 

p CO) is directly related to the partial pressure of oxygen at the temperature given. Figure 16 

presents a diagram of this type, log 10(p CO2/p CO) vs T, of the FeO-SiO 2-O 2 partial system, 

calculated by [1997Fab]. It agrees very well with the diagram of [1948Dar] and with results of 

[1932Sch, 1946Cir, 1952Mic, 1951Sch, 1927Gre2, 1966Sch2]. The potential diagram for 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

6 20 

Fe–O–Si 

equilibrium between liquid and silica, calculated at 1250, 1300 and 1350˚C is presented in 

Fig. 17. This diagram demonstrates that the content of Fe 2O 3 in slag equilibrated with SiO 2 at 

fixed partial pressure of oxygen does not depend on the temperature in the calculated 

temperature region. The calculated diagrams agree well with the experimental data of 

[1952Mic, 1982Ois]. 


The reaction of dissolution of silicon and oxygen in liquid iron was studied in many works 

[1950Hil, 1952Gok, 1961Hsi, 1967Buz, 1969Nov, 1970For, 1974Ark, 1977She, 1981Ave, 

2005Shi]. The thermodynamic treatment of experimental results is based on the following 

reaction: SiO 2(s)=[Si]+2[O], where symbols in square brackets are concentrations of components 

in liquid Fe expressed in mass%. This equilibrium was thermodynamically treated by the 

mass action law expressing the product of activities of O and Si in Fe melt by an equilibrium 

constant [1952Gok] (corrected in [1953Chi]), 1967Buz, 1969Nov, 1973Iye, 1974Sig, 1977She, 

1981Ave, 1986Zin, 1999Ma, 2005Mik, 2005Shi]. The first-order interaction parameters at 

1600˚C recommended by [1974Sig] are e Si O= – 0.131, e O Si= – 0.23, e O O= – 0.20, e Si Si= 0.11. 

A modified Wagner formalism taking into account the formation of SiO associates was used by 

[2004Jun2] to calculate deoxidation equilibria in liquid iron at 1550-1650˚C. [1998Lee] used 

the ionic liquid model to describe deoxidation equilibria in liquid iron at 1600˚C. Calculated 

solubilities of O and Si in liquid Fe at 1545, 1600 and 1650˚C from [1997Sel] are presented in 

Fig. 18. The results are in good agreement with [1952Gok]. 

The activities of Si and O in liquid iron alloys were studied by [1967Sch, 1973Vla, 

1986Zin] using the emf technique. The emf method was used to derive the Gibbs energy of 

formation of Fe 2SiO 4 (fayalite) in the works of [1964Tay, 1981Lev]. The activity of FeO in the 

FeO-SiO 2 system was measured by gas equilibration technique [1951Sch, 1959Bod, 1980Ban, 

2004Fre]. Vapor pressure measurements were performed by [1971Dis] to determine FeO 

activities at high temperatures. Calculated FeO activities at 1263, 1315, 1364, 1407˚C from 

[1997Fab] are presented in Fig.19a. They agree well with [1951Sch, 1959Bod]. Calculated FeO 

activities at 1785, 1880 and 1960˚C are presented in Fig. 19b. They reproduce the experimental 

data of [1971Dis] within the uncertainty limits. Calculations of FeO activities in liquid, 

performed in the present evaluation using the thermodynamic database of [1997Fab] show 

reasonable agreement with data of [2004Fre] at 1550 and 1600˚C. 

Ban-ya et al. [1982Ban] measured enthalpies of mixing of FeO-SiO 2 melts in Fe crucibles 

at 1420˚C. The calculated enthalpy of mixing of FeO-SiO 2 melts in equilibrium with metallic 

Fe from [1997Fab] is presented in Fig. 20. 

A review of experimental data for thermodynamic values H, S and Cp for phases in the 

FeO-Fe2O3-SiO2 system is presented by [2004Fab]. There are calorimetric data available 

for the enthalpy of formation of fayalite [1952Kin], entropy derived from adiabatic calorimetry 

measurements [1982Rob], enthalpy of fusion obtained by drop calorimetry [1953Orr, 

1984Ste], enthalpy increment obtained by drop calorimetry [1953Orr] and heat capacity 

measurements by differential scanning calorimetry [1982Wat]. For the high-pressure 

phases γ-spinel Fe 2SiO 4 the enthalpy of transformation was obtained by solution calorimetry 

[1979Nav] and drop calorimetry [1989Aka], entropy was derived from adiabatic 

calorimetry data [2007Yon] and heat capacity was obtained by differential scanning calorimetry 

[1982Wat]. Enthalpy of formation of ferrosilite FeSiO3 was obtained by solution 



MSIT 1

calorimetry [1979Nav] and heat capacity was measured by differential solution calorimetry 

[1982Wat]. The thermodynamic data for high-pressure phases were also calculated [1997Fab] 

using available phase equilibria and calorimetric data along with equations of state to take into 

account pressure contribution to Gibbs energy. In calculations, phase equilibrium data of 

[1980Boh] were used for ferrosilite and data of [1965Aki, 1977Aki, 1979Oht, 1987Yag] for 

γFe 2SiO 4. 

There are several thermodynamic assessments of the whole Fe-O-Si system [1979Kau, 

1980Goe, 1985Bjo, 1993Wu, 1997Fab, 1997Sel, 1999Rom, 2004Jun1, 2007Jak] using different 

models for the liquid phase. [1979Kau] used the substitutional solution model, [1997Sel] used 

the ionic liquid model and [1980Goe, 1985Bjo, 2002Dav] used the associate model. [1993Wu, 

1999Rom] assessed the FeO-SiO 2 partial system using the quasichemical model. The quasichemical 

model was also used by [2004Jun1, 2007Jak] to assess thermodynamic parameters in 

the FeO-Fe 2O 3-SiO 2 system. 

The thermodynamic description of [1997Fab] using the ionic liquid model is recommended 

in the present work, because it reproduces well experimental data at 1 bar and at high 

pressures. Thermodynamic values calculated by [1997Fab] are presented in Tables 4 and 5. 



7 

For geophysical applications data like compressibilities, thermal expansions and seismic wave 

velocities of Fe-containing silicates are important, measured for example by static compression, 

ultrasonic and Brillouin scattering. The bulk elastic modulus and its pressure derivative 

are usually derived from static compression experiments. Sound velocities are derived from 

Brillouin spectroscopic data. Thermal expansion is usually studied by in-situ XRD measurements. 

Review papers are devoted to thermal expansion of spinels [1985Tay] and to thermoelastic 

properties of phases in the FeO-Fe 2O 3-SiO 2 system including high-pressure phases 

[2004Fab]. 

Magnetic properties of orthoferrosilite FeSiO 3 were determined by susceptibility and 

magnetization measurements as well as by Mössbauer spectroscopy [1986Reg]. From these 

data the temperature of magnetic ordering was obtained as 40 K. The electric field gradient for 

Fe2SiO4 (fayalite) was determined by Mössbauer spectroscopy of a single crystal [2002Lot]. 

Magnetic properties of spinel and spinelloid structure in the Fe 2SiO 4-Fe 3O 4 system were 

measured by [2001Yam1, 2004Kon]. Electric properties of spinel solid solutions in the 

Fe 2SiO 4-Fe 3O 4 system were measured by [2001Yam2]. Magnetic properties of the mineral 

iscorite Fe 7SiO 10 was measured by [1985Mod]. Paramagnetic behavior was found at temperatures 

above –23˚C, weak ferromagnetism was found at temperatures below –23˚C. 

Hardness of oxide scales on Fe-Si alloys is important to determine hot-rolling conditions 

for production of outstanding steels. Microhardness measurements on Fe-Si alloys (up to 

3 mass% Si) at room temperature and high temperatures were performed by [2006Ama] after 

oxidation at 800 and 1000˚C. 

Recently attention was focused on synthesis and properties of nanocomposite materials in 

the Fe-O-Si system for potential applications in electronics and optics [2006Kim]. The 

alternating current electrical conductivity of gel-derived glass of composition 55Fe 2O 3- 

45SiO 2 (mol%) was measured by [2006Bas] after reduction at 650˚C and further heattreatment 

in air at 500˚C to grow Fe-core Fe 3O 4 shell nanostructure, which forms a percolate 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

8 20 

Fe–O–Si 

network within silica gel. Magnetic properties of nanocomposite Fe-SiO 2 powders were 

studied by [2006Kim]. 

[2003Kap] studied the contact angle of liquid Fe on a SiO 2 substrate under Ar and CO- 

CO 2-Ar atmospheres in the temperature range 1550-1560˚C using X-rays and the sessile-drop 

method. The angle was found to be around 135˚. Fayalite slag formed due to reaction between 

substrate and Fe was found to accumulate around the drop. The results are of relevance to 

explain the mechanism of corrosion of SiO2 containing refractory materials by liquid Fe. 

Experimental studies of material properties are presented in Table 6. 

Miscellaneous 

Conditions for nucleation of oxide particles during deoxidation are reviewed and recent 

experimental studies of the nucleation of SiO2 are described by [1972Sig]. The critical 

supersaturation is discussed and influence of the rate of mixing of deoxidant addition on 

the number of particles of deoxidation products is considered. Several studies are devoted to 

internal oxidation of Fe-Si alloys [1960Sch, 1984Tak, 1986Wie1, 1986Wie2, 1986Tak, 

2006Tak]. Diffusion coefficients of oxygen in Fe-Si alloys were derived from experimental 

data in [1960Sch, 1984Tak, 1986Tak]. [1987Lee] studied initial oxidation of Fe-Si alloys at 

25˚C by different kinds of surface spectroscopies. [1976Mor] studied transition from external 

to internal oxidation in Fe-Si alloys as function of oxygen partial pressure. [1971Log] studied 

morphology and structure of wustite-fayalite scale formed on Fe-Si alloys during oxidation by 

CO2/CO gas mixtures at 1000˚C. [1982Rol] studied oxidation and creep of Fe-Si alloys. 

[1998Won] reported precipitation kinetics of Fe contamination at a Si-SiO 2 interface during 

dry oxidation at 900˚C based on TEM and atomic force microscopy. 

[1967Eib] investigated crystal structure of fayalite Fe 2SiO 4 by Mössbauer spectroscopy as 

function of temperature. Splitting of lines, which became more pronounced at high temperatures, 

confirms that Fe +3 occupies both non-equivalent octahedral sites of the fayalite structure. 

[1992Bec] investigated fayalite Fe 2SiO 4 at elevated temperatures by Mössbauer 

spectroscopy, also. The pO2 dependent broadening of Mössbauer lines was discussed in context 

of fayalite crystal structure. Kinetics of fayalite formation from FeO and SiO2 were investigated 

in [1992Bec]. 

Ross et al. [1999Ros1, 1999Ros2] obtained Raman spectra and electronic absorption 

spectra for clinoferrosilite at high pressures. Transformation of low-clinoferrosilite to highclinoferrosilite 

with pressure increase and back with pressure decrease was observed in-situ 

[1999Ros1]. [1999Ros2] showed that high FeSiO 3 (space group C2/c) gained additional 

stabilization energy at high pressure due to crystal field effect of Fe +2 in octahedral sites. 

Results of Ito [1991Ito] on interaction between molten iron and silicate at high pressure 

and temperature indicate that certain amount of SiO2 dissolves into liquid iron from silicate 

melt. These results confirm that Si and O may be important alloying light elements of Earth’s 

core if core segregation proceeds in magmatic ocean of the proto-Earth. 

[2001Bel] constructed a molecular dynamic model of the FeO-SiO 2 system using Born- 

Mayer pair potential. The potential includes effective dipole-dipole interaction for Fe-Si pairs 

obtained from experimental data for the Gibbs energy of solution. 



MSIT 1

. Table 1 

Investigations of the Fe-O-Si Phase Relations, Structures and Thermodynamics 


[1927Gre1] Phase equilibria in gas furnace, 

temperature control by optical 

pyrometry, quenching, microscopic study 

[1927Gre2] Melting in electric furnace in air, 

temperature measurement by optical 

pyrometry, chemical analysis 

[1932Bow] Phase equilibria in presence of Fe, 

chemical analysis, microscopic study 


Range Studied 

1700˚C, FeO-SiO2, liquid miscibility gap 

1660˚C, FeO-Fe2O3-SiO2, liquid miscibility 

gap 

1100-1800˚C, Fe-FeO-SiO2 

[1932Sch] Equilibration with CO/CO2 gas mixtures 900˚C, Fe2O3-10SiO2,Fe2O3-SiO2, 3Fe2O3- SiO2 

[1939Cro] Phase equilibria in Fe- and siliceous 

crucibles, microscopic study, chemical 

analysis 

1200-1600˚C, Fe-FeO-Fe2O3-SiO2 [1948Dar] Equilibration with CO/CO 2 gas mixtures 900-1600˚C Fe-O-Si log 10(P CO2/P CO) in the 

range between –2 and 4 

[1950Hil] Phase equilibria in SiO2, MgO, Al2O3 crucibles in Ar atmosphere 

[1951Sch] Equilibration with CO/CO2 gas mixtures in 

Fe-crucibles, chemical analysis 

[1952Gok] Equilibration Fe-O-Si alloys in SiO2 crucibles with H2O/H2 gas mixture, 

quenching and chemical analysis 

1550, 1600, 1650˚C, Fe-Si alloys 

0.001-10 mass% Si 

1263, 1315, 1364, 1407, FeO-SiO 2 (up to 

50 mass% SiO2) in presence of Fe 

1545-1650˚C, up to 15 at.% Si, H 2O/H 2 in 

the range 0.002-0.326 

[1952Kin] HF solution calorimetry 25˚C, Fe2SiO4 (fayalite) enthalpy of 

formation 

[1952Mic] Equilibration with CO/CO2 gas mixtures, 

SiO2 crucibles 

1250, 1300, 1350˚C, FeO-Fe2O3-SiO2 [1953Orr] Drop-calorimetry 25-1451˚C, Fe2SiO4 (heat content, 

enthalpy of fusion) 

[1953Sch] Equilibration in Pt-crucibles in nitrogen 

atmosphere, quenching, optical 

microscopy 

1250-1450˚C, FeO-Fe2O3-SiO2 [1955All] Equilibration in Fe crucibles in CO/CO 2 

gas mixtures, quenching, XRD, optical 

microscopy 

[1955Mua] Equilibration with CO 2/H 2, quenching, 

XRD, optical microscopy 

[1955Sch] Thermodynamic calculations of isoactivity 

lines 



MSIT 1 


1150-1400˚C; FeO-Fe 2SiO 4 in presence of 

Fe 

1200-1473˚C, p(O 2) in the range 

10 –10.9 -1 atm, FeO-Fe 2O 3-SiO 2 

1350˚C, FeO-Fe 2O 3-SiO 2 (FeO from 40 to 

100 mass%, Fe 2O 3 from 0 to 60 mass%) 

9 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

10 20 

Fe–O–Si 



[1957Tur] Equilibration with CO/CO 2 gas mixtures, 

chemical analysis after quenching 

[1959Bod] Equilibration with H2O/H2 gas mixtures, 

chemical analysis after quenching 

[1960Sch] Heat treatment in H2O/H2 and CO/CO2 atmosphere 

[1962Tur] Calculations of activities of SiO 2, FeO, 

Fe 2O 3 from phase equilibrium data 

[1964Lin] Piston-cylinder high-pressure apparatus, 

XRD 


Range Studied 

1550˚C, FeO-Fe 2O 3-SiO 2 

1265, 1305, 1365˚C, FeO-SiO 2 in presence 

of Fe 

820-1056˚C, Fe-Si alloys 0.24-1.6 mass% Si 

1550˚C, FeO-Fe 2O 3-SiO 2 

1150˚C, 1.8 GPa; 1400˚C, 4.5 GPa; 

Fe 2SiO 4+SiO 2 

[1964Tay] EMF 750-1200˚C, Fe2SiO4, Gibbs energy of 

formation 

[1965Aki] Tetahedral-anvil high-pressure apparatus, 

XRD 

700-1200˚C, 4-7 GPa; Fe2SiO4 [1966Sch2] Equilibration with CO/CO2 gas mixtures, 

XRD, optical microscopy 

[1967Aki] Tetahedral-anvil high-pressure apparatus, 

XRD 

[1967Buz] Phase equilibria in SiO2 crucibles in Ar 

atmosphere, XRD 

1000-1200˚C, solid phase oxygen buffers 

in Fe-O, Fe-SiO 2-Fe 2SiO 4,Fe 2SiO 4-Fe 3O 4- 

SiO 2 systems 

800-1700˚C, 2-7.6 GPa; Fe2SiO4 (α = γ 

transition, melting) 

1600˚C, Fe-Si alloys 0.01-15.5 mass% Si 

[1967Eib] XRD, Mössbauer spectroscopy –193-727˚C, Fe 2SiO 4 

[1967Sch] EMF 1600˚C, Fe-Si alloys equilibrated with SiO2 1.39-3.13 mass% Si 

[1969Kul] Thermodynamic calculations of partial 

pressures of species in gas phase 

1600˚C, FexO-SiO2 [1969Nov] Phase equilibria in SiO 2 crucibles, 


[1970Nis] Equilibrium in Ar atmosphere, chemical 

analysis 

[1971Dis] Equilibration of levitated Fe beads with 

molten FeO-SiO 2 slag 

[1971Log] Heat treatment with CO/CO 2 mixture, 

optical, electron microscopy, microprobe, 

metallography, chemical analysis 

1600˚C, Fe-Si alloys 0.008-50 mass% Si 

1550˚C, up to 0.07 at.% Si 

1785-1960˚C, FeO-SiO 2 (in equilibrium 

with Fe) activity of FeO 

1000˚C, Fe-Si alloy, 1.5 mass% Si 

[1972Sig] Polarography 1550˚C, Fe-Si (0.48 and 1.17 mass% Si) 

[1973Iye] Calculations based on phase equilibria 1200-1730˚C, Fe-Si-O 

[1973Vla] EMF 1550-1650˚C, Fe-Si-O melt Si 

0.01-2 mass% 



MSIT 1



[1974Ark] Equilibration in Ar atmosphere, chemical 

analysis 

[1976Mor] Heat treatment in gas mixture H 2O/H 2, 

Chemical analysis, IR-spectroscopy 

[1977Aki] Cubic-anvil high pressure apparatus, 

in-situ XRD 

[1977She] Equilibration in Ar atmosphere, chemical 

analysis 

[1978Hew] Hydrothermal system using hydrogen 

diffusion membrane 


Range Studied 

1600˚C, Fe-Si alloys 0.008-100 mass% Si 

850˚C, Fe-3 mass% Si 

600-1100˚C, p(GPa) = 3.64+0.0025T(˚C) 

Fe 2SiO 4 (α = γ transformation) 

1600, 1650˚C, Fe-Si alloys 0.01-40 mass% 

Si 

650-850˚C, 0.1 GPa, Fe2SiO4+Fe3O4+SiO2 

(QFM) buffer 

[1979Kau] Calphad 25-2127˚C, Fe2O3-SiO2,Fe3O4-SiO2, FeO-SiO2 

[1979Nav] Solution calorimetry (2PbO·B2O3 melt), 713˚C, αFe2SiO4, γFe2SiO4, FeSiO3 high pressure synthesis, XRD, microprobe, 

microscopy, calculations 

Enthalpy of transformation and reactions 

[1979Oht] Multianvil high pressure apparatus, XRD, 

optical microscopy 

[1980Ban] Equilibration with H2O/H2 gas mixture in 

iron crucibles 

[1980Boh] Piston-cylinder high pressure apparatus, 

XRD, electron microprobe 

[1980Goe] Thermodynamic calculations based on 

associate model for liquid 

[1981Ave] Equilibrium in H 2O-H 2-Ar mixture in SiO 2 

crucibles 

1000-2700˚C, 5-20 GPa, αFe 2SiO 4, 

γFe 2SiO 4 melting 

1400˚C, FexO-SiO2, activity of FexO 

700-1050˚C, 1-1.6 GPa, FeSiO 3 

1100-1400˚C, Fe-FeO-Fe 2O 3-SiO 2 

1600, 1650, 1700˚C, Fe-Si alloys with 

0.005-2.32 mass% Si 

[1981Fuj] Zone melting technique 1530-1535˚C, δFe-Si alloy up to 0.1 mass 

%Si 

[1981Lev] EMF 1100-1300˚C, Gibbs energy of formation 

of Fe2SiO4 [1982Ban] High-temperature isoperibolic 

calorimetry 


1420˚C, Fe xO-SiO 2 x(SiO 2) from 0 to 

20 mol% 

11 

[1982Ois] EMF 1200, 1300˚C, SiO2 saturated iron silicate 

slag in the range from Fe to Fe3O4 saturation 

[1982Rob] Adiabatic calorimetry –268-108˚C, Fe2SiO4 (fayalite) 

[1982Rol] XRD, optical and electron metallography 700-800˚C, pO2 = 2·10 3 -1.013·10 5 Pa, 16 N/ 

mm 2 tensil stress, Fe-Si (1 and 4 mass% Si) 

[1982Wat] Differential scanning calorimetry 77-427˚C, α- and γFe2SiO4, FeSiO3 clinopyroxene (heat capacity) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

12 20 

Fe–O–Si 



[1983Kuh] XRD, SEM, IR-spectroscopy, X-ray 

photoelectron spectroscopy 

[1983Mye] Thermogravimetric gas mixing furnace, 

CO 2/H 2 gas mixtures, oxygen partial 

pressure measurement with ZrO 2 

electrode, equilibrium control 


Range Studied 

850˚C, Fe-Si alloys 10-40 mass% Si 

800-1300˚C, solid phase oxygen buffers 

in Fe-O, Fe-SiO 2-Fe 2SiO 4,Fe 2SiO 4-Fe 3O 4- 

SiO 2 systems 

[1983Web] Piston-cylinder, XRD 1250˚C, 2 GPa, FeSiO3 triclinic structure 

[1984Kat] Multianvil high-pressure apparatus, XRD, 

electron microprobe 

1250-1550˚C, 5-9 GPa, Fe2SiO4-FeSiO3 [1984Ste] Drop calorimetry 712-1432˚C, Fe2SiO4 (fayalite) 

[1984Sue] High-temperature XRD, FeSiO3 hydrothermal synthesis at 800˚C and 

2 GPa 

1050˚C, FeSiO3 [1984Tak] XRD, electron microprobe analysis 950-1050˚C, γ-Fe-Si alloys with 0.07-0.92 

mass% Si 

[1985Bjo] Calphad, associate model 1100-1900˚C, Fe-FeO-Fe2O3-SiO2 [1985Mod] XRD, electron microprobe analysis 900˚C, Fe 7(Si 0.94Fe 0.06)O 10 

[1985Sas] Thermodynamic calculations, central 

atom model 

1315-1600˚C, FeO-SiO2 

[1986Tak] XRD, microprobe analysis 800-900˚C, Fe-Si alloys (0.07-0.4 mass% 

Si) 

[1986Wie1] Light microscopy, SEM, microprobe 

analysis 

1450˚C, Fe-Si alloys (up to 3 mass% Si) 

[1986Wie2] TGA, XRD, microprobe analysis, SEM, IR 850˚C, Fe-Si alloys (0.5-3 mass% Si) 

[1986Zin] EMF 1600-1670˚C, 0.043-0.391 mass% Si 

(activity Si and O in liquid Fe) 

[1987Lee] Surface spectroscopies: Auger Electron 

(AES), Electron Energy Loss (EELS), X-ray 

photoelectron (XPS) 

25˚C, Fe-8.75 at.% Si at initial stage of 

oxidation at very low P O2 

[1987One] EMF 627-1147˚C, Fe+Fe 2SiO 4+SiO 2 

627-1147˚C, Fe 3O 4+Fe 2SiO 4+SiO 2 

[1987Yag] Multianvil high-pressure apparatus, in situ 

XRD combined with synchrotron 

radiation 

800-1200˚C, 4-6 GPa, Fe 2SiO 4 α = γ 

transition 

[1989Aka] H-Tsolution calorimetry, XRD 702˚C, Fe2SiO4, enthalpy of α = γ 

transformation 

[1989Jac] EMF 623-1127˚C, Fe+Fe2SiO4+SiO2 807-1067˚C, Fe3O4+Fe2SiO4+SiO2 DOI: 10.1007/978-3-540-70890-2_20 Landolt‐Börnstein 


MSIT 1




Range Studied 

[1990Din] XRD 900˚C, 7 GPa (synthesis) of Fe2SiO4 (γ-spinel), crystal structure 

[1992Bec] High-temperature Mössbauer 

spectroscopy 

500-1130˚C, pO2 = 5·10 –14 , αFe2SiO4 [1992Ros] Multi-anvil high pressure apparatus, 

microprobe, XRD 

1200˚C, 7 GPa, Fe 2SiO 4-Fe 3O 4 

[1993Tyu] Thermodynamic calculations 1300˚C, FeO-SiO2 (in presence of Fe), FeO 

activity 

[1994Hug] Single-crystal X-ray in diamond-anvil cell T = 800-1200˚C, p = 1-8 GPa, FeSiO3 

[1994Mat] Thermodynamic calculations 1250˚C, FeO-SiO 2 (in presence of Fe), O 2 

activity 

[1996Hug] Piston-cylinder high-pressure apparatus, 

single crystal XRD in diamond anvil cell, 

TEM 

Synthesis at 1100˚C, 3 GPa; FeSiO3, upto 

4.6 GPa 

[1997Fab] CALPHAD assessment, ionic liquid model pressure up to p = 20 GPa and 

temperature up to 2000˚C, Fe-FeO-Fe 2O 3- 

SiO 2 

[1997Hug] Piston-cylinder high-pressure apparatus, 

multianvil high-pressure apparatus, XRD 

950˚C, 2 GPa, ortho FeSiO3, 1100˚C, 

9 GPa, clino FeSiO 3, 20-821˚C, unit-cell 

parameters 

[1997Li] EMF 1550˚C, Fe-2.5 mass% Si under CO2 

blowing (activity of O and Si) 

[1997Oht] Multi-anvil high pressure apparatus 1200˚C, 4-10 GPa, Fe2SiO4-Fe3O4 [1997Sel] CALPHAD assessment, ionic liquid model p =10 5 Pa, temperature up to 2000˚C, 

Fe-FeO-Fe 2O 3-SiO 2 

[1997Woo] Multi-anvil high pressure apparatus, XRD 

of quenched samples, TEM 

[1998Ang] Belt high-pressure apparatus, single 

crystal XRD, electron microprobe 


800-1300˚C, 5-8 GPa, ortho=high-clino 

FeSiO 3 transition 

13 

1200˚C, 4 GPa (synthesis) of Fe 2.57Si 0.43O 4, 

XRD spectra at 25˚C 

[1998Lee] Calculation with ionic liquid model 1600˚C, Fe-O-Si alloys with content of Si 

(up to 10 mass%) and O (up to 0.1 mass%) 

[1998Won] TEM, atomic force microscopy 900˚C, Fe contamination of Si-SiO2 interface 

[1998Woo] Piston-cylinder high-pressure apparatus, 

XRD 

1100˚C, 5.6 GPa, Fe2.45Si0.55O4 [1999Ma] Thermodynamic calculations 1600˚C, Fe-O-Si alloys with content of Si 

(up to 0.01 mass%) and O (up to 0.25 

mass%) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

14 20 

Fe–O–Si 



[1999Rom] CALPHAD assessment, quasichemical 

model 

[1999Ros1] Synthesis in multianvil high-pressure 

apparatus, XRD, Raman spectra at high 

pressure (diamond anvil cell) 

[1999Ros2] Synthesis in multianvil high-pressure 

apparatus, XRD, Mössbauer spectra, 

electronic absorbtion spectra at high 

pressure (diamond anvil cell) 

[2000Haz] Multi-anvil high pressure apparatus, 

single crystal X-ray in diamond anvil cell 


Range Studied 

1000-1800˚C, FeO-SiO 2 in presence of Fe. 

1100˚C, 9 GPa (synthesis), 1.57-175 GPa: 

low-high clinoferrosilite (FeSiO 3) 

transition 

1200˚C, 8 GPa (synthesis) FeSiO 3, spectra 

measurements from 1 atm to 5 GPa 

Synthesis at 6 GPa, 1200˚C, crystal 

structure study up to 8.95 GPa, Fe 2SiO 4- 

Fe 3O 4 

[2000Woo] Multi-anvil high-pressure apparatus 900-1200˚C, 2-9 GPa, Fe 2SiO 4-Fe 3O 4 

[2001Fri] Compound energy formalism 1130˚C, Fe2SiO4 nonstoichiometry, mole 

fraction of Fe +3 and vacancies at pO2 in 

the range 10 –14 -10 –8 atm 

[2001Ott] Polymeric model of liquid 1600˚C, activity of FeO in FeO-SiO2 in 

presence of Fe 

[2001Zha] Thermodynamic calculation 1600˚C, activity of FeO in FeO-SiO2 in 

presence of Fe 

[2004Fre] Equilibration with gas mixtures, 

thermodynamic calculations 

1550-1600˚C, FeO-SiO2-O2 [2004Jun1] CALPHAD assessment, modified 

quasichemical model 

[2004Jun2] Assessment, modified Wagner’s 

formalism 

400-2000˚C, Fe-FeO-SiO 2-O 2 

1550-1650˚C, 10 –3 -100 mass% Si 

equilibrium between liquid Fe and solid 

SiO 2 

[2004Tyu] Thermodynamic calculation 25˚C, Fe-Si-O 

[2005Ake] TEM, energy dispersive X-ray 

microanalysis (EDX), electron energy loss 

spectroscopy (EELS) 

1200˚C, 6 GPa (synthesis), Fe7SiO10 [2005Mik] Numerical analysis on Si deoxidation of 

molten Fe using Darken formalism 

[2005Shi] Equilibrium study in inert atmosphere, 

chemical analysis, gravimetry 

1550-1650˚C, up to 2.1 mass% Si and 

0.036 mass% O 

1600˚C, Fe-Si (0.1-70 mass% Si) in 

equilibrium with SiO 2 

[2006Ama] XRD, microprobe, SEM Fe-Si (0-3 mass% Si) after oxidation at 

800, 1000˚C 



MSIT 1




Range Studied 

[2006Bas] TEM, Mössbauer spectroscopy 500-650˚C, 55Fe2O3-45SiO2 (mol%) glass 

after reduction and heat treatment to 

produce Fe-core Fe3O4 shell 

nanostructure 

[2006Kim] Chemical vapor condensation, XRD, TEM 700-1100˚C, Fe/SiO2 nanocomposite 

[2006Tak] Hot-compression test at 1000˚C, Raman 

spectroscopy, X-ray absorption analysis, 

in-situ XRD up to 900˚C 

[2007Jak] CALPHAD assessment, modified 

quasichemical model 

1100, 1200˚C, Fe-Si (up to 3 mass% Si) in 

gas 74%N 2-17%H 2O-8%CO 2-1%O 2 

1000-2000˚C, Fe-FeO-Fe 2O 3-O 2 

[2007Yon] Adiabatic calorimetry –268-30˚C, γFe 2SiO 4 (heat capacity, 

standard entropy) 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 


Lattice 

Parameters 


15 

(αδFe) cI2 

Im3m a = 293.15 pure Fe at 1390˚C [Mas2] 

(δFe) W 

1538 - 1394 a = 286.65 pure Fe at 25˚C [Mas2] 

(αFe) 

< 912 



1394 - 912 Fm3m 

Cu 


P63/mmc 

Mg 

c = 396.0 

(Si) cF8 a = 543.06 at 25˚C [Mas2] 

< 1414 Fd3m 

C (diamond) 

α1,Fe3Si cF16 ordered D03 modification of Fe with 11 

to 30 at.% Si [1982Kub, Mas2] 

≤ 1235 Fm3m 

BiF3 a = 565 [V-C2] 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

16 20 

Fe–O–Si 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 

Lattice 

Parameters 


α2, Fe-S cP2 ordered B2 modification of Fe with 10 

to 22 at.% Si [1982Kub, Mas2] 

≤ 1280 Pm3m 

CsCl a = 281 [V-C2] 

Fe2Si hP6 33.0 to 34.5 at.% Si [Mas2] 

1212 - 1040 P3m1 a = 405.2 ± 0.2 [V-C2] 

Fe2Si c = 508.55 ± 0.3 

Fe5Si3 hP16 37.5 at.% Si [1982Kub] 

1060 - 825 P63/mmc a = 675.9 ± 0.5 [V-C2] 

Mn5Si3 c = 472.0 ± 0.5 


≤ 1410 P213 FeSi 

a = 451.7 ± 0.5 [V-C2] 

FeSi2(h) tP3 69.5 to 73.0 at.% Si [Mas2] 

1220 - 937 P4/mmm a = 269.01 [V-C2] 

βFeSi2 c = 513.4 

FeSi2(r) oC48 66.7 at.% Si [1982Kub] 

≤ 982 Cmca a = 986.3 ± 0.7 [V-C2] 

αFeSi2 b = 779.1 ± 0.6 

c = 783.3 ± 0.6 

Fe2O3 hR30 ~60 at.% O 

< 1457 R3c a = 503.42 ± 0.03 [V-C2] 

Al2O3 c = 1374.83 ± 0.04 

FexO cF8 wustite, 0.845 ≤ x ≤ 0.961 

1424 - 570 Fm3m 

NaCl 

a = 435.35 at 1000˚C [V-C2] 

Fe3O4+y Fe3O4 < 1596 

cF56 

Fd3m a = 841.1 magnetite, 57.1 to 58.0 at.% O 

MgAl2O4 at 200˚C [V-C2] 

αQ, SiO2 hP9 α-Quartz 

< 573 P3221 a = 491.38 ± 2 at 25˚C [V-C2] 

SiO2 (low 

quartz) 

c = 540.52 ± 2 [L-B] 

βQ, SiO2 hP9 β-Quartz 

867-573 P6222 a = 502.0 at 600˚C [V-C2] 

SiO2 (high 

quartz) 

c = 552.3 

a = 503.8 

c = 546 

[L-B] 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 

Lattice 

Parameters 


SiO2 Low-Tridymite mC144 a = 1854 at 25˚C [L-B] 

(monoclinic) Cc b = 501 metastable 

< 60 SiO2 (monoclinic 

tridymite) 

c = 2579 

β = 117˚40´ 

SiO2 Low-Tridymite oC24 a = 874 at 220˚C [L-B] 

(orthorhombic) C2221 b = 505 metastable 

350 - 160 SiO2 (orthorhomb. 

tridymite) 

c = 824 


17 

Tr, SiO2 hP12 High-Tridymite 

1470 - 350 P63/mmc a = 505.2 ± 0.9 at 550˚C [V-C2] 

SiO2 (high 

tridymite) 

b = 827 ± 2 

a = 503 

b = 822 [L-B] 

SiO2 tP12 Low-Cristobalite 

< 250 P41212 a = 497.8 25˚C [V-C2] 

SiO2 (low 

cristobalite) 

c = 694.8 

a = 497 ± 3 

c = 691 ± 3 

[L-B] 

Cr, SiO2 cF104 High-Cristobalite 

1723 - 250 Fd3m a = 716.6 220˚C [V-C2] 

SiO2 (high 

cristobalite) 

a = 712.97 ± 0.08 300˚C [L-B] 

Coes, SiO2 mC48 Coesite, stable between 3-9.5 GPa 

C2/c a = 709.8 ± 0.2 [V-C2] 

SiO2 (coesite) b = 1233.4 ± 0.3 

c = 714.8 ± 0.2 

γ = 120.10˚ 

St, SiO2 tP6 Stishovite, stable above 9.5GPa 

P42/mnm a = 417.97 ± 0.02 at 25˚C [V-C2] 

TiO2 c = 266.69 ± 0.01 

αFe2SiO4 oP28 a = 1045.97 Mineral fayalite, end-member of olivine 

solid solution [2002Lot] 

Pnma b = 608.18 

Mg2SiO4 c = 481.50 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

18 20 

Fe–O–Si 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 

Lattice 

Parameters 


γFe2SiO4 cF56 

Fd3m 

MgAl2O4 at p > 9 GPa γ-spinel forms continuous 

solid solution Fe3–xSixO4 with 0 < x



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 

Lattice 

Parameters 


Fe3–xSixO4 oI56 structure wadsleite, β-spinel [2000Woo] 

Imma a = 586.64 Spd V, x = 0.45 

Mn2GeO4 b = 891.32 

c = 836.4 

a = 585.7 

b = 889.1 

c = 835.4 

Spd V, x = 0.54 [1997Oht] 

a = 585.61 

b = 1189.29 

c = 836.83 

Spd III, x = 0.548 [2000Woo] 

a = 584.9 

b = 1185.57 

c = 837.72 

Spd III, x = 0.67 [2000Haz] 

a = 585.93 

b = 1798.0 

c = 838.4 

Spd II, x = 0.43 [1998Ang], x = 0.4346 

[2000Woo] 

Fe7SiO10 mP36 a = 2133.6 stable at 5-6 GPa [2000Woo], mineral 

iscorite [1985Mod] 

P21/m or P2/m b = 306.79 

β = 98.06 

or 

I12/m1 

[2005Ake] 

. Table 3 




Fe 


Si O 

19 

L1 +LFe Ð L + SiO2(Cr) 1664 U1 L 17.19 21.85 60.96 

L1 1.00 32.67 66.34 

L Ð Fe2O3+Fe3O4+SiO2(Tr) 1443 E1 L 31.02 8.53 60.45 

L+(γFe) Ð FexO+αFe2SiO4 1180 U5 L 33.00 11.10 55.90 

L+(γFe) Ð αFe2SiO4 + SiO2 1178 U6 L 23.93 17.34 58.73 

L+FexOÐ Fe3O4 + αFe2SiO4 1160 U9 L 30.78 12.10 57.12 

L Ð Fe3O4+ αFe2SiO4 +(γFe) 1137 E5 L 25.96 15.46 58.58 

FexO Ð Fe3O4+(αFe)+αFe2SiO4 559 E6 - - - - 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

20 20 

Fe–O–Si 

. Table 4 


Reaction or Transformation T [˚C] 

Quantity, per mol of atoms 


1/7 {Fe(α) + Si+2O2=αFe2SiO4} 25 H = –211.05 [2004Fab] 

1/7 {2Fe(α) + Si+2O2=γFe2SiO4} 25 H = –209.296 [2004Fab] 

1/5{Fe(α) + Si+1.5O2=αFeSiO3} 25 H = –238.529 [2004Fab] 

. Table 5 

Thermodynamic Properties of Single Phases 

Phase 

Temperature 

Range [˚C] Property, per mole of atoms [J, mol, K] Comments 

αFe 2SiO 4 2525 - 1177 S = 21.57·C p = 25.146 – 0.001258·T + 3.53·10 –6 ·T 2 – 

555571·T –2 

γFe 2SiO 4 2525 - 1527 S = 20.975·C p= 23.9371 + 0.004018·T – 

8.07814·10 5 ·T –2 + 1.11769·10 8 ·T –3 – 509.2·T –1 

FeSiO 3(ortho) 2525 - 1527 S = 19.32·C p = 22.0296 + 0.003044·T – 1.66832·10 6 ·T –2 

+ 1.83445·10 8 ·T –3 + 1878·T –1 

. Table 6 

Investigations of the Fe-O-Si Materials Properties 

Reference 



[2004Fab] 

[2004Fab] 

[2004Fab] 

[1985Mod] Magnetic susceptibility Magnetic properties of Fe7SiO10 (iscorite) 

[1986Reg] Susceptibility and magnetization, 


Magnetic properties of ortho FeSiO3 [1987Yag] In-situ XRD 25-1000˚C, 5.3 GPa Thermal expansion of αFe 2SiO 4 and γFe 2SiO 4 

[2000Haz] Single crystal X-ray in diamond 

anvil cell 

Isothermal bulk modulus and it’s pressure 

derivative for modified spinel in the Fe 3O 4- 

Fe 2SiO 4 join 

[2001Yam1] Magnetization Curie and Neel temperature, magnetic 

properties for spinel structures in the Fe3O4- Fe2SiO4 join 

[2001Yam2] Resistivity at –265-27˚C Electric conductivity 

[2002Lot] Mössbauer spectroscopy Electric field gradient in fayalite Fe2SiO4 [2003Kap] X-ray sessile method at 

1550-1560˚C 

Contact angle between liquid Fe and SiO 2 

substrate 



MSIT 1


Reference 



[2004Kon] Susceptibility at –192-700˚C Curie temperature, magnetic properties for 

spinel and spinelloid structures in the Fe 3O 4- 

Fe 2SiO 4 join 

[2006Ama] Vickers mictro-hardness 

measurement at room 

temperature and 1000˚C 

[2006Bas] Impedance measurements over 

100 Hz - 6 MHz at –153-167˚C 

[2006Kim] Vibration sample magnetometer at 

25˚C and 20 kOe 



MSIT 1 


Hardness of oxide scales Fe (0-3)Si after 

oxidation at 800 and 1000˚C 

Electric conductivity 55Fe 2O 3-45SiO 2 glass after 

reduction and heat treatment 

Magnetization of Fe/SiO 2 nanocomposite 

21 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

22 20 

Fe–O–Si 

. Fig. 1 

Fe-O-Si. p-T phase diagram of FeSiO 3 



MSIT 1

. Fig. 2 

Fe-O-Si. p-T phase diagram for the SiO 2 system at high pressures 



MSIT 1 


23 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

24 20 

Fe–O–Si 

. Fig. 3 

Fe-O-Si. p-T phase diagram for the FeO-SiO 2 system at high pressures up to 20 GPa from 

[2004Fab]. The melting curve from the experimental study of [1979Oht] is shown by a dashed 

line 



MSIT 1

. Fig. 4 

Fe-O-Si. p-x phase diagram of the Fe 3O 4-Fe 2SiO 4 system at 1100˚C 



MSIT 1 


25 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

26 20 

Fe–O–Si 

. Fig. 5 

Fe-O-Si. Phase diagram of the FeO-Fe 2O 3-SiO 2 at O 2 partial pressure of air 



MSIT 1


. Fig. 6 

Fe-O-Si. Phase diagram of the Fe 2O 3-SiO 2 quasibinary system (p O2 = 1 bar) 



MSIT 1 

27 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

28 20 

Fe–O–Si 

. Fig. 7a 

Fe-O-Si. Phase diagram of the FeO-SiO 2 system in presence of metallic Fe 



MSIT 1

. Fig. 7b 

Fe-O-Si. Content of Fe 2O 3 in liquid vs SiO 2 content 



MSIT 1 


29 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

30 20 

Fe–O–Si 

. Fig. 8a 

Fe-O-Si. Phase diagram of the Fe 2SiO 4-FeSiO 3 system at high pressure, p = 6 GPa 



MSIT 1


. Fig. 8b 

Fe-O-Si. Phase diagram of the Fe 2SiO 4-FeSiO 3 system at high pressure, p = 9 GPa 



MSIT 1 

31 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

32 20 

. Fig. 9a 

Fe-O-Si. Reaction scheme, part 1 

Fe–O–Si 



MSIT 1

. Fig. 9b 




MSIT 1 


33 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

34 20 

. Fig. 9c 


Fe–O–Si 



MSIT 1


. Fig. 10 

Fe-O-Si. Calculated liquidus surface projection of the FeO-Fe 2O 3-SiO 2 system 



MSIT 1 

35 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

36 20 

Fe–O–Si 

. Fig. 11 

Fe-O-Si. Schematic liquidus surface projection 



MSIT 1


. Fig. 12 

Fe-O-Si. Schematic liquidus relations of the FeO-SiO 2 system at high pressures 



MSIT 1 

37 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

38 20 

Fe–O–Si 

. Fig. 13 

Fe-O-Si. p-T phase diagram of the composition Fe 2SiO 4 



MSIT 1


. Fig. 14a 

Fe-O-Si. Isothermal sections of the FeO-Fe 2O 3-SiO 2 system calculated at 1300˚C 



MSIT 1 

39 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

40 20 

Fe–O–Si 

. Fig. 14b 

Fe-O-Si. Isothermal section of the FeO-Fe 2O 3-SiO 2 system calculated at 1450˚C 



MSIT 1

. Fig. 15 

Fe-O-Si. Partial isothermal section at 1600˚C 



MSIT 1 


41 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

42 20 

Fe–O–Si 

. Fig. 16 

Fe-O-Si. Potential diagram log 10 (p CO/p CO2) vs temperature. The relation between CO 2/CO ratio 

and oxygen partial pressure is based on the SGTE thermodynamic database: log 10 (p CO2/p CO) = 

(7312/T–2.215)log 10 (p O2) 



MSIT 1


43 

. Fig. 17 

Fe-O-Si. Liquid in equilibrium with solid SiO 2 at 1250-1350˚C vs oxygen partial pressure. The lines 

go from iron to magnetite saturation 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

44 20 

Fe–O–Si 

. Fig. 18 

Fe-O-Si. Calculated solubility of silica in liquid iron at 1545, 1600 and 1650˚C 



MSIT 1


. Fig. 19a 

Fe-O-Si. Calculated activity of FeO in liquid FeO-SiO 2 in equilibrium with metallic Fe at 1263, 

1315, 1364 and 1407˚C 



MSIT 1 

45 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

46 20 

Fe–O–Si 

. Fig. 19b 

Fe-O-Si. Calculated activity of FeO in liquid FeO-SiO 2 in equilibrium with metallic Fe at 1785, 




MSIT 1


. Fig. 20 

Fe-O-Si. Enthalpy of mixing of the FeO-SiO 2 liquid in equilibrium with metallic Fe 



MSIT 1 

47 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

48 20 

Fe–O–Si 

References 

[1927Gre1] Greig, J.W., “Immiscibility in Silicate Melts”, Amer. J. Sci., 13(15), 133–154 (1927) (Experimental, Phase 


[1927Gre2] Greig, J.W., “On Liquid Immiscibility in the System FeO-Fe2O3-Al2O3-SiO2”, Amer. J. Sci., 14(5Ser.), 

473–484 (1927) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 5) 

[1932Bow] Bowen, N.L., Schairer, J.F., “The FeO-SiO 2 System”, Amer. J. Sci., 24, 177–213 (1932) (Experimental, 


[1932Sch] Schenck, R., Franz, H., Laymann, A., “Investigation of Equilibria of Reduction and Oxidation of Iron”, 

Z. Anorg. Allg. Chem. 206, 129–151 (1932) (Experimental, Phase Relations, 3) 

[1937Wen] Wentrup, H., “The Phase Diagram of Sulphide Inclusions in Steel” (in German), Techn. Mitt. Krupp, 5, 

131–152 (1937) (Morphology, Phase Diagram, Phase Relations, Review, 27) 

[1939Cro] Crook, W.J., “The Series Iron Oxides-Silica”, J. Am. Ceram. Soc., 22, 322–334 (1939) (Experimental, 

Morphology, Phase Diagram, Phase Relations, 15) 

[1943Whi] White, J., “The Physical Chemistry of Open-Hearth Slags”, J. Iron Steel Inst., London, 148, 579–694 

(1943) (Phase Diagram, Phase Relations, Review, 195) 

[1946Cir] Cirilli, V., “Study of Balance Reduction with Carbon Oxide of the Iron Oxides in Presence of Silica”, 

Gazz. Chim. Ital., 76, 331–338 (1946) as quoted in [1997Fab] 

[1948Dar] Darken, L.S., “Melting Points of Iron Oxides on Silica; Phase Equilibria in the System Fe-O-Si as a 

Function of Gas Composition and Temperature”, J. Am. Chem. Soc., 70, 2046–2053 (1948) (Experimental, 

Phase Diagram, Phase Relations, Theory, 12) 

[1950Hil] Hilty, D.C., Crafts, W., “Solubility of Oxygen in Liquid Iron Containing Silicon and Manganese”, 

Trans. Am. Inst. Min. Metall. Eng., 188, 425–436 (1950) (Experimental, Phase Relations, 18) 

[1951Sch] Schumann, Jr.R., Ensio, P.J., “Thermodynamics of Iron Silicate Slag: Slag Saturated with γ Iron”, Trans. 

AIME, 191, 401–411 (1951) (Experimental, Phase Relations, Thermodyn., Phase Diagram, 15) 

[1952Gok] Gokcen, N.A., Chipman, J.C., “Silicon-Oxygen Equilibrium in Liquid Iron”, Trans. Amer. Inst. Min. 

Met Eng., 194, 171–181 (1952) (Calculation, Experimental, Phase Diagram, Phase Relations, Thermodyn., 

21) 

[1952Kin] King, E.F., “Heat of Formation of Manganous Metasilicate (Rhodonite) and Ferrous Orthosilicate 

(Fayalite)”, J. Am. Chem. Soc., 74, 4446–4448 (1952) (Experimental, Thermodyn., 3) 

[1952Mic] Michal, E.J., Schuhmann, Jr.R., “Thermodynamics of Iron-Silicate Slags: Slags Saturated with Solid 

Silica”, Trans. AIME, 194, 723–728 (1952) (Calculation, Experimental, Thermodyn., 6) 

[1953Chi] Chipman, J., Gokcen, A., “Silicon-Oxygen Equilibrium in Liquid Iron - A Revision”, Trans. Am. Inst. 

Min. Metall. Eng., 197(8), 1017–1018 (1953) (Calculation, Phase Relations, Thermodyn., 10) 

[1953Sch] Schumann, R.Jr., Powell, R.G., Michal, E.J., “Constitution of the FeO-Fe 2O 3-SiO 2 System at Slagmaking 

Temperatures”, Trans. Amer. Inst. Min. Met. Eng.,, 197, 1097–1104 (1953) (Experimental, Morphology, 


[1953Orr] Orr, R.I., “High Temperature Heat Contents of Magnesium Orthosilicate and Ferrous Orthosilicate”, J. 

Am. Chem. Soc., 75, 528–529 (1953) (Experimental, Thermodyn., 9) 

[1955All] Allen, W.C., Snow, R.B., “The Orthosilicate-Iron Oxide Portion of the System CaO-FeO-SiO 2”, J. Am. 

Ceram. Soc., 38(8), 264–280 (1955) (Experimental, Phase Diagram, Phase Relations, 12) 

[1955Mua] Muan, A., “Phase Equilibria in the System FeO-Fe2O3-SiO2”, Trans. Amer. Inst. Min. Met. Eng., 203, 

965–976 (1955) (Experimental, Phase Diagram, Phase Relations, 16) 

[1955Sch] Schuhmann, R., “Application of Gibbs-Duhem Equations to Ternary Systems”, Acta Metall., 3, 219–226 

(1955) (Phase Diagram, Phase Relations, Theory, Thermodyn., Calculation, 15) 

[1957Fit] Fitterer, G.R., “The Physical Chemistry of Steelmaking - A Tribute to Dr. C. H. Herty, Jr.”, Proc. 40th 

Nat. Open Hearth Steel Comm. Iron Steel Division, AIME, Pittsburgh, Pennsylvania, 8-10 April 

(1957), Mathews, D.R., Kennedy, E.J., Shearman, R.W., Lovell, K.S., (Eds.), Metall. Soc. Amer. Inst. Min. 

Metall. Petrol. Eng., 40, 281–303 (1957) (Assessment, Morphology, Phase Diagram, Phase Relations, 


[1957Tur] Turkdogan, E.T., Bills, P.M., “A Thermodynamic Study of FeO-Fe 2O 3-SiO 2, FeO-Fe 2O 3-P 2O 5 and FeO- 

Fe 2O 3-SiO 2-P 2O 5 Molten Systems”, J. Iron Steel Inst., London, 186, 329–339 (1957) (Experimental, 


[1959Bod] Bodsworth, C., “The Activity of Ferrous Oxide in Silicate Melts”, J. Iron Steel Inst., London, 193, 13–24 

(1959) (Experimental, Kinetics, Phase Diagram, Phase Relations, Thermodyn., 25) 



MSIT 1


49 

[1959Phi] Phillips, B., Muan, A., “Phase Equilibria in the System CaO-Iron Oxide-SiO 2 in Air”, J. Am. Ceram. 

Soc., 42, 413–423 (1959) (Experimental, Phase Diagram, Phase Relations, 18) 

[1960Sch] Schenck, H., Schmidtmann, E., Mueller, H., “Influence of the Thermal Treatment and Alloy 

Composition on the Internal Oxidation of Iron Alloys” (in German), Arch. Eisenhuettenwes., 31, 121 

(1960) (Experimental, Morphology, Thermodyn., 43) 

[1961Hsi] Hsi, C.-C., Polyakov, A.Ya., Samarin, A.M., “Oxygen Solubility in Liquid Fe-Si Alloys at Atmospheric 

Pressure and under Vacuum” (in Russian), Izv. Akad. Nauk SSSR, (Tekhn.), (2), 115–118 (1961) 


[1962Tur] Turkdogan, E.T., “Activities of Oxides in SiO 2-FeO-Fe 2O 3 Melts”, Trans. Metall. Soc. AIME, 224, 

294–299 (1962) (Assessment, Calculation, Phase Relations, Thermodyn., 17) 

[1964Lin] Lindsley, D.H., MacGregor, I.D., Davis, B.T.C., “Ferrosilite (FeSiO3) Synthesis at High Pressures and 

Temperatures”, Science, 144, 73–74 (1964) (Experimental, Phase Relations, 6) 

[1964Tay] Taylor, R.W., Schmalzried, H., “The Free Energy of Formation of Some Titanates, Silicates, and 

Magnesium Aluminate from Measurements Made With Galvanic Cells”, J. Phys. Chem., 68(9), 

2444–2449 (1964) (Experimental, Phase Relations, Thermodyn., 24) 

[1965Aki] Akimoto, S., Fujisawa, I., Katsura, T., “The Olivine-Spinel Transition in Fe 2SiO 4 and Ni 2SiO 4”, 

J. Geophys. Res., 70(8), 1969–1977 (1965) (Experimental, Phase Relations, 23) 

[1965Mua] Muan, A., Osborn, E.F., “Fe-Si-O” in “Phase Equilibria Among Oxides in Steelmaking”, Addison-Wesley 

Publ. Comp., 53–69 (1965) (Experimental, Phase Diagram, Phase Relations, Review, 6) 

[1965Val] Vallet, P., Raccah, P, “Thermodynamic Properties of Solid Iron (II) Oxide”, Mem. Sci. Rev. Met., 62, 

1–29 (1965) as quoted in [1997Fab] 

[1966Sch1] Schenck, H., Steinmetz, E., “Activity, Standard Condition and Coefficient of Activity” (in German), 

Stahleisen-Sonderberichte, Düsseldorf: Verlag Stahleisen, (7), 1–36 (1966) (Review, 161) 

[1966Sch2] Schwerdtfeger, K., Muan, A., Darken, L.S., “Activities in Olivine and Pyroxenoid Solid Solutions of the 

System Fe-Mn-Si-O at 1150˚C”, Trans. Metall. Soc. AIME, 236, 201–211 (1966) (Experimental, Phase 

Diagram, Phase Relations, Thermodyn., 27) 

[1967Aki] Akimoto, S.-I., Komada, E., Kushiro, I., “Effect of Pressure on the Melting of Olivine and Spinel 

Polymorph of Fe 2SiO 4”, J. Geophys. Res., 72(2), 679–686 (1967) (Experimental, Phase Relations, 


[1967Buz] Buzek, Z., Schindlerova, V., Macoszek, M., “The Influence of Cr, Mn, V, Si, Ti, Al, Zr, Ce and Ca on the 

Activity and Solubility of Oxygen in Liquid Iron”, Sb. Ved. Pr. Vys. Sk. Banske Ostrave, Rada Hutn., 

13(2-3), 175–193 (1967) (Experimental, Phase Relations, Thermodyn., 26) 

[1967Eib] Eibschuetz, M., Ganiel, U., “Mössbauer Studies of Fe 3+ in Paramagnetic Fayalite (Fe 2SiO 4)”, Sol. State 

Comm., 5(4), 267–270 (1967) (Experimental, Crys. Structure, 12) 

[1967Lin] Lindsley, D.H., “Pressure-Temperature Relations in the System FeO-SiO 2”, Year Book-Carnegie Inst. 

(Washington), 65, 226–230 (1967) (Experimental, Kinetics, Phase Relations, Thermodyn., 11) 

[1967Sch] Schwerdtfeger, K., “Measurement of Oxygen Activity in Iron, Iron-Silicon, Manganese, and Iron- 

Manganese Melts Using Solid Electrolyte Galvanic Cells”, Trans. Nat. Res. Inst. Met. (Jpn.), 239, 

1267–1281 (1967) (Electrochemistry, Experimental, Thermodyn., 30) 

[1969Kul] Kulikov, I.S., “Thermal Dissociation of Compounds” (in Russian), Metallurgia, Moscow, 533–562 (1969) 

(Calculation, Phys. Prop., Thermodyn., 136) 

[1969Nov] Novokhatsky, I.A., Belov, B.F., “Concentration Dependence of the Solubility of Oxygen in Alloys” (in 

Russian), Izv. Akad. Nauk SSSR, Met., (3), 15–26 (1969) (Experimental, Phase Relations, 29) 

[1970For] Forward, G., Elliott, J.F., Kuwabara, T., “Formation of Silica and Silicates During the Solidilication of 

Fe-O-Si Alloys”, Metall. Trans., 1, 2889–2898 (1970) (Experimental, Phase Relations, 18) 

[1970Nis] Nishikawa, K., Kusano, A., Ito, K., Sano, K., “The Effect of Alloying Elements on the Solubility of 

Oxygen in Delta-Iron”, Trans. Iron Steel Inst. Jpn., 10, 83–88 (1970) (Experimental, Kinetics, Phase 


[1971Dis] Distin, P.A., Whiteway, S.G., Masson, C.R., “Solubility of Oxygen in Liquid Iron from 1785 to 1960˚C. 

A New Technique for Study of Slag-Metal Equilibria”, Can. Metall. Quat., 10, 73–78 (1971) (Experimental, 


[1971Log] Logani, R.C., Smeltzer, W.W., “Development of the Wustite-Fayalite Scale on an Iron-1.5 wt.% Silicon 

Alloy at 1000˚C”, Oxidation of Metals, 3(1), 15–32 (1971) (Experimental, Phase Relations, 28) 

[1972Sig] Sigworth, G.K., Elliott, J.F., “Conditions for Nucleation of Oxides in Fe-O-Si Alloys”, Can. Metall. 

Quart., 11(2), 337–346 (1972) (Review, Thermodyn., 36) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

50 20 

Fe–O–Si 

[1973Vla] Vladimirov, L.P., Kopitsa, N.M., Sumenkova, V.V., “Activity of Oxygen and Silicon in Fe-O-Si Alloys”, 

Russ. Metall., 5, 61–65 (1973) (Experimental, Thermodyn., 13) 

[1973Iye] Iyengar, R.K., Philbrook, W.O., “Application of Thermodynamics of Heterogeneous Phase Equilibria 

to the Construction of the Fe-O-Si Ternary Phase Diagram”, Metall. Trans., 4, 2181–2188 (1973) 

(Theory, Phase Relations, 13) 

[1974Ark] Arkahrov, V.I., Belov, B.F., Novokhatskii, I.A., “The Solubility of Oxygen in Metallic Melts” (in 

Russian), Ukr. Khim. Zh. (Russ. Ed.), 40(2), 129–134 (1974) (Experimental, Phase Relations, Thermodyn., 

15) 

[1974Sig] Sigworth, G.K., Elliott, J.F., “The Thermodynamics of Liquid Dilute Iron Alloys”, Met. Sci., 8, 298–310 


[1976Mor] Morito, N., Ichida, T., “Transaction from External to Internal Oxidation in Fe-Si Alloy as a Function of 

Oxygen Potential of the Ambient Atmosphere”, Scr. Metall., 10, 619–622 (1976) (Experimental, Phase 


[1977Aki] Akimoto, S., Yagi, T., Inoue, K., “High Temperature-Pressure Phase Boundaries in Silicate Systems 

Using in Situ X-Ray Diffraction”, High-Pressure Research (Applicat. Geophys.), 15, 585–602 (1977) 


[1977She] Shevtsov, V.E., Brovkov, V.A., Lekhtmets, V.L., “Thermodynamics of Oxygen Solutions in Fe-Si Melts” 

(in Russian), Izv. VUZ Chern. Metall, (11), 42–45 (1977) (Experimental, Kinetics, 13) 

[1978Hew] Hewitt, D.A., “A Redetermination of the Fayalite-Magnetite-Quartz Equilibrium Between 650˚C and 

850˚C”, Amer. J. Sci., 278, 715–724 (1978) (Experimental, Thermodyn., 20) 

[1979Kau] Kaufman, L., “Calculation of Quasibinary and Quasiternary Oxide Systems II”, Calphad, 3(1), 27–44 

(1979) (Phase Relations, Phase Diagram, Thermodyn., Calculation, 5) 

[1979Nav] Navrotsky, A., Pintchovski, F.S., Akimoto, S., “Calorimetric Study of the Stability of High Pressure 

Phases in the Systems CoO-SiO 2 and "FeO"-SiO 2, and Calculation of Phase Diagrams in MO-SiO 2 

Systems”, Phys. Earth Planet. Interiors, 19, 275–292 (1979) (Calculation, Experimental, Phase Relations, 


[1979Oht] Ohtani, E., “Melting Relation of Fe 2SiO 4 up to about 200 kbar”, J. Phys. Earth, 27, 189–208 (1979) 

(Experimental, Morphology, Phase Diagram, Phase Relations, 34) 

[1980Ban] Ban-Ya, S., Chiba, A., Hikosaka, A., “Thermodynamics of Fe(t)O-M(x)O(y) (M(x)O(y) = CaO, SiO 2, 

TiO 2 and Al 2O 3) Binary Melts Saturated with Solid Iron” “Austral.-Jap. Extractive Metall. Symp.”, 

Sydney, Australia 16-18 July 1980, Australian Inst. Min. Metall., 23, 457–467 (1980) (Experimental, 


[1980Boh] Bohlen, S.R., Essene, E.J., Boettcher, A.L., “Reinvestigation and Application of Olivine- 

Quartz-Orthopyroxene Barometry”, Earth Planet. Sci. Letters, 47, 1–10 (1980) (Experimental, Phase 


[1980Goe] Goel, R.P., Kellogg, H.H., Larrain, J., “Mathematical Description of the Thermodynamic Properties of 

the System Fe-O and Fe-O-SiO 2”, Metall. Mater. Trans. B, 11B, 107–117 (1980) (Phase Diagram, 

Theory, 30) 

[1981Ave] Averbukh, S.M., Smirnov, L.A., Popel, S.I., “Equilibrium of Silicon with Oxygen in Molten Iron” (in 

Russian), Izv. VUZ Chern. Metall, (11), 5–11 (1981) (Experimental, Kinetics, Thermodyn., 14) 

[1981Fuj] Fujisawa, T., Nomura, M., Sakao, H., “Silicon-Oxygen Equilibrium in Delta Iron at the Solid-Liquid 

Equilibrium Temperature”, Trans. Iron Steel Inst. Jpn., 21(9), 624–631 (1981) (Experimental, Thermodyn., 

29) 

[1981Jac] Jacobson, E., Rosen, E., “Thermodynamic Study of High Temperature Equilibria. 25. Solid State 

emf Studies of the Systems Fe-FeO, Ni-NiO and Co-CoO in the Temperature Range 1000-1600˚C”, 

Scand. J. Metall., 10, 39–43 (1981) (Electrochemistry, Experimental, Thermodyn., Phase Relations, 9) 

[1981Lev] Levitskii, V.A., Popov, S.G., Gerasimov, Y.I., “Studies on the Thermodynamics of Complex Oxides of 

Iron Subgroup Metals” (in Russian), in “Fiz. Khim. Okislov Met.”, Balakirev (Ed.), Nauka, Moscow, 


[1981Sch] Schwab, R.G., Küstner, D., “ The Equilibrium Fugacities of Important Oxygen Buffers in Technology 

and Petrology”, Neues Jb. Mineral. Abhandlungen, 140, 111–141 (1981) as quoted in [1987One] 

[1982Ban] Ban-Ya, S., Iguchi, Y., Honda H., “Heat of Mixing of Liquid Fe tO-SiO 2 Slag” in “Proc. International 

Symposium on the Physical Chemistry of Iron and Steelmaking”, Toronto, III/39-III-44 (1982) (Experimental, 






MSIT 1


51 

[1982Ois] Oishi, T., Goto, T., Kahayara, Y., Ono, K., Moriyama, J., “Oxygen Pressure Measurements of Silica 

Saturated Iron-Oxygen-Silicon Dioxide Melts by the EMF Method Using Zirconia Solid Electrolyte”, 

Metall. Mater. Trans. B, 13B, 423–427 (1982) (Experimental, Thermodyn., Phase Relations, 11) 

[1982Rob] Robie, R.A., Finch, C.B., Hemingway, B.S., “Heat Capacity and Entropy of Fayalite (Fe 2SiO 4) between 

5.1 and 383 K: Comparison of Calorimetric and Equilibrium Values for the QFM Buffer Reaction”, Am. 

Mineral., 67, 463–469 (1982) (Experimental, Thermodyn., 34) 

[1982Rol] Rolls, R., Shahhosseini, M.H., “Effect of Creep on the Oxidation Characteristics of Fe-Si Alloys at 

973-1073 K”, Oxidation of Metals, 18(3/4), 115–126 (1982) (Experimental, Mechan. Prop., 24) 

[1982Wat] Watanabe, H., “Thermochemical Properties of Synthetic High-Pressure Compounds Relevant to the 

Earths Mantle”, High-Press. Research in Geophys., 441–464 (1982) (Experimental, Thermodyn., 78) 

[1983Kuh] Kuhn, A.T., Wakeman, D., El Roubi, E.Y., Collins, G.C.S., “Anodic Dissolution and Oxygen Evolution 

on Binary and Ternary Iron-Silicon Alloys”, Electr. Acta, 28(4), 515–527 (1983) (Experimental, Phase 


[1983Mye] Myers, J., Eugster, H.P., “The System Fe-O-Si - Oxygen Buffer Calibrations to 1500 K”, Contribution to 

Mineralogy and Petrology, 82(1), 75–90 (1983) (Experimental, Thermodyn., 53) 

[1983Web] Weber, H.P., “Ferrosilite, the High Temperature Polymorph of FeSiO 3”, Acta Crystallogr., 39C(1), 1–3 


[1984Kat] Kato, T., Ohtani, E., Kumazawa, M., “Effect of High Pressure on the Melting Relation of the Fe 2SiO 4- 

FeSiO 3 System”, J. Phys. Earth, 32, 97–111 (1984) (Experimental, Phase Relations, Thermodyn., 23) 

[1984Ste] Stebbins, J.F., Carmichael, I.S.E., “The Heat of Fusion of Fayalite”, Am. Mineral., 69, 292–297 (1984) 


[1984Sue] Sueno, S., Kimata, M., Prewitt, C.T., “The Crystal Structure of High Clinoferrosilite”, Am. Mineral., 

69(3-4), 264–269 (1984) (Experimental, Crys. Structure, 14) 

[1984Tak] Takada, J., Kashiwagi, K., Adachi, M., “Internal Oxidation of Fe-Si Alloys in γ-Phase Region”, J. Mater. 

Sci., 19(10), 3451–3458 (1984) (Experimental, Phase Relations, 19) 

[1985Bjo] Bjoerkman, B., “An Assessment of the System Fe-O-Si Using a Structure Based Model for the Liquid 

Silicate”, Calphad, 9(3), 271–282 (1985) (Thermodyn., Phase Relations, Assessment, 37) 

[1985Jac] Jacobson, E., “Solid State EMF Studies of the Systems FeO-Fe 2O 3 and Fe 3O 4-Fe 2O 3 in the Temperature 

Range 1000-1600 K”, Scand. J. Metall., 14, 252–256 (Experimental, Thermodyn., 21) 

[1985Mod] Modaressi, A., Malaman, B., Gleitzer, C., Tilley, R.J.D., “Preparation and Study of the Oxysilicate of the 

Mixed Valency Fe 7(SiO 4)O 6 (Iscorite)” (in French), J. Solid State Chem., 60, 107–114 (1985) (Crys. 


[1985Sas] Sastri, P., Lahiri, A.K., “Applicability of Central Atoms Models to Binary Silicate and Aluminate Melts”, 

Metall. Trans. B, 16, 325–331 (1985) (Calculation, Experimental, Theory, Thermodyn., 35) 

[1985Tay] Taylor, D., “Thermal Expansion Data. VI. Complex Oxides, AB 2O 4, the Spinels”, Br. Ceram. Trans. J., 

84(4), 121–127 (1985) (Calculation, Crys. Structure, Review, 99) 

[1986Reg] Regnard, J.R., Guillen, R., Wiedenmann, A., Fillion, G., Hafner, S., Langer, K., “Mössbauer and 

Magnetic Studies of Orthorhombic FeSiO 3”, Hyperfine Interact., 28, 589–592 (1986) (Crys. Structure, 

Mag. Prop., Experimental, 8) 

[1986Tak] Takada, J., Adachi, M., “Determination of Diffusion Coefficient of Oxygen in α-Iron from Internal 

Oxidation Measurements in Fe-Si Alloys”, J. Mater. Sci., 21(6), 2133–2137 (1986) (Experimental, Phase 

Relations, Kinetics, 12) 

[1986Wie1] Wiesner, U., “On the Internal and External Oxidation in Fe-Si- Alloys” (in German), Neue Huette, 

31(9), 330–3331 (1986) (Experimental, Phase Relations, 12) 

[1986Wie2] Wiesner, U., Kunze, J., “On the Oxidation and Decarbonizing Behavior of Fe-Si Alloys” (in German), 

Neue Huette, 31(7), 250–253 (1986) (Experimental, Phase Relations, 16) 

[1986Zin] Zinevich, T.N., Batalin, G.I., “Mutual Effect of Silicon and Oxygen on their Thermodynamic 

Activity in the Fe-O-Si Melts” (in Russian), Ukr. Khim. Zh., 52(3), 242–247 (1986) (Experimental, 


[1987Lee] Lee, Y.P., Bevolo, A. J., Lynch, D.W., “Studies of the Initial Oxidation of Fe-Si Alloys by AES, XPS and 

EELS”, Surface Sci., 188(1/2), 267–286 (1987) (Experimental, Phase Relations, 35) 

[1987One] OŃeill, H.St.C., “Quartz-Fayalite-Iron and Quartz-Fayalite-Magnetite Equilibria and the Free Energy 

of Formation of Fayalite (Fe 2SiO 4) and Magnetite (Fe 3O 4)”, Am. Mineral., 72, 67–75 (1987) (Experimental, 

Thermodyn., 34 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

52 20 

Fe–O–Si 

[1987Yag] Yagi, T., Akaogi, M., Shimomura, O., Suzuki, T., Akimoto, S.-i., “In Situ Observation of Olivine-Spinel 

Phase Transformation in Fe 2SiO 4 Using Synchrotron Radiation”, J. Geophys. Res., 92(B7), 6207–6213 

(1987) (Calculation, Experimental, Phase Relations, Thermodyn., 29) 

[1988One] OŃeill, H.St.C., “Systems Fe-O and Cu-O: Thermodynamic data for the Equilibria Fe-“FeO”, 

Fe-Fe 3O 4, “FeO”-Fe 3O 4,Fe 3O 4-Fe 2O 3, Cu-Cu 2O and Cu 2O-CuO from emf Measurements”, Am. Mineral., 

73, 470–486 (1988) (Experimental, Thermodyn., 46) 

[1989Aka] Akaogi, M., Ito, E., Navrotsky, A., “Olivine-Modified Spinel-Spinel Transitions in the System 

Mg 2SiO 4-Fe 2SiO 4: Calorimetric Measurements, Thermochemical Calculation, and Geophysical Application”, 

J. Geophys. Res., 94(B11), 15671–15685 (1989) (Experimental, Phase Diagram, Phase Relations, 


[1989And] Anderson, W.W., Svendsen, B., Ahrens, T.J., “Phase Relations in Iron rich System and Implications for 

the Earth’s Core”, Phys. Earth Inter., 55, 208–220 (1989) (Review, Phase Relations, 48) 

[1989Jac] Jacob, K.T., Kale, G.M., Iyengar, G.N.K., “Chemical Potentials of Oxygen for Fayalite-Quartz-Iron and 

Fayalite-Quartz-Magnetite Equilibria”, Metall. Trans. B, 20, 679–685 (1989) (Experimental, Thermodyn., 

37) 

[1989Rag] Raghavan, V., “The Fe-O-Si System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Met., 

Calcutta, 5, 260–277 (1989) (Review, Phase Relations, Phase Diagram, 36) 

[1989Sve] Svendsen, B., Anderson, W.W., Ahrens, T.J., Bass, J.D., “Ideal Fe-FeS, Fe-FeO Phase Relations and 

Earth’s Core”, Phys. Earth Inter., 55, 154–186 (1989) (Review, Phase Relations, 68) 

[1990Din] Ding, J., Li, D.-Y., “X-Ray Powder Structural Analysis of the Spinel Polymorph of Fe 2SiO 4”, Powder 

Diffr., 5(4), 221–222 (1990) (Crys. Structure, Experimental, 16) 

[1990Wri] Wriedt, H.A., “The O-Si (Oxygen-Silicon) System”, Bull. Alloy Phase Diagrams, 11(1), 43–61 (1990) 


[1991Ito] Ito, E., Katsura, T., “Dissolution of Silicon and Oxygen in Molten Iron at High Pressure and 

Temperature”, Proc. Japan Acad., Ser. B, 67(9), 153–158 (1991) (Phase Relations, Experimental, 14) 

[1991Sun] Sundman, B., “An Assessment of the Fe-O System”, J. Phase Equilib., 12(1), 127–140 (1991) (Phase 

Relations, Phase Diagram, Assessment, 53) 

[1992Bec] Becker, K.D., Dreher, S., Wissmann, S., “A High-Temperature Mössbauer Study of Fayalite, Fe 2SiO 4: 

Cation Diffusion and Reactivity”, Ber. Bunsen-Ges. Phys. Chem., 96(11), 1778–1783 (1992) (Experimental, 

Crys. Structure, 21) 

[1992Hal] Hallstedt, B., “Thermodynamic Assessment of the Silicon-Oxygen System”, Calphad, 16(1), 53–61 

(1992) (Calculation, Phase Diagram, Phase Relations, Thermodyn., 22) 

[1992Ros] Ross, C.R., Armbruster, T., Canil, D., “Crystal-structure Refinement of a Spinelloid in the System 

Fe 3O 4-Fe 2SiO 4”, Am. Mineral., 77, 507–511 (1992) (Experimental, Crys. Structure, 17) 

[1993Tyu] Tyurin, A.G., “Thermodynamics of Molecular and Ionic Solutions”, Russ. Metall. (Engl. Transl.), (2), 

39–47 (1993), translated from Izv. RAN, Met., (2), 48–56 (1993) (Theory, Thermodyn., 35) 

[1993Wu] Wu, P., Eriksson, G., Pelton, A.D., Blander, M., “Prediction of the Thermodynamic Properties and 

Phase Diagrams of Silicate Systems – Evaluation of the FeO-MgO-SiO 2 System”, ISIJ Int., 33(1) 26–35 

(1993) (Assessment, Phase Diagram, Phase Relations, Thermodyn., Calculation, 55) 

[1994Hug] HughJones, D.A., Woodland, A.B., Angel, R.J., “The Structure of High-Pressure C2/c Ferrosilite and 

Crystal-Chemistry of High-Pressure C2/c Pyroxenes”, Am. Mineral., 79, 1032–1041 (1994) (Experimental, 


[1994Mat] Matousek, J.W., “Equilibrium Oxygen Pressures of Iron Silicate Slags”, Metall. Mat. Trans. B, 25(3), 

463–465 (1994) (Thermodyn., Calculation, 12) 

[1996Boe] Boeher, R., “Experimental Constraints on Melting Conditions Relevant to Core Formation”, Geochim. 

Cosmochim. Acta, 60(7), 1109–1112 (Review, Phase Relations, 30) 

[1996Hug] HughJones, D., Sharp, T., Angel, R., Woodland, A., “The Transition of Orthoferrosilite to High- 

Pressure C2/c Clinoferrosilite at Ambient Temperature”, Eur. J. Mineral., 8, 1337–1345 (1996) (Experimental, 


[1996Sax] Saxena, S.K., “Earth Mineralogical Model: Gibbs Free Energy Minimization in the System MgO-FeO- 

SiO 2”, Geochim. Cosmochim. Acta, 60, 2379–2395 (1996) (Assessment, Thermodyn., Phase Relations, 

125) 

[1997Fab] Fabrichnaya, O.B., Sundman, B., “The Assessment of Thermodynamic Parameters in the Fe-O and 

Fe-O-Si Systems”, Geochim. Cosmochim. Acta, 61(21), 4539–4555 (1997) (Assessment, Thermodyn., 




MSIT 1


53 

[1997Hug] HughJones D., “Thermal Expansion of MgSiO 3 and FeSiO 3 Ortho- and Cinopyroxenes”, Am. Mineral. 

82, 689–696 (1997) (Experimental, Crys. Structure, 31) 

[1997Li] Li, G.Q., Suito, H., “Electrochemical Measurement of Critical Supersaturation in Fe-O-M (M = Al, Si, 

and Zr) and Fe-O-Al-M (M = C, Mn, Cr, Si, and Ti) Melts by Solid Electrolyte Galvanic Cell”, ISIJ Int., 


[1997Oht] Ohtaka, O., Tobe, H., Yamanaka, T., “Phase Equilibria for the Fe 2SiO 4-Fe 3O 4 System Under High 

Pressure”, Phys. Chem. Miner., 24(8), 555–560 (1997) (Experimental, Morphology, Phase Relations, 25) 

[1997Sel] Selleby, M., “An Assessment of the Fe-O-Si System”, Metall. Mater. Trans. B, 28, 563–576 (1997) 

(Assessment, Experimental, Kinetics, Phase Diagram, Phase Relations, Phys. Prop., 45) 

[1997Woo] Woodland, A.B., Angel, R.J., “Reversal of the Orthoferrosilite- High-P Clinoferrosilite Transition, a 

Phase Diagram for FeSiO3 and Implications for the Mineralogy of the Earth‘s Upper Mantle”, Eur. 

J. Mineral, 9, 245–254 (1997) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 33) 

[1998Ang] Angel, R.J., Woodland, A.B., “Crystal Structure of Spinelloid II in the System Fe 3O 4-Fe 2SiO 4”, Eur. 

J. Mineral, 10, 607–611 (1998) (Crys. Structure, Experimental, 23) 

[1998Lee] Lee, B.-J., “Thermodynamic Calculation for Stability of Oxides in Steel Systems” (in Japanese), 

J. Korean Inst. Met., 36(2), 217–224 (1998) (Calculation, Thermodyn., 57) 

[1998Won] Wong-Leung, J., Eagelsham, D.J., Sapjeta, J., Jacobson, D.C., Poate, J.M., “The Precipitation of the 

Si-SiO 2 Interface”, J. Appl. Phys., 83(1), 580–584 (1998) (Experimental, Phase Relations, 19) 

[1998Woo] Woodland, A.B., Angel, R.J., “Crystal Structure of a New Spinelloid with the Wadsleyite Structure in 

the System Fe 2SiO 4 -Fe 3O 4 and Implications for the Earth‘s Mantle”, Am. Mineral., 83, 404–408 (1998) 


[1999Ma] Ma, Z., Janke, D., “Oxygen and Nitrogen Reactions in Fe-X and Fe-Cr-Ni-X Melts”, Steel Research, 

70(10), 395–402 (1999) (Calculation, Thermodyn., 69) 

[1999Rom] Romero-Serrano, A., Pelton, A.D., “Thermodynamic Analysis of Binary and Ternary Silicate Systems 

by a Structural Model”, ISIJ Int., 39(5), 399–408 (1999) (Assessment, Phase Relations, Thermodyn., 23) 

[1999Ros1] Ross, N.L., Reynard, B.R., “The Effect of Iron on the P2 1/c to C2/c Transition in (Mg,Fe)SiO 3 

Clinopyroxenes”, Eur. J. Mineral, 11(3), 585–589 (1999) (Experimental, Optical Prop., Phase Relations, 

18) 

[1999Ros2] Ross, N.L., Sowerby, J.R., “High-Pressure Crystal-Field Spectra of Single-Crystal Clinoferrosilite”, Eur. 

J. Mineral, 11, 791–801 (1999) (Experimental, Phase Relations, Thermodyn., 29) 

[2000Haz] Hazen, R.M., Yang, H.X., Prewitt, C.T., “High-pressure Crystal Chemistry of Fe +3 -wadsleite, 

β-Fe 2.33Si 0.67O 4”, Am. Mineral., 85, 778–783 (2000) (Experimental, Crys. Structure, 37) 

[2000Woo] Woodland, A.B., Angel, R.J., “Phase Relations in the System Fayalite-Magnetite at High Pressures and 

Temperatures”, Contrib. Mineral. Petrol., 139, 734–747 (2000) (Experimental, Phase Relations, 44) 

[2001Bel] Belashchenko, D.K., Ostrovski, O.I., Skvortsov, L.V., “Molecular Dynamic Simulation of Binary CaO- 

FeO, MgO-SiO 2, FeO-SiO 2 and Ternary CaO-FeO-SiO 2 Systems”, Thermochim. Acta, 372, 153–163 

(2001) (Calculation, Thermodyn., 20) 

[2001Fri] Frisk, K., Selleby, M., “The Compound Energy Formalism: Applications”, J. Alloys Compd., 320(2), 

177–188 (2001) (Assessment, Phase Relations, Review, 41) 

[2001Zha] Zhang, J., Wang, P., “The Widespread Applicability of the Mass Action Law to Metallurgical Melts and 

Organic Solutions”, Calphad, 25(2), 343–354 (2001) (Calculation, Thermodyn., 19) 

[2001Ott] Ottonello, G., “Thermodynamic Constraints Arising from the Polymeric Approach to Silicate Slags: 

the System CaO-FeO-SiO 2 as an Example”, J. Non-Cryst. Solids, 282, 72–85 (2001) (Assessment, Phase 


[2001Yam1] Yamanaka, T., Shimazu, H., Ota, K., “Magnetic Properties of Fe 2SiO 4-Fe 3O 4 Spinel Solid Solutions”, 

Phys. Chem. Miner., 28, 102–109 (2001) (Crys. Structure, Magn. Properties, Experimental, 28) 

[2001Yam2] Yamanaka, T., Shimazu, H., Ota, K., “Electric Conductivity of Fe 2SiO 4-Fe 3O 4 Spinel Solid Solutions”, 

Phys. Chem. Miner., 28, 110–118 (2001) (Crys. Structure, Electr. Prop., Experimental, 35) 

[2002Che] Chen, G.Q., Ahrens, T.J., Stolper, E.M., “Schock-Wave Equations of State of Molten and Solid 

Fayalite”, Phys. Earth Planet. Inter., 134, 35–52 (2002) (Experimental, Mechan. Prop., 54) 

[2002Dav] Davies, R.H., Dinsdale, A.T., Gisby, J.A., Robinson, J.A.J., Martin, S.M., “MTDATA - Thermodynamic 

and Phase Equilibrium Software from the National Physical Laboratory”, Calphad, 26(2), 229–271 

(2002) (Calculation, Phase Relations, Thermodyn., 29) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

54 20 

Fe–O–Si 

[2002Lot] Lottermoser, W., Steiner, K., Grodzicki, M., Jiang, K., Scharfetter, G., Bats, J. W., Redhammer, G., 

Treutmann, W., Hosoya, S., Amthauer, G., “The Electric Field Gradient in Synthetic Fayalite α-Fe 2SiO 4 

at Moderate Temperatures”, Phys. Chem. Miner., 29, 112–121 (2002) (Crys. Structure, Electr. Prop., 


[2003Kap] Kapilashrami, E., Lahiri, A.K., Cramb, A.W., Seetharaman, S., “Investigation of the Reaction between 

Oxygen-Containing Iron and SiO 2 Substrate by X-Ray Sessile-Drop Technique”, Metall. Mater. Trans. B, 

34b(5), 647–652 (2003) (Interface Phenomena, Experimental, 11) 

[2004Fab] Fabrichnaya, O., Saxena, S.K., Richet, P., Westrum, E.F., “Thermodynamic Data, Model and Phase 

Diagrams in Multicomponent Oxide Systems”, Springer Verlag, Berlin Heidelberg, (2004) (Review, Phase 

Diagram, Thermodyn., Phys. Prop., 479) 

[2004Fre] Fredriksson, P., Seetharaman, S., “Thermodynamics Activities of FeO in some Binary FeO-Containing 

Slags”, Steel Res., 75, 240–246 (2004) (Calculation, Experimental, Thermodyn., 23) 

[2004Jun1] Jung, I.-H., Decterov, S.A., Pelton, A.D., “Critical Evaluation and Optimization in the FeO- 

Fe 2O 3-MgO-SiO 2 System”, Metall. Mater. Trans. B, 35b(5), 877–889 (2004) (Calculation, Theory, 


[2004Jun2] Jung, I.-H., Decterov, S.A., Pelton, A.D., “A Thermodynamic Model for Deoxidation Equilibria in 

Steel”, Metall. Mater. Trans. B, 35b(3), 493–507 (2004) (Calculation, Theory, Thermodyn., 100) 

[2004Kon] Kontny, A., Woodland, A.B., Koch, M., “Temperature-Dependent Magnetic Susceptibility Behaviour of 

Spinelloid and Spinel Solid Solutions in the Systems Fe 2SiO 4-Fe 3O 4 and (Fe,Mg) 2SiO 4-Fe 3O 4”, Phys. 

Chem. Miner., 31, 28–40 (2004) (Experimental, Magn. Prop., Phase Relations, 36) 

[2004Tyu] Tyurin, A.G., “Thermodynamic Analysis of the Silicon Effect on Chemical and Electrochemical 

Stability of Iron-Chromium Alloys”, Prot. Met., 40(1), 14–22 (2004) (Calculation, Phase Diagram, 

Phase Relations, Thermodyn., 17) 

[2005Ake] van Aken, P.A., Miehe, G., Woodland, A.B., Angel, R.J., “Crystal Structure and Cation Distribution in 

Fe 7SiO 10 (Iscorite)”, Eur. J. Mineral, 17, 723–731 (2005) (Crys. Structure, Experimental, Phys. Prop., 13) 

[2005Mik] Miki, T., Hino, M., “Numerical Analysis on Si Deoxidation of Molten Fe, Ni, Fe-Ni, Fe-Cr, Fe-Cr-Ni, 

Ni-Cu and Ni-Co Alloys by Quadratic Formalism”, ISIJ Int., 45(12), 1848–1855 (2005) (Calculation, 

Phase Diagram, Thermodyn., Phase Relations, 27) 

[2005Shi] Shibaev, S.S., Krasovskii, P.V., Grigorovitch, K.V., “Solubility of Oxygen in Iron-Silicon Melts in 

Equilibrium with Silica at 1873 K”, ISIJ Int., 45(9), 1243–1247 (2005) (Experimental, Phase Diagram, 


[2006Ama] Amano, T., Okazaki, M., Takezawa, Y., Shiino, A., Takeda, M., Onishi, T., Seto, K., Ohkubo, A., 

Shishido, T., “Hardness of Oxide Scales on Fe-Si Alloys at Room- and High-Temperatures”, Mat. Sci. 

Forum, 522–523, 469–476 (2006) (Experimental, Kinetics, Mechan. Prop., Morphology, Phase Relations, 

15) 

[2006Bas] Basu, S., Macdonald, J.R., Chakravorty, D., “Conductivity Relaxation in the Interfacial Phase of Iron 

Core-Iron Oxide Shell Nanocomposites”, J. Mater. Res., 21(7), 1704–1711 (2006) (Crys. Structure, 

Experimental, Morphology, Nano, 24) 

[2006Kim] Kim, J.C., Lee, J.W., Park, B.Y., Choi, C.J., “Synthesis and Magnetic Properties of Fe/SiO 2 Nanocomposite 

Powders by the Chemical Vapor Condensation Process”, Mat. Sci. Forum, 510–511, 762–765 

(2006) (Crys. Structure, Experimental, Morphology, Nano, 7) 

[2006Tak] Takeda, M., Onishi, T., “Oxidation Behavior and Scale Properties on the Si Containing Steels”, Mater. 

Sci. Forum, 522–523, 477–488 (2006) (Crys. Structure, Experimental, Kinetics, Morphology, Phase 


[2007Jak] Jak, E., Hayes, P., Pelton, A., Decterov, S., “Thermodynamic optimization of the FeO-Fe 2O 3-SiO 2 (Fe- 

O-Si) system by FactSage”, Int. J. Mater. Res., 98(9), 847–854 (Assessment, Phase Diagram, Thermodyn., 

Phase Relations, Calculation, 55) 

[2007Yon] Yong, W., Dachs, E., Withers, A.C., Essene, E.J., “Heat Capacity of γ-Fe 2SiO 4 Between 5 and 303 K and 

Derived Thermodynamic Properties”, Phys. Chem. Min., 34, 121–127, (2007) (Experimental, Thermodyn., 

30) 



MSIT 1


55 

[L-B] Landolt-Boernstein, Numerical Data and Functional Relationships in Science and Technology (New 

Series). Group 3 (Crystal and Solid State Physics), Vol. 6, Eckerlin, P., Kandler, H. and Stegherr, A., 

Structure Data of Elements and Intermetallic Phases (1971); Vol. 7, Pies, W. and Weiss, A., Crystal 

Structure of Inorganic Compounds, Part c, Key Elements: N, P, As, Sb, Bi, C (1979); Group 4: Macroscopic 

and Technical Properties of Matter, Vol. 5, Predel, B., Phase Equilibria, Crystallographic and Thermodynamic 

Data of Binary Alloys, Subvol. a: Ac-Au … Au-Zr (1991); Springer-Verlag, Berlin. 


(1990) 





MSIT 1 

DOI: 10.1007/978-3-540-70890-2_20 

ß Springer 2009

Iron – Oxygen – Uranium 


Pankaj Nerikar, Hans Jürgen Seifert, Pierre Perrot 

Introduction 

The Fe-O-U system is a key system in the disposal of nuclear waste where iron oxide is used 

with uranium waste and finds relevance in the prediction of high temperature phase behavior 

of corium. Two ternary compounds have been reported for the Fe-O-U system: UFeO 4 and 

UFe 2O 6 which seems to be stable only under high pressures [1978Col]. The experimental work 

is summarized in Table 1. The Fe-O-U ternary system was reviewed by [1989Rag]. [1964Eva] 

and [1983Smi] have constructed isothermal sections at different temperatures and partial 

pressures. [1973Buz] has reported the solubility of oxygen in (Fe,U) liquid alloys at 1600˚C. 


The Fe-U and O-U binary systems are accepted from the critical assessments of [2003Cha] and 

[2004Che], respectively. A precise model of the solid and liquid oxide solutions taking into 

account the oxygen vacancies in the O-U system may be found in [2002Gue]. The O-U binary 

phase diagram from [2004Che] is presented in Fig. 1. The Fe-O phase diagram is accepted 

from the assessment by [1991Sun]. 


The crystallographic data for the phases present in the Fe-O-U system and their ranges of 

stability are summarized in Table 2. 


Table 3 lists the invariant reactions of the Fe-O-U ternary system from investigation of 

[1964Eva]. They have identified two ternary eutectic points which occur at oxygen partial 

pressures of 0.028 and 0.011 bar, respectively. 


Fe–O–U 21 

1 

[1989Rag] gave the Fe-O-U isothermal section at 400˚C from the experimental investigations 

of [1983Smi]. This diagram, shown in Fig. 2, is compatible with the well known fact that Fe 3O 4 

oxidizes into Fe 2O 3 at lower oxygen pressures than UO 2 oxidizes into U 4O 9. Unfortunately, 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_21 

ß Springer 2009

2 21 

Fe–O–U 

neither [1964Eva] nor [1983Smi] took into account the ternary compound UFeO 4 obtained 

from the reaction: 

2U 3O 8+3Fe 2O Ð UFeO 4+0.5O 2. 


[1964Eva] have carefully investigated the equilibrium relationships between uranium and iron 

oxides as a function of oxygen pressure (586-21300 Pa) and temperature (1200-1460˚C). 

Figures 3 to 8 show the projected isobaric sections under oxygen pressures of 21300 (air 

atmosphere), 7093, 3456, 1773, 892 and 586 Pa, respectively. It must be pointed out that the 

diagrams presented are not vertical sections because the phases in equilibrium are strongly 

dependent of the oxygen pressure. For instance, under air atmosphere Fe 2O 3, stable under 

1415˚C loses its oxygen to give Fe3O4 above that temperature as shown in Fig. 3. The transition 

Fe2O3 Ð Fe3O4 occurs at 1359, 1328, 1306, 1289 and 1273˚C under 7093, 3456, 1773, 892 and 

586 Pa of oxygen pressure, respectively. In the same way, the transition U 3O 8 Ð UO 2 occurs at 

1448, 1385, 1358, 1316 and 1296˚C under 7093, 3456, 1773, 892 and 586 Pa of oxygen pressure, 

respectively. The three phases UO 2-Fe 2O 3-Fe 3O 4 coexist in the solid state at 1248˚C under 200 

Pa of oxygen pressure. 


The ferric-ferrous buffer (mixture Fe 3O 4-Fe 2O 3) found naturally may be used to stabilize the 

state of oxidation IV of uranium [1983Smi]. 

Fe-U oxides can be used in an energetically efficient way as catalysts for the partial 

oxidation of propane and propene into formaldehyde which is an industrially important 

intermediate [2003Tay] in addition to the applications mentioned in the Introduction. 

. Table 1 

Investigations of the Fe-O-U Phase Relations, Structures and Thermodynamics 


[1964Eva] Thermogravimetric analysis under 

controlled oxygen pressures 


Studied 

UO 2-U 3O 8-Fe 2O 3-Fe 3O 4, 1260-1460˚C, 586 to 

21300 Pa of oxygen pressure 

[1973Buz] Interaction parameters measurements Liquid Fe-O-U alloy (< 10 mass% U, 

. Table 2 



Temperature Range 

[˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 

Fe–O–U 21 

Lattice 

Parameters 


(αU) oC4 a = 285.37 at 25˚C [Mas2] 

< 668 Cmcm b = 586.95 

αU c=495.48 

(βU) tP30 a = 1075.9 at 25˚C [Mas2] 

776 - 668 P42/mnm βU 

c = 565.6 

(γU) cI2 a = 352.4 [Mas2] 

1135 - 776 Im3m 

W 

(Fe) cI2 a = 286.65 at 25˚C [Mas2] 

1538 - 1394 Im3m a = 293.15 at > 1394˚C [Mas2] 

< 912 W 

(γFe) cF4 a = 364.67 at 25˚C [Mas2] 

1394 - 912 Fm3m 

Cu 

Fe2U cF24 a = 705.5 [2003Cha] 

< 1235 Fd3m 

Cu2Mg FeU6 tI28 a = 1024.99 [2003Cha] 

< 829 I4/mcm 

MnU6 c = 525.00 

Fe1–xO (wüstite) cF8 0.05 < x < 0.12 [1991Sun] 

1422 - 569 Fm3m a = 431.0 x = 0.05 

NaCl a = 429.3 x = 0.12 

Fe3O4 (r) oP56 a = 1186.8 [V-C2] 

< 580 Pbcm b = 1185.1 

Fe3O4 (r) c=1675.2 

Fe3O4 (h) (magnetite) cF56 a = 839.6 at 25˚C 

1597 - 580 Fd3m 

MgAl204 a = 854.5 at 1000˚C [V-C2] 

αFe2O3 (hematite) hR30 a = 503.42 at 600˚C [Mas2, V-C2] 

< 1451 R3c 

Al2O3 c = 1374.83 

βFe2O3 cI80 

Ia3 

Mn2O3 a = 939.3 metastable phase [V-C2] 



MSIT 1 

3 

DOI: 10.1007/978-3-540-70890-2_21 

ß Springer 2009

4 21 

Fe–O–U 




[˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 

Lattice 

Parameters 


γFe2O3 (maghemite) tP60 a = 833.96 metatable phase [V-C2] 

P41212 Mn5Si2 (?) 

c = 832.21 

UO2 cF12 a = 547.0 from 62.7 to 66.7 at.% O [2004Che] 

< 2852 Fm3m 

CaF2 U4O9 cI832 a = 2176 [2004Che] 

< 1123 I432 or 

I4132 U3O8 oC44 a = 706.9 [2004Che] 

< 1870 Cmcm b = 1144.5 

c = 830.3 

UO3 cP4 a = 414.6 [2004Che] 

< 669 Pm3m 

ReO3 * UFeO4 oP* a = 488.80 [1989Rag] 

Pbcn b = 1193.7 

c = 511.0 

* UFe2O6 hP* a = 504.0 ± 0.1 [1978Col] High pressure phase (600˚C, 

P31m 

PbSb2O6 c = 469.2 ± 0.1 3 GPa) 

. Table 3 




U Fe O 

L Ð U3O8 +Fe2O3 +Fe3O4 1318 E1 L 13.50 21.76 64.74 

L Ð U3O8 +UO2 +Fe3O4 1326 E2 L 14.65 20.75 64.60 



MSIT 1

. Fig. 1 

Fe-O-U. The calculated O-U equilibrium phase diagram 



MSIT 1 

Fe–O–U 21 

5 

DOI: 10.1007/978-3-540-70890-2_21 

ß Springer 2009

6 21 

Fe–O–U 

. Fig. 2 

Fe-O-U. Isothermal section at 400˚C 



MSIT 1

. Fig. 3 

Fe-O-U. Isobaric section under 21300 Pa of oxygen (1355 and 1415˚C) 



MSIT 1 

Fe–O–U 21 

7 

DOI: 10.1007/978-3-540-70890-2_21 

ß Springer 2009

8 21 

Fe–O–U 

. Fig. 4 

Fe-O-U. Isobaric section under 7093 Pa of oxygen (1328, 1359 and 1448˚C) 



MSIT 1

. Fig. 5 




MSIT 1 

Fe–O–U 21 

9 

DOI: 10.1007/978-3-540-70890-2_21 

ß Springer 2009

10 21 

Fe–O–U 

. Fig. 6 




MSIT 1

. Fig. 7 




MSIT 1 

Fe–O–U 21 

11 

DOI: 10.1007/978-3-540-70890-2_21 

ß Springer 2009

12 21 

Fe–O–U 

. Fig. 8 




MSIT 1

References 

Fe–O–U 21 

13 

[1964Eva] Evans, W.D.J., White, J., “Equilibrium Relationships in the System UO 2-Fe 3O 4-O”, Trans. Brit. Ceram. 

Soc., 63(12), 705–724 (1964) (Phase Diagram, Thermodyn., Experimental, *, #, 10) 


Iron at 1600˚C”, Int. Symp. Metallurgical Chemistry - Applications in Ferrous Metallurgy, Iron and Steel 

Inst, London, 173–177 (1973) (Crys. Structure, Experimental, Review, 8) 

[1978Col] Collomb, A., Capponi, J.J., Gondrand, M., Joubert, J.C., “Hydrothermal Synthesis of Some Mixed 

Oxides A 6+ B 3+ O6 under High Pressures” (in French), J. Solid State Chem., 23, 315–319 (1978) (Crys. 


[1983Smi] Smith, D.K., Freeborn, W.P., Scheetz, B.E., “Compatibility Relationships in the U-Fe-O (-H) at 400˚C: 

The Implications of the Ferric-Ferrous Buffer for the Immobilization of Uranium and Transuranic 

Elements”, Mater. Res. Soc.: Symp. Proc., Sci. Basis Nucl. Waste Managt., 15(6), 91–95 (1983) (Experimental, 

*, 6) 

[1989Rag] Raghavan, V., “The Fe-O-U (Iron-Oxygen-Uranium) System”, Phase Diagrams of Ternary Iron Alloys 

(Indian Inst. Metals, Ed.) 5, 332–335 (1989) (Phase Diagram, Review, 6) 


Diagram, Thermodyn., Assessment, #, 53) 

[2002Gue] Gueneau, C., Baichi, M., Labroche, D., Chatillon, C., Sundman, B., “Thermodynamic Assessment of the 

Uranium-Oxygen System”, J. Nucl. Mater., 304, 161–175 (2002) (Assessment, Phase Diagram, Phase 

Relations, Thermodyn., #, 88) 

[2003Cha] Chatain, S., Gueneau, C., Labroche D., Rogez, J., Dugne, O., “Thermodynamic Assessment of the Fe-U 

Binary System”, J. Phase Equilib., 24(2), 122–131 (2003) (Thermodyn., Assessment, Review, #, 34) 

[2003Tay] Taylor, S.H., Hutchings, G.J., Palacios, M.-L., Lee, D.F., “The Partial Oxidation of Propane to 

Formaldehyde Using Uranium Mixed Oxide Catalysts”, Catal. Today, 81, 171–178 (2003) (Catalysis, 

Experimental, Interface Phenomena, 9) 

[2004Che] Chevalier, P.-Y., Fischer, E., Cheynet, B., “Progress in the Thermodynamic Modelling of the O-U-Zr 

Ternary System”, Calphad, 28, 15–40 (2004) (Assessment, Calculation, Phase Diagram, Thermodyn., 92) 


(1990) 





MSIT 1 

DOI: 10.1007/978-3-540-70890-2_21 

ß Springer 2009

Iron – Oxygen – Tungsten 



Introduction 

The phase relationships in the Fe-O-W system are of great interest from a number of different 

aspects. In particular, ternary phases of this system have been the subject of many experimental 

studies aimed to establish the correlation among their structural, magnetic and conducting 

properties because these phases have found application in the direct conversion of solar to 

electrical energy [1999Gus]. Moreover, the WO 3/Fe 2O 3 composite is the best material for the 

manufacture of nanostructured photo-electrodes owing to its enhanced photocurrent-voltage 

characteristics [2007Luo]. Multi-component systems of transition metal oxides (in particular, 

of tungsten and iron) are of interest because of the catalytic properties of their components, 

which can be used to oxidize organic substances. 

However, information about the constitution of the Fe-O-W system is incomplete. 

Experimental studies of phase equilibria have dealt with the WO 3-Fe 2O 3 temperature-composition 

section [1978Gar, 1978Tru, 1993Wal] along with partial sections of the Fe-O-W system 

at 1100˚C [1977Eks], 1000˚C [1969Sch, 1970Kot, 1977Gel] and 900˚C [1972Sch]. Further 

determinations of the phase relations are needed, especially for the liquid-solid equilibria. 

Publications devoted to the experimental study of the phase relations, crystal structures 

and thermodynamics are listed in Table 1. Reviews of the literature relating to phase equilibria 

and crystal structures of the Fe-O-W phases have been presented in [1976Jeh, 1989Rag]. 


The Fe-O boundary binary system is accepted as compiled in [Mas2]. The O-W boundary 

system is taken from the important review of [1989Wri], which has been reproduced in 

[Mas2]. The Fe-W boundary binary system is accepted according to the thermodynamic 

assessment of [1987Gus] as accepted by [1988Fer]. This diagram differs from that given by 

[Mas2] in relation to the μ (W 6Fe 7) phase field. The δ (WFe) phase is considered as 

metastable. 


Fe–O–W 22 

1 

Crystallographic data for the known unary, binary and ternary Fe-O-W phases are given in 

Table 2. No solubility of the third element in the binary phases has been reported. 

The crystal structure of the τ1, WFeO4, phase has been widely reported in the literature 

[1930Bro, 1957Koz, 1967Uel, 1968Cid, 1970Kle, 1972Sle, 1974Lyo, 1982Sie, 1991Sch, 1993Yu, 

2003Yu, 2006McK]. The phase possesses a monoclinic symmetry with a value of the β angle of 

about 90˚, according to practically unanimous agreement of the different investigators. The 

hydrothermal synthesis of WFeO 4 crystals has been studied by [1970Kle]. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_22 

ß Springer 2009

2 22 

Fe–O–W 

For quite a long period of time, the τ 2,WFe 2O 6, ternary phase was considered as occurring 

in two polymorphic varieties. The low-temperature form possessing a columbite type 

structure, forming at 800˚C, undergoes a monotropic transformation at 950˚C to a hightemperature 

modification with a αPbO 2 structure. But [1993Wal] established that the 

low-temperature modification, designated as τ 2y¯, WFe 2O 6 (r) in Table 2, being formed at 

650-800˚C, transforms monotropically into a monoclinic modification (τ2´, WFe2O6 (h1)) 

during heating up to 750-900˚C. At 950˚C, the latter undergoes an enantiotropic polymorphic 

transformation to the τ 2,WFe 2O 6 (h 2) phase with a αPbO 2 structure, that was earlier described 

in the literature as the high-temperature form of the compound. The crystal structure of the 

τ 2 phase has been reported in [1957Koz, 1966Tru, 1973Par, 1974Sen, 1976Wei, 1977Pin, 

1982Lei1, 1982Lei2, 1988Bir]. The τ 3,WFe 0.1O 3 and τ 4,W 0.99Fe 0.01O 2.80, phases were observed 

by [1977Eks, 1978McC]. 

Other reported ternary phases are not stable. The WFeO x (0.4 ≤ x ≤ 1.0) and W 3Fe 3O 

phases were reported by [1954Sch1] and [1954Sch2], respectively, but subsequently, their 

existence in the equilibrium state has not been confirmed. Consequently, the W3Fe3O 

phase was not seen by [1970Kot] in their investigations at 1000˚C, and it was concluded 

that this phase had been stabilized by the presence of nitrogen in samples used the studies 

undertaken by [1954Sch2]. Neither phase was found in studies at 1000˚C undertaken by 

[1977Gel]. The tungstate Fe 2(WO 4) 3 (or W 3Fe 2O 12) was reported by [1985Har, 1987Mai, 

2003Sri]. It was found to decompose at temperatures above 450˚C to give Fe 2WO 6 which, at 

750˚C, loses oxygen to give 2FeWO 4 +WO 3.[2003Sri] found it very difficult to prepare 

this phase by solid state synthesis starting from the component oxides, but proposed that 

aqueous solutions of ferrous ammonium sulfate and sodium tungstate be used as precursor 

materials. 


Phase relationships in the WO 2-WO 3-WFe 2O 6 partial system at 1100˚C were studied by 

[1977Eks]. The samples used in the investigations were obtained from WO4H2 and Fe2O3 

starting materials. Firstly, WO3 oxide was prepared by heating WO4H2 in air at about 827˚C 

for several days, and WO 2 was prepared from the trioxide by reduction in a stream of a H 2/ 

H 2O gas mixture at 750˚C. In order to obtain a suitable partial pressure of water, the hydrogen 

gas was allowed to bubble through water held at a temperature of 85˚C. Appropriate amounts 

of the oxides were thoroughly mixed and sealed in evacuated silica tubes or in Pt ampoules and 

heated at a temperature of 1100˚C for periods ranging from 3 days up to 3 months. On the 

basis of X-ray diffraction, and optical and electron microscopy studies, a partial isothermal 

section for 1100˚C was constructed; it is shown in Fig. 1 with amendments to ensure 

compatibility with the phase boundaries in the accepted O-W phase diagram. The W24O68 

phase that was observed by [1989Wri] in mixtures of WO 3 and W that had been annealed at 

1100˚C is added, and equilibria involving this phase are given with dashed lines. The W 20O 58 

phase that was reported by [1977Eks] as being stable at this temperature, is shown as it is a 

member of the W nO 3n–2 series of compositions. No evidence for Fe substituting in any 

significant amount for W in the binary tungsten oxides was found by [1977Eks]. The “irontungsten 

bronze” WFe xO 3 phases in this region were found to be metastable. 

Phase equilibria at 1000˚C were investigated by [1969Sch, 1970Kot, 1977Gel]. [1969Sch] 

prepared samples of Fe3O4, FeO, WFeO3, WFeO4 and WO2 by annealing in evacuated quartz 



MSIT 1

ampoules, followed by further heating of to enable the reactions between them to progress. 

It was reported that at 1000˚C, the τ 1 phase possesses a wide homogeneity range enclosed by 

the WO 2-FeO and WO 3-FeO lines. [1970Kot] prepared samples at 20 compositions around 

W 3Fe 3O in a two stage process. Firstly, mixtures of Fe, W and Fe 2O 3 were sintered for 100 h at 

1000˚C in evacuated Vycor capsules. This was followed by crushing, pressing and sintering 

again for 100 h at 1000˚C. The so-called W 3Fe 3O phase with a Ti 2Ni-type structure reported by 

[1954Sch2], was not observed. Instead, the Fe2O3 oxide was found to react with the metals to 

produce binary metallic phases. [1977Gel] annealed samples in evacuated quartz tubes at a 

temperature of 1000˚C for between 2 and 10 days followed by cooling in air. An isothermal 

section for the W-WO 2-τ 1-τ 2-Fe 2O 3-Fe region was proposed. It is presented in Fig. 2 with 

small corrections introduced to take into account the phase boundaries of the accepted binary 

systems. In particular, (δαFe) and (γFe) were introduced instead of (Fe) as presented by 

[1977Gel]; the three-phase region τ 1 + δα +(γFe) was added (marked by dashed lines). The 

boundary tie line (W)-τ 1 of the (W) + μ + τ 1 three-phase region is plotted, also by dashed 

lines. As noted in the review of [1989Rag], the phase boundaries of the τ1 phase field could not 

be determined accurately owing to experimental difficulties and therefore this boundary is 

drawn with dashed lines. 

Phase relationships in the W-WO 3-Fe 2O 3-Fe partial system were studied by [1972Sch] at 

900˚C by determining chemical equilibria under CO/CO 2 atmospheres. It was reported 

that at 900˚C, the τ 1 phase dissolves 32 mol% Fe 3O 4. Generally, the characteristics of 

phase relations proposed by [1972Sch] are similar to those reported by [1969Sch, 1970Kot, 

1977Gel] at 1000˚C but the participation of the λ phase was ignored. 


Fe–O–W 22 

3 

The WO 3-Fe 2O 3 temperature-composition section was presented in [1978Gar, 1978Tru, 

1993Wal] as well as in the review of [1989Rag] as quasibinary but actually, the solid liquid 

equilibria as well as the oxidation state of the phases depend strongly on the imposed oxygen 

pressure. The heat treatment of WO 3 and Fe 2O 3 pelletized mixtures was carried out in the 

temperature range 1150-1000˚C [1978Gar]. The temperature-composition section was constructed 

from X-ray diffraction and optical microscopy studies. The congruent melting of the 

τ 2 phase at 1142 ± 5˚C, together with two eutectic equilibria between this phase and WO 3 and 

Fe 2O 3 at the temperatures of 1050˚C and 1120 ± 5˚C, respectively, were proposed. At the same 

time, both [1974Sen] and [1978Tru] reported the incongruent melting of τ 2; at 1130 and 

1156 ± 4˚C, respectively. According to the data of [1978Tru], eutectic solidification takes place 

only in the WO 3-τ 2 part of the system (the eutectic point is placed at 1051˚C and 26 mol. % 

Fe 2O 3). Both [1978Gar] and [1978Tru] concluded that no visible solubility or homogeneity 

range exists for the compounds of this section. Later, the section was studied by [1993Wal] 

using both X-ray diffraction and differential thermal analysis techniques. Samples were 

prepared from mixtures of WO 3 and Fe 2O 3 oxides in appropriate ratios. These mixtures 

were homogenized by powdering, pressing and heating at 900˚C for 24 h and at 950˚C for 

24 h. DTA measurements were performed at temperatures between 20 and 1200˚C. On the 

basis of the experimental results obtained, a temperature-composition section for WO 3-Fe 2O 3 

was constructed. It is presented in Fig. 3 with corrections relating to the locations of the phase 

boundaries in the accepted O-Fe and O-W systems. With a view to eliminating ambiguity in 

the designations of the phase fields containing the different modifications of the τ2 and WO3 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_22 

ß Springer 2009

4 22 

Fe–O–W 

phases, the lower temperature limit of the section was increased to slightly higher than 950˚C 

(contrary to about 900˚C in [1993Wal]). The incongruent melting temperature of τ 2, (WFe 2O 6 

(h 2)) was accepted as 1100 ± 10˚C. 


The thermodynamic properties of dilute solutions of oxygen in Fe-W alloys were studied by 

[1965Tan] by means of hydrogen-water vapor equilibria measurements. The reaction studied 

was H 2 (gas) + O (solution) Ð H 2O (gas). The equilibrium constant for this reaction is: K = 

p H2O/(p H2 {% O}), where p H2O and p H2 are the partial pressures of water vapor and hydrogen 

and {%O} is the amount of dissolved oxygen in mass%. It was shown for the W 20Fe 80 (mass%; 

W 7.06Fe 92.94 in at.%) alloy that at 1550˚C, the equilibrium constant is relatively independent of 

the oxygen content in the range up to 0.1 mass% O. For this alloy, the relationship between the 

equilibrium constant and temperature in the temperature range 1550-1700˚C is: log10 K= 

{(6917 ± 20)/T)} – (3.05 ± 0.01). The interaction parameter for tungsten contents up to 20 

mass% is ε O W = 0.008. Later, the oxygen activity in an iron melt containing up to 32 mass% W 

was determined by [1971Fis] using solid electrolyte cells. The value of interaction parameter in 

the range of compositions 3.86 to 31.5 mass% W at 1600˚C was obtained as ε O W = 0.011. 

Using equilibria under CO/CO 2 gas mixtures, [1972Sch] established that at 900˚C, 

the values of Δ rG for the reactions “FeO” + WO 3 Ð WFeO 4 and Fe 2O 3 +WO 3 Ð WFe 2O 6 

are –43.1 ± 5.0 and –95.3 ± 23.4 kJ·mol –1 , respectively. 

The heat capacity of WFeO4 was measured by [1974Lyo] in the temperature range 5-550 K 

by adiabatic calorimetry. The temperature of the maximum heat capacity of the antiferromagnetic 

anomaly was found to be (75.25 ± 0.1) K. [1980Amo] used high temperature 

solution calorimetry to determine the enthalpy of reaction for WO 3 (solid, 298.15 K) + FeO 

(solid, 298.15 K) Ð WFeO 4 (solid, 298.15 K) giving Δ rH 0 (WFeO 4, solid, 298.15 K) = 

– (77.1 ± 6.0) kJ·mol –1 . The Gibbs energy of formation of the τ 1, WFeO 4 phase was determined 

by [1980Kle, 1983Kle] by emf measurements using solid galvanic cells using a ThO 2 

electrolyte. The following equation was obtained for the temperature range 1180-1330 K 

(907 to 1057˚C): – 1138200 + 299.2 T ± 2200 J·mol –1 . Standard entropy values for the 

WFeO 4 compound were used by [1988Bag] to calculate (H 0 298 - H 0 0). Good agreement was 

observed between calculated and experimental data. 


Fe-O-W alloys are of great interest for a number of practical applications in modern technology, 

in particular in relation to energetics, as catalysts in the chemical industry (W3Fe2O12), as 

nanostructured photoelectrodes (WO 3/Fe 2O 3 composite) etc. The experimental techniques 

used in the investigation of physical properties of Fe-O-W alloys are listed in Table 3. 

P-type conduction has been reported from thermopower investigations of WFeO 4 

[1991Sch]. The non-stoichiometric samples were produced under slightly oxidizing conditions 

and exhibited a reduced electrical resistivity which appears to be related to the presence 

of an enhanced Fe 3+ content in addition to Fe 2+ . This compound was reported by 

[2001Kaw] as possessing antiferromagnetic properties with a Néel temperature of 70 K. 

Magnetic susceptibility and EPR measurements using modifications of the τ2, WFe2O6, 



MSIT 1

phase at low temperatures [1995Gus] revealed a significant paramagnetic contribution, 

probably resulting from local distortions of the antiferromagnetic bulk structure induced by 

a disturbed cation ordering or the presence of Fe 2+ ions. The high-electrical resistivity found 

for the modifications of the τ 2 phase as observed by [1999Gus] are consistent with the presence 

of the dominant antiferromagnetic component of the compounds. 

Electrodes of WO 3/Fe 2O 3 were prepared on a FTO substrate by [2007Luo] using a sol-gel 

method, and subsequently, their photoelectrochemical properties were studied in a threeelectrode 

cell. The semiconductor electrodes generated an anode photocurrent, which suggested 

they were n-type semiconductors. 

Miscellaneous 

Fe–O–W 22 

5 

The kinetics of the reactions between iron oxides and WO 3 were studied by [1957Koz]. The 

kinetics of oxidation in air of the alloy Fe90.23W9.77 (mass%; in at.% - Fe96.82W3.18) at the 

temperatures of 740, 830, 900 and 960˚C were investigated by [1962Yat]. An ‘induction period’ 

of the oxidation lasting from 5 to 20 h at temperatures from 740 to 900˚C was noted. It was 

established that the resultant oxide film consisted of three layers. The kinetics of crystallization 

of WFeO 4 was studied by [1984Buh] using hydrothermally reacting the metal (II)-chlorides 

and sodium tungstate in a special autoclave, at 300 and 400˚C and a pressure of 1 kbar. The 

rates of crystallization were determined by continual removal of the reactants from the 

autoclave. At both temperatures, a decrease in the tungstate concentration in the solution 

followed first order reaction kinetics. The rate constants of the reactions were calculated and 

the Jerofejev equation was used to describe the kinetics. In order to explain the experimentally 

observed influence of the gases on the synthesis of iron tungstate (Fe 2O 3 +WO 3 + WFe 2O 6), 

different solid-solid mechanisms [1984Tho2] and gas-solid mechanisms [1984Tho3] have 

been considered. Comparisons between the theoretical and experimental kinetics curves show 

that diffusion in the solid state is not the only limiting step in the synthesis, and the strong 

influence of gases on the reaction kinetics confirms this conclusion [1984Tho2]. In 

[1984Tho3], a gas-solid mechanism for the synthesis of iron tungstate and a description of 

its elementary steps (tungsten oxide volatilization, gaseous diffusion and condensation) have 

been developed, and new kinetics laws for pure volatilization or condensation have been given. 

It was noted that some experimental results agreed with models of sublimation or condensation, 

but the comparison between experimental and theoretical kinetics curves indicated that 

the iron tungstate synthesis is governed at 800 or 760˚C by a mixed regime of volatilization and 

diffusion in the solid phase. Ferric tungstate W 3Fe 2O 12 was investigated by [1985Har] asa 

catalyst for the selective oxidation of methanol and was shown to have very different properties 

from ferric molybdate for this application. Over the molybdate, the predominant reaction 

is the oxidation of methanol to formaldehyde, whereas over the tungstate it is dehydration to 

dimethyl ether. Structural changes of coprecipitated and mechanically mixed iron/tungsten 

oxides occurring during calcination and reduction were studied by [1987Mai]. The temperature 

dependence of the EPR spectrum for the τ 2, (WFe 2O 6 (r)) phase has been investigated by 

[1998Gus] over the temperature range 40-260 K. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_22 

ß Springer 2009

6 22 

Fe–O–W 

. Table 1 

Investigations of the Fe-O-W Phase Relations, Structures and Thermodynamics 


[1930Bro] X-ray powder diffraction (XRD) WFeO 4 

Temperature / Composition 

/ Phase Range Studied 

[1954Sch1] XRD (Guinier technique) WFeOx (x = 0.4 to 1.0) 

[1954Sch2] XRD (Guinier technique) W3Fe3O, WO2 [1957Koz] Diffusion annealing, XRD, chemical analysis WFeO 4, WFe 2O 6 

[1965Tan] Hydrogen-water vapor equilibrium 1550-1700˚C, 70-100 mass% 

Fe, ≤ 0.12 mass% O 

[1966Tru] XRD 1200˚C, 1000˚C, the WO3- Fe2O3 section 

[1967Uel] XRD WFeO4 [1968Cid] XRD on single crystal, chemical analysis WFeO 4 

[1969Sch] Solid state reactions in evacuated quartz ampoules, Xray 

diffraction 

1000˚C, 50 to 75 at.% O 

[1970Kle] Hydrothermal synthesis, XRD, thermal analysis 600-375˚C, 

p = 400-1700 atm, WFeO 4 

[1970Kot] Sintering, XRD, optical microscopy 1000˚C, composition range 

around W3Fe3O [1971Fis] Solid electrolyte cells 1600˚C 

[1972Sch] Equilibria measurements under CO/CO2 gas mixture 900˚C, the W-WO3-Fe2O3-Fe partial system 

[1972Sle] XRD (Haegg-Guinier camera) WFeO4 [1973Par] Annealing, XRD WFe 2O 6 

[1974Lyo] Adiabatic calorimetry (Mark II adiabatic cryostat, Mark 

IV adiabatic thermostat) 

5-550 K, WFeO 4 

[1974Sen] Annealing, XRD WFe 2O 6 

[1976Wei] Neutron diffraction WFe 2O 6 

[1977Eks] Heating of WO4H2 in air, reduction of WO3, X-ray 

powder diffraction, optical microscopy, electron 

microscopy 

1100˚C, the WO2-WO3- 

Fe 2WO 6 partial system 

[1977Gel] Annealing, XRD (Guinier camera) 1000˚C, the W-WO2-τ1-τ2- 

Fe2O3-Fe region 

[1977Pin] XRD, neutron diffraction WFe2O6 [1978Gar] Annealing, quenching, XRD, reflected light microscopy 1150-1000˚C, the WO3-Fe2O3 section 

[1978McC] Heating, pressurizing; optical microscopy XRD, 

Weissenberg X-ray technique 

≤ 1100˚C, the WO3-Fe section 



MSIT 1



Temperature / Composition 

/ Phase Range Studied 

[1980Amo] High-temperature solution calorimetry 667˚C, 25˚C, WFeO 4, FeO + 

WO 3 

[1980Kle] Emf measurements 907-1057˚C, WFeO 4 

[1982Lei1] Solid state reactions, XRD, (Debye- Scherrer technique) WFe 2O 6 

[1982Sie] Solid state reactions, single crystals synthesis, XRD WFeO 4 

[1985Har] XRD Fe2(WO4)3, preparation, 

catalytic properties 

[1987Mai] XRD, DTA Fe2(WO4) 3, preparation, 

decomposition 

[1988Bir] Calcination in air, Mössbauer, XRD WFe2O6 [1991Sch] Single crystals and polycrystalline samples 

preparations, XRD (Laue technique) 

WFeO 4 

[1993Wal] Annealing, DTA, XRD 950˚C, 900˚C, the WO3-Fe2O3 section 

[1993Yu] Single crystals preparation, XRD, electron microprobe 

analysis 

WFeO4 [2003Sri] XRD, XRD Preparation of Fe2(WO4) 3 and 

calcination in air 

[2003Yu] Hydrothermal treating, XRD WFeO4 [2006McK] XRD, Mössbauer WFeO4; WFeO4 +C 

[2007Luo] Sol-gel method; XRD, UV-visible transmission 

spectroscopy, SEM, EDS 



MSIT 1 

Fe–O–W 22 

WO 3,Fe 2O 3, the WO 3/Fe 2O 3 

composites 

7 

DOI: 10.1007/978-3-540-70890-2_22 

ß Springer 2009

8 22 

Fe–O–W 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


(W) cI2 a =316.52 at 25˚C [Mas2] 

< 3422 Im3m 

W 

Dissolves 2.6 at.% Fe at 1637˚C 

δα, (δFe,αFe) cI2 

Im3m 

(δFe) W a = 293.15 at 1394˚C [Mas2] 

1538 - 1394 Dissolves 14.3 at.% W at 1548˚C 

(αFe) (Ferrite) 

< 912 


(γFe) (Austenite) cF4 a = 364.67 at 915˚C [Mas2] 

1394 - 912 Fm3m 

Cu 

Dissolves 1.2 at.% W at 1100˚C [Mas2] 

(εFe) hP2 a = 246.8 at 25˚C, > 13 GPa [Mas2] 

P63/mmc Mg 

c = 396.0 

λ,WFe2 hP12 a = 473.7 [1986Nag, 1987Gus] 

< 1062 P63/mmc MgZn2 c = 770.0 C14 structure 

μ, W6Fe7 hR39 ~56 to 59.5 at.% Fe 

< 1641 R3m D85structure [1989Rag] 

W6Fe7 a = 476.4 ±⊊0.3 [V-C2] 

c = 2585 ±⊊2 

δ, WFe oP* 

P212121 MoNi 

- metastable [1988Fer] 

FeO (Wüstite) cF8 actually (Fe1–xO with 0.05 < x < 0.12) 

1422 - 569 Fm3m a = 431.2 x = 0.05 [V-C2] 

NaCl a = 429.3 x=0.12 [V-C2] 

αFe3O4 (r) oP56 a = 1186.8 [V-C2] 

< 580 Pbcm b = 1185.1 

Fe3O4 I c=1675.2 

βFe3O4 (h) 

(Magnetite) 

cF56 inverse Spinel 

1597 - 580 Fd3m a = 854.5 at 1000˚C [V-C2] 

MgAl2O4 (Spinel) 

a = 839.6 at 25˚C [V-C2] 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


αFe2O3 (Hematite) hR30 a = 503.42 [1989Rag] 

< 1457 R3c αAl2O3 (Corundum) 

c=1374.83 

βFe2O3 cI80 metastable phase 

Ia3 

βMn2O3 (Bixbyite) 

a = 939.3 [V-C2] 

γFe 2O 3 

(Maghemite) 

cF56 metastable phase 

Fd3m a = 834 

MgAl2O4 

[1989Rag] 

Fe–O–W 22 

εFe2O3 m*100 metastable 

a = 1299 

b = 1021 

c = 844 

β = 95.33 

[V-C2] 

WO2 mP12 a = 555.6 ~ 66.7 at.% O [1989Wri] 

< 1530 P21/c b = 489.31 

VO2 c = 565.77 

β = 120.42˚ 

W18O49 mP67 a = 1832.4 ~73.1 at.% O [1989Wri] 

> 1700 - 585 P2/m b = 378.4 

W18O49 c = 1403.5 

β = 115.20˚ 

W24O68 m*92 a = 1931 ~ 73.9 at.% O [1989Wri] 

W24O68 b = 378.1 

c = 1707 

β= 104.4˚ 

W20O58 mP78 a = 1205 74.4 at.% O; member of the WnO3n–2 series 

P2/m b = 376.7 [1989Wri] 

W20O58 c = 2359 

β = 85.47˚ 

W24O70 mP94 a = 1207 74.5 at.% O; member of the WnO3n–2 series 

W24O70 b = 378 

c = 2890 

β = 98.6˚ 

[1989Wri] 

W25O73 mP98 a = 1193 74.5 at.% O; member of the WnO3n-2 series 

P2/c b = 382 [1989Wri] 

W25O73 c = 5972 

β = 98.3˚ 



MSIT 1 

9 

DOI: 10.1007/978-3-540-70890-2_22 

ß Springer 2009

10 22 

Fe–O–W 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


W25O74 mP99 a = 1190 74.7 at.% O; probable member of the WnO3n–1 P2/m b = 382.6 series [1989Wri] labelled as WO2.96 W25O73 c = 2982 

β = 98.4˚ 

WO3 (h4) tP8 (?) 75.0 at.% O [1989Wri] labelled as WO3-A 1474 - 1230 P4/nmm (?) 

WO3 (h4) a = 525.7 

c=391.2 

T = 1260˚C [1989Wri] 

WO3 (h3) tP8 75.0 at.% O; labelled as WO3-B 1230 - 900 P4/nmm a = 527.2 T = 950˚C [1989Wri] 

WO3 (h3) c=392.0 

WO3 (h2) tP8 75.0 at.% O; labelled as WO3-C 900 - 740 P4/nmn a = 525.0 T = 770˚C [1989Wri] 

WO3 (h2) a 

c=391.5 

WO3 (h1) oP32 75.0 at.% O; labelled as WO3-D 740 - 330 Pmnb a = 734.1 T = 480˚C [1989Wri] 

WO3 (h1) a 

b = 757.0 

c=775.4 

WO3 (r) mP32 75.0 at.% O; labelled as WO3-E 330 - 17 P21/n a = 730.6 at 25˚C [1989Wri] 

WO3 (r) a 

b = 754.0 

c=769.2 

β = 90.881˚ 

WO3 (l1) aP32 75.0 at.% O; labelled as WO3-F 

17 - (–40) P1 a = 730.9 at 25˚C [1989Wri] 

WO3 (l1) b = 752.2 

c=767.8 

α = 88.81˚ 

β = 90.92˚ 

γ = 90.93˚ 

WO3 (l2) mP16 75.0 at.% O; labelled as WO3-G (–40) - (–143) Pc a = 527.5 T = –70˚C [1989Wri] 

WO3 (l2) b = 515.5 

c=767.2 

β = 91.7˚ 

WO3 (l3) (–143) - (–208) 

- - 75.0 at.% O; labelled as WO3-H [1989Wri] 

WO3 (l4) (–208) - (–233) 

- - 75.0 at.% O; labelled as WO3-J [1989Wri] 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


WO3 (l5) (–233) - (–257) 

- - 75.0 at.% O; labelled as WO3-K [1989Wri] 

WO3 (l6) < –257 

- - 75.0 at.% O; labelled as WO3-M [1989Wri] 

τ 1, WFeO 4 

(Ferberite) 

mP12 a = 473.4 [1989Rag, 2003Yu] 

P2/c b = 570.9 

WFeO4 c=496.3 

β = 90˚ 

τ2, WFe2O6 (h2) oP9 a = 457.6 [1982Lei1, 1989Rag] labelled as γWFe2O6 1100 - 900 Pbcn b = 1676.6 [1999Gus] 

αPbO2 c=496.7 

τ2´, WFe2O6 (h1) m** - labelled as βWFe2O6 840 - 750 - [1999Gus] 

τ2´´, WFe2O6 (r) oP9 a = 1374.9 [1973Par, 1993Wal] labelled as αWFe2O6 < 800 Pbcn b = 1679.3 [1999Gus] 

columbite c=995.8 

τ3, WFe0.1O3 h** a = 742.2 iron-tungsten bronze [1978McC] 

- c=376.6 

τ4,W0.99Fe0.01O2.80 tP* a = 2329 [1977Eks] 

P421m - 

c = 379.4 

WFeOx hP3 a = 431 x = 0.4 to 1.0 [1954Sch1] 

P63/mmc Fe2N c = 275 

W3Fe3O cF96 

Fd3m 

Ti2Ni a = 1096 ± 1 [1954Sch2] 

W3Fe2O12 - a = 1586 or Fe2(WO4) 3 

b = 929.5 

c=1842 

β = 125.1˚ 

metastable phase [2003Sri] 

a)Often described as a slightly distorted ReO 3-type [1989Wri, Mas2] 



MSIT 1 

Fe–O–W 22 

11 

DOI: 10.1007/978-3-540-70890-2_22 

ß Springer 2009

12 22 

Fe–O–W 

. Table 3 

Investigations of the Fe-O-W Materials Properties 


[1967Uel] Neutron diffraction Antiferromagnetic ordering 

[1976Wei] Neutron diffraction Magnetic structure of the τ2, WFe2O6 (h2) 

phase 

[1977Gel] Picnometer method, Mössbauer 

spectroscopy 

Density, electronic structure 

[1977Pin] Neutron diffraction Magnetic structure of the τ 2, WFe 2O 6 (h 2) 

phase 

[1981Bha] Electrical conductivity and thermoelectric 

power measurements 

[1982Lei1] Faraday balance method van der Pauw 

technique, photoelectrolytic 

measurements 

[1982Sie] Hydrostatic technique, 

thermogravimetric analysis (Cahn 

electrobalance), Faraday balance method, 

van der Pauw technique 

d.c. and a.c. electrical conductivity, 

thermoelectric power of the τ 2, WFe 2O 6 

(h 2) phase 

The τ 2, WFe 2O 6 (h 2) phase: magnetic 

susceptibility, dependence of 

photocurrent on anode potential, 

electrical resistivity, quantum efficiency 

The τ 1, WFeO 4 phase: density, stability 

towards oxidation, electrical resistivity, 

magnetic susceptibility 

[1984Tho1] Thermomagnetic analysis The τ2, WFe2O6 (h2) phase - magnetic 

susceptibility 

[1988Bir] Mössbauer spectroscopy Mössbauer parameters for the WFe2O6 phase containing samples 

[1991Sch] Electrical resistivity measurements 

(Wheatstone- and Schering-type bridges), 

thermoelectric power measurements 

[1995Gus] EPR measurements (a standard X-band 

spectrometer Bruker 200D), d.c. magnetic 

measurements (vibrating sample 

magnetometer) 


spectrometer Radiopan R-10), NMR 

technique 


spectrometer Radiopan SEX-104), d.c. 

electrical resistivity measurements 

(Keithley 181 electrometer) 

The τ 1, WFeO 4 phase: d.c. and a.c. 

electrical resistivity, thermoelectric power 

The WFe 2O 6 phases: d.c. magnetic 

susceptibility, EPR spectra 

The τ 2, WFe 2O 6 (r) phase - EPR spectra 

The WFe 2O 6 phases: electrical resistivity, 

EPR spectra 

[2001Kaw] Mössbauer spectroscopy The τ1, WFeO4 phase: electronic structure 

[2003Yu] TEM, selected area electron diffraction 

(SAED) 

Morphology of nanorods 



MSIT 1



[2006Azi] X-ray photoelectron spectroscopy (XPS), 

atomic force microscopy 

[2006Eji] Optical (absorption and reflection) 

spectroscopy, ultraviolet photoelectron 

spectroscopy (UPS) 

[2007Luo] CH1600B electrochemical analysis, monochrome 

filters, photometry 



MSIT 1 

Fe–O–W 22 

The (WO 3) 1–x-(Fe 2O 3) x thin films: 

optical density, electrochromic properties 

Single WFeO 4 microcrystals: absorption 

coefficient and reflectance spectra, 

valence band photoelectrons spectra 

Photocurrent under different applied 

potentials, incident photon conversion 

efficiency (IPCE), light intensity 

13 

DOI: 10.1007/978-3-540-70890-2_22 

ß Springer 2009

14 22 

Fe–O–W 

. Fig. 1 

Fe-O-W. Partial isothermal section at 1100˚C 



MSIT 1

. Fig. 2 

Fe-O-W. Partial isothermal section at 1000˚C 



MSIT 1 

Fe–O–W 22 

15 

DOI: 10.1007/978-3-540-70890-2_22 

ß Springer 2009

16 22 

Fe–O–W 

. Fig. 3 

Fe-O-W. Temperature - composition section WO 3-Fe 2O 3 



MSIT 1

References 

Fe–O–W 22 

17 

[1930Bro] Broch, E.K., “Investigation of Crystal Structures of Wolframit-Type and Sheelit-Type Compounds” (in 

German), Mat.-Nat. Klasse, (8), 3–62 (1930) (Crys. Structure, Experimental, Review, 64) 

[1954Sch1] Schoenberg, N., “On the Existence of Metallic Ternary Oxides Me’Me’’O with the Metal Atoms in 

Hexagonal Close-Packing”, Acta Chem. Scand., 8 (4), 630–632 (1954) (Crys. Structure, Experimental, 5) 

[1954Sch2] Schoenberg, N., “On the Existence of Ternary Transition Metal Oxides”, Acta Chem. Scand., 8(6), 


[1957Koz] Kozmanov, Yu.D., “An X-Ray Study of the Reaction Between Solid Iron Oxides and the Oxides of 

Tungsten and Molybdenum” (in Russian), Zh. Fiz. Khim., 31(8), 1861–1865 (1957) (Crys. Structure, 

Experimental, Kinetics, 6) 

[1962Yat] Yatsyuk, M.A., Solomko, V.Ya., “Kinetics of Oxidation of the Iron Alloy with 9.77% of Tungsten at 

740-960˚C” (in Russian), Zh. Prikl. Khim., 35(10), 2336–2338 (1962) (Morphology, Experimental, 

Kinetics, 2) 

[1965Tan] Tankins, E.S., Thomas, M.K., Erthal, J.F., Williams, F.S., “The Activity of Oxygen in Liquid Iron- 

Molybdenum and Iron-Tungsten Alloys”, Trans. Am. Soc. Met., 58(3), 245–252 (1965) (Phase Relations, 

Thermodyn., Experimental, 10) 

[1966Tru] Trunov, V.K., Kovba, L.M., “Interaction of Molybdenum and Tungsten Trioxides with Iron (III) and 

Chromium (II) Oxides”, Izv. Akad. Nauk SSSR, Neorg. Mater., 2(1), 151–154 (1966) (Crys. Structure, 

Experimental) as quoted by [1978Gar] 

[1967Uel] Uelkue, D., “Investigations of Crystal Structure and Magnetic Structure of the Ferberits FeWO 4” (in 

German), Z. Kristallogr., 124(3), 192–219 (1967) (Crys. Structure, Experimental, Magn. Prop., 15) 

[1968Cid] Cid-Dresdner, H., Escobar, C., “The Crystal Structure of Ferberite, FeWO 4”, Z. Kristallogr., 127, 61–72 


[1969Sch] Schroecke, H., “Solid Phase Equilibria in the Fe-Mn-W-O System” (in German), Neues Jahrb. Mineral, 

Abhandl., 110(2), 115–127 (1969) (Phase Diagram, Phase Relations, Experimental, *, 24) 

[1970Kle] Klevtsov, P.V., Novgorodtseva, N.A., Kharchenko, L.Yu., “Hydrothermal Synthesis of FeWO 4 Crystals” 

(in Russian), Kristallografiya, 15(3), 609–610 (1970) (Crys. Structure, Experimental, 9) 

[1970Kot] Kotyk, M., Stadelmaier, H.H., “Study of Filled Ti 2Ni-Type Phases with Hf, Ta, and W”, Metall. Trans., 1, 

899–903 (1970) (Crys. Structure, Morphology, Phase Diagram, Phase Relations, Experimental, *, 16) 

[1971Fis] Fischer, W.A., Janke, D., “The Activity of Oxygen in Iron Melts Containing Molybdenum, Tungsten, 

Niobium or Tantalum” (in German), Arch. Eisenhuettenwes., 42(10), 695–698 (1971) (Thermodyn., 


[1972Sch] Schmahl, N.G., Dillenburg, H., “Phase Equilibria and Thermodynamics of the Ternary Systems 

Fe-Mo-O and Fe-W-O” (in German), Z. Physik. Chem. Neue Folge, 77, 113–126 (1972) (Phase Diagram, 

Phase Relations, Thermodyn., Experimental, 40) 

[1972Sle] Sleight, A.W., “Accurate Cell Dimensions for ABO 4 Molybdates and Tungstates”, Acta Crystallogr., B28, 


[1973Par] Parant, C., Bernier, J.C., Michel, A., “Two Orthorhombic Forms of Iron Tungstate” (in French), Compt. 

Rend., Ser. C, 276C, 495–497 (1973) (Crys. Structure, Experimental, 10) 

[1974Lyo] Lyon, W.G., Westrum, E.F., Jr., “Heat Capacities of Zinc Tungstate and Ferrous Tungstate from 5 to 

550 K”, J. Chem. Thermodyn., 6, 763–780 (1974) (Crys. Structure, Thermodyn., Calculation, Experimental, 

39) 

[1974Sen] Senegas, J., Galy, J., “The Double Oxide Fe 2WO 6. I. Crystal Structure and Filiation Structures” (in 

French), J. Solid State Chem., 10, 5–11 (1974) (Crys. Structure, Experimental, 8) 

[1976Jeh] Jehn, H., “Wolfram” (in German), in “Gase und Kohlenstoff in Metallen”, Springer-Verlag Berlin 

Heidelberg New York, 552–563 (1976) (Phase Diagram, Phase Relations, Thermodyn., Review, Kinetics, 


[1976Wei] Weitzel, H., “Magnetic Structures of NiNb 2O 6 and Fe 2WO 6” (in German), Acta Crystallogr., Sect. A: 

Found. Crystallogr., A32, 592–597 (1976) (Crys. Structure, Experimental, Magn. Prop., 16) 

[1977Eks] Ekstroem, T., Tilley, R.J.D., “Phase Relations in the Dioxide-Trioxide Region of Some 3d Transition 

Metal-W-O Ternary Systems”, J. Solid State Chem., 22, 331–340 (1977) (Crys. Structure, Phase Relations, 

Experimental, #, 30) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_22 

ß Springer 2009

18 22 

Fe–O–W 

[1977Gel] Geller, R., Kostakis, G., Trumm, A., Weitzel, H., Schroecke, H., “Examinations in the System Fe-W-O” 

(in German), Neues Jahrb. Mineral. Abh., 129(2), 211–231 (1977) (Phase Diagram, Phase Relations, 

Experimental, Phys. Prop., #, 18) 

[1977Pin] Pinto, H., Melamud, M., Shaked, H., “Magnetic Structure of Fe 2WO 6, a Neutron Diffraction Study”, 

Acta Crystallogr., Sect. A: Found. Crystallogr., A33, 663–667 (1977) (Crys. Structure, Experimental, 


[1978Gar] Gardiner, C.F., Chang, L.L.Y., “Phase Relations in the Systems Cr 2O 3-WO 3 and Fe 2O 3-WO 3”, J. Am. 

Ceram. Soc., 61(7), 376 (1978) (Crys. Structure, Phase Diagram, Phase Relations, Experimental, 4) 

[1978McC] McColm, I.J., Steadman, R., Wilson, S.J., “Iron-Promoted Phases in the Tungsten-Oxygen System”, 

J. Solid State Chem., 23, 33–42 (1978) (Crys. Structure, Morphology, Phase Relations, Experimental, 27) 

[1978Tru] Trumm, A., “Phase Diagram of the Fe 2O 3-WO 3 System” (in German), Neues Jahrb. Mineral., Monatsh., 

(11), 481–484 (1978) (Phase Diagram, Phase Relations, Experimental, *) as quoted by [1989Rag] and 

[1993Wal] 

[1980Amo] Amosse, J., Mathieu, J.C., “The Enthalpies of Formation of FeWO 4, MnWO 4, and their Solid Solutions”, 

J. Chem. Thermodyn., 12(7), 683–689 (1980) (Thermodyn., Experimental, 16) 

[1980Kle] Kleykamp, H., “Thermodynamics of the Systems Fe-W, Fe-W-O and Fe-W-C” (in German), J. Less- 

Common Met., 71(1), 127–134 (1980) (Thermodyn., Experimental, 23) 

[1981Bha] Bharati, R., Singh, R.A., “The Electrical Properties of Fe 2WO 6”, J. Mater. Sci., 16, 511–514 (1981) 

(Morphology, Experimental, Electr. Prop., 19) 

[1982Lei1] Leiva, H., Dwight, K., Wold, A., “Preparation and Characterization of Conducting Iron Tungstates”, 

J. Solid State Chem., 42, 41–46 (1982) (Crys. Structure, Experimental, Electr. Prop., Magn. Prop., 

Optical Prop., 23) 

[1982Lei2] Leiva, H., Sieber, K., Khazai, B., Dwight, K., Wold, A., “Structural and Electronic Relationships 

between Conducting Iron Niobates and Iron Tungstates”, J. Solid State Chem., 44, 113–118 (1982) 

(Crys. Structure, Review, Theory, Electronic Structure, 20) 

[1982Sie] Sieber, K., Kourtakis, K., Kershaw, R., Dwight, K., Wold, A., “Preparation and Photoelectronic 

Properties of FeWO 4”, Mater. Res. Bull., 17 (6), 721–725 (1982) (Crys. Structure, Experimental, Electr. 

Prop., Optical Prop., 13) 

[1983Kle] Kleykamp, H., “Experimental Aspects of Solid Galvanic Cell Methods for Thermodynamic Studies on 

Alloys”, Ber. Bunsen-Ges. Phys. Chem., 87(9), 777–781 (1983) (Phase Diagram, Phase Relations, Thermodyn., 

Review, 32) 

[1984Buh] Buhl, J.C., Willgallis, A., “Kinetics and Mechanism of Huebnerite (MnWO 4) and Ferberite (FeWO 4). 

Crystallization under Hydrothermal Conditions”, Z. Naturforsch., Teil A, 39A (10), 963–965 (1984) 

(Morphology, Experimental, Kinetics, 18) 

[1984Tho1] Thomas, G., Ropital, F., “Influence of Gas on the Summary of Iron Tungstate Fe 2WO 6 1. Experimental 

Study” (in French), Mater. Chem. Phys., 11, 549–562 (1984) (Morphology, Experimental, Magn. 

Prop., 16) 

[1984Tho2] Thomas, G., Ropital, F., “Influence of Gas on the Summary of Iron Tungstate Fe 2WO 6 2. Study of 

Mechanism Solide-Solide” (in French), Mater. Chem. Phys., 11, 563–575 (1984) (Morphology, Experimental, 

Kinetics, 9) 

[1984Tho3] Thomas, G., Ropital, F., “Influence of Gas on the Summary of Iron Tungstate Fe 2WO 6 3. Study of 

Machinery Gas-Solid” (in French), Mater. Chem. Phys., 11, 577–590 (1984) (Morphology, Calculation, 

Experimental, Kinetics, 4) 

[1985Har] Harrison, W.T.A., Chowdhry, U., Machiels, C.J., Sleight, A.W., Cheetham, A.K., “Preparation of Ferric 

Tungstate and its Catalytic behavior Toward Methanol”, J. Solid State Chem., 60, 101–106 (1985) (Crys. 

Structure, Experimental, Kinetics, 23) 

[1986Nag] Nagender Naidu, S.V., Sriramamurthy, A.M., Rama Rao, P., “Fe-W (Iron-Tungsten)”, J. Alloy Phase 

Diagrams, 2(3), 176–188 (1986) (Crys. Structure, Phase Diagram, Phase Relations, Review, 80) 

[1987Gus] Gustafson, P., “A Thermodynamic Evaluation of the C-Fe-W System”, Metall. Trans. A, 18A(2), 175–188 

(1987) (Phase Diagram, Phase Relations, Thermodyn., Assessment, 53) 

[1987Mai] Maiti, G.C., Loechner, U., Baerns, M., “Studies on the Reduction of Iron/Tungsten Mixed Oxides”, 

Thermochim. Acta, 112, 221–229 (1987) (Crys. Structure, Experimental, Kinetics, 61) 

[1988Bag] Bagdavadze, D.I., Tsagareishvili, D.Sh., Tskhadaya, R.A., Gvelesiani, G.G., “Method of Computation of 

Enthalpy Increment of Crystalline Inorganic Compounds at 0-298.15 K Temperature Range” (in 

Russian), Izv. Akad. Nauk Gruz. SSR, Ser. Khim, 14(3), 199–206 (1988) (Thermodyn., Calculation, 

Review, 8) 



MSIT 1

Fe–O–W 22 

19 

[1988Bir] Birchall, T., Hallett, C., Vaillancourt, A., Ruebenbauer, K., “A Study of Iron-Tungsten Oxides and Iron- 

Chromium-Tungsten Oxides”, Can. J. Chem., 66(4), 698–702 (1988) (Crys. Structure, Experimental, 

Electronic Structure, 18) 

[1988Fer] Fernandez-Guillermet, A., “Thermodynamic Calculation of the Fe-Co-W Phase Diagram”, 

Z. Metallkd., 79(10), 633–642 (1988) (Phase Diagram, Phase Relations, Assessment, Thermodyn., 34) 

[1989Rag] Raghavan, V., “The Fe-O-W (Iron-Oxygen-Tungsten) System” in “Phase Diagrams of Ternary Iron 

Alloys”, Indian Inst. Metal., Calcutta, 5, 349–354 (1989) (Crys. Structure, Phase Diagram, Review, #, 17) 

[1989Wri] Wriedt, H.A., “The O-W (Oxygen-Tungsten) System”, Bull. Alloy Phase Diagrams, 10(4), 368–384 

(1989) (Crys. Structure, Phase Diagram, Phase Relations, Assessment, Review, 154) 

[1991Sch] Schmidbauer, E., Schanz, U., Yu, F.J., “Electrical Transport Properties of Mono- and Polycrystalline 

FeWO4”, J. Phys.: Condens. Matter, (3), 5341–5352 (1991) (Crys. Structure, Experimental, Electr. 

Prop., 28) 

[1993Wal] Walczak, J., Rychlowska-Himmel, I., “Phase Equilibria in the Systems Fe 2O 3-WO 3 and FeVO 4-WO 3”, 

Thermochim. Acta, 221(1), 115–121 (1993) (Phase Diagram, Phase Relations, Experimental, #, 20) 

[1993Yu] Yu, F., Schanz, U., Schmidbauer, E., “Single Crystal Growth of FeWO 4 and CuWO 4”, J. Cryst. Growth, 

132, 606–608 (1993) (Crys. Structure, Morphology, Experimental, 13) 

[1995Gus] Guskos, N., Sadlowski, L., Typek, J., Likodimos, V., Gamari-Seale, H., Bojanowski, B., Wabia, M., 

Walczak, J., Rychlowska-Himmel, I., “Magnetic and EPR Studies of α-, β- and γ-Fe 2WO 6 Phases at Low 

Temperatures”, J. Solid State Chem., 120, 216–222 (1995) (Morphology, Experimental, Electronic 


[1998Gus] Guskos, N., Typek, J., Wabia, M., Likodimos, V., Fuks, H., Rychlowska-Himmel, I., Walczak, J., “Phase 

Transition Study in α-Fe 2WO 6 Compound by EPR”, Appl. Magn. Resonance, 14(2-3), 397–402 (1998) 

(Morphology, Experimental, Electronic Structure, Magn. Prop., 13) 

[1999Gus] Guskos, N., Likodimos, V., Glenis, S., Patapis, S.K., Palilis, L.C., Typek, J., Wabia, M., Rychlowska- 

Himmel, I., “Electrical Transport and EPR Properties of the α, β, and γ Phases of Fe 2WO 6”, Phys. Rev. B, 

60 (11), 7687–7690 (1999) (Morphology, Experimental, Electr. Prop., Magn. Prop., 27) 

[2001Kaw] Kawanaka, H., Miyamoto, R., Nishihara, Y., “Electronic State of Iron Oxides FeWO 4 (Mössbauer 

Study)”, J. Magn. Soc. Jpn., 25(4, part 2), 715–718 (2001) (Morphology, Experimental, Electronic 

Structure, Magn. Prop.) cited from abstract 

[2003Sri] Sriraman, A.K., Tyagi, A.K., “A New Method of Fe 2(WO 4) 3 Preparation and its Thermal Stability”, 

Thermochim. Acta, 406, 29–33 (2003) (Crys. Structure, Experimental, 8) 

[2003Yu] Yu, S.-H., Liu, B., Mo, M.-S., Huang, J.-H., Liu, X.-M., Qian, Y.-T., “General Synthesis of Single-Crystal 

Tungstate Nanorods/Nanowires: A Facile, Low-Temperature Solution Approach”, Adv. Func. Mater., 13 

(8), 639–647 (2003) (Crys. Structure, Morphology, Experimental, 55) 

[2006Azi] Azimirad, R., Akhavan, O., Moshfegh, A.Z., “An Investigation on Electrochromic Properties of 

(WO 3) 1–x-(Fe 2O 3) x Thin Films”, Thin Solid Films, 515, 644–647 (2006) (Morphology, Experimental, 

Optical Prop., 16) 

[2006Eji] Ejima, T., Banse, T., Takatsuka, H., Kondo, Y., Ishino, M., Kimura, N., Watanabe, M., Matsubara, I., 

“Microscopic Optical and Photoelectron Measurements of MWO 4 (M = Mn, Fe, and Ni)”, J. Lumin., 

119–120, 59–63 (2006) (Morphology, Experimental, Optical Prop., 20) 

[2006McK] McKenzie, K.J.D., Temuujin, J., McCammon, C., Senna, M., “Mechanochemical Activation of Mixtures 

of Wolframite (FeWO 4) with Carbon, Studied by 57 Fe Mössbauer Spectroscopy”, J. Eur. Ceram. Soc., 26, 


[2007Luo] Luo, W., Yu, T., Wang, Y., Li, Z., Ye, J., Zou, Z., “Enhanced Photocurrent-Voltage Characteristics of 

WO 3/Fe 2O 3 Nano-Electrodes”, J. Phys. D: Appl. Phys., 40, 1091–1096 (2007) (Crys. Structure, Morphology, 



(1990) 





MSIT 1 

DOI: 10.1007/978-3-540-70890-2_22 

ß Springer 2009

Iron – Oxygen – Yttrium 


Pierre Perrot 

Introduction 

The Fe-O-Y system has provided much interest because of the ferrimagnetic garnet Y 3Fe 5O 12, 

known as YIG (Yttrium Iron Garnet) interesting for its applications in microwave devices. 

This garnet has an incongruent melting and the knowledge of its crystallization field is of 

interest for the single crystals growth. The main experimental results about the Fe-O-Y 

diagram are presented in Table 1. A review was presented by [1989Rag]. No Calphad 

assessment has been carried out. 


The Fe-Y system is accepted from the assessment of [1992Zha]. The Fe-O system is accepted 

from [Mas2], where it is mainly based on the fundamental work of [1945Dar, 1946Dar]. Later 

it has been carefully assessed by [1991Sun, 1995Kow]. The O-Y binary system is accepted from 

[1990Car]. 


Fe–O–Y 23 

1 

Solid phases are presented in Table 2. 

τ 1,YFeO 3 presents a congruent melting at 1720˚C and has a perowskite like structure, 

explained by the small size of the Fe 3+ ion which has the minimum radius (55 pm) to occupy 

the octahedra sites of the oxygen lattice [2004Li] so that a stable perowskite structure cannot 

be expected. 

τ2,YFe2O4, was observed by [1975Kim] and its stability above 1010˚C was confirmed by 

[1979Pie, 1980Mat]. However, [2004Kit] considers τ 2 as metastable at 1100˚C. 

τ 3,Y 3Fe 5O 12 presents an incongruent melting at 1555˚C under air and at 1582˚C under 

pure O 2 [1962Hoo]. Its non stoichiometry has been clearly put into evidence by [1961Hoo]on 

samples water quenched from 1400˚C to 1540˚C and confirmed by [1980Vor]. Its composition 

range varies from 37 to 37.5 mol% Y 2O 3, which means that Fe may substitute Y to a small 

extent in the Y sublattice. Under low oxygen potentials, τ 3 may loose oxygen leading to 

Y 3Fe 5O 12–δ (δ < 0.9). A DTA analysis of τ 3 was carried out by [1963Ber], but it is probable 

that the sample hold unreacted Fe2O3 because the observed peaks correspond to the oxygen 

loss by Fe 2O 3 under air (1380˚C) and to the eutectic Fe 3O 4-τ 3 (1469˚C). 

τ 5,YFe 3+xO 1.5(4+x) was synthesized by [2004Sug1] under radiofrequency Ar-O 2 thermal 

plasma and was shown to be paramagnetic [2004Sug2]. The values of x are not well determined 

because τ 5 was contaminated with by-products such as γFe 2O 3 and τ 1,YFeO 3. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_23 

ß Springer 2009

2 23 

Fe–O–Y 

The crystal parameter constant for 0.1 < x < 1 is an indication that τ 5 may be a stoichiometric 

compound whose exact composition has to be defined. 


The αY2O3-αFe2O3 quasibinary system under air atmosphere is presented in Fig. 1 according 

to the measurements of [1958Nie, 1962Hoo, 1975Lev]. This system is not truly binary because 

Fe 2O 3 looses its oxygen to form Fe 3O 4 above a temperature which increases with the imposed 

oxygen potential (1380˚C under air, 1460˚C under 0.1 MPa of O 2 pressure). The Fe 2O 3-τ 1, 

YFeO 3 part of the diagram is reproduced from [1975Lev]. The incongruent melting point of 

τ 3,Y 3Fe 5O 12 depends also on the imposed oxygen potential: 1495˚C under pure CO 2, 1555˚C 

under air and 1582˚C under 0.1 MPa of O 2 pressure [1961Hoo, 1962Hoo]. 


The liquidus lines in the Y 3Fe 5O 12-Fe 2O 3-FeO part of the diagram, investigated by [1962Hoo], 

are shown in Fig. 2 together with some solidus lines. The primary crystallization field of the 

garnet τ 3,Y 3Fe 5O 12 is narrow, opposite to thee wide primary crystallization field of τ 1,YFeO 3. 

The ternary eutectic E was measured at 1453˚C under 90 kPa of oxygen pressure. The ternary 

transformation point U1 was measured at 1465˚C under an oxygen pressure lower than 10 Pa 

which is the oxygen pressure of pure CO2 at the same temperature. The ternary transformation 

point U 2 is estimated lower than 1420˚C under an oxygen pressure lower than 0.1 Pa 

which is the oxygen pressure of the equilibrium FeO-Fe 3O 4 at 1420˚C. The maximum on the 

EU 1 line is estimated at a temperature higher than 1469˚C. 


The isothermal section at 1200˚C, mainly from [1975Kim], is represented in Fig. 3. The 

isothermal section at 1000˚C shown in Fig. 4 is drawn from the thermodynamic measurements 

of [1977Tre, 1978Pie, 1983Fet]. The difference between both sections comes from the phases in 

equilibrium with τ 1,YFeO 3. Below 1078˚C, τ 1 is in equilibrium with Fe and FeO, whereas above 

1080˚C, τ 1 is in equilibrium with FeO and Fe 3O 4.[2004Kit] presents a phase diagram at 1100˚ 

C which agrees with that presented at 1200˚C by [1975Kim], but considers τ 2,YFe 2O 4 as a 

metastable compound. Y is a stronger oxidizer than Fe and, whatever the temperature, pure Fe 

and (Fe-Y) intermetallic compounds are in equilibrium with Y2O3. Between 700 and 1200˚C, 

under low oxygen pressure (0.04 Pa), pure Fe oxidizes into FeO, Fe3O4 and Fe2O3 whereas 

Y-doped Fe oxidizes with formation of τ 1,YFeO 3 and τ 2,YFe 2O 4 [1999Cau, 2001Cau]. Under 

0.1 MPa of O 2 pressure, Fe-Yalloys are oxidized at 700-800˚C with formation of τ 1,YFeO 3 and 

τ 3,Y 3Fe 5O 12 together with iron oxides [1999Li], so that Y cannot prevent the Fe oxidation. In 

low oxygen pressures generated by H 2-CO 2 mixtures (~10 –15 Pa at 700˚C), yttrium-iron oxides 

are observed together with pure Y 2O 3 [1998Niu], which form a non protective layer. 



MSIT 1


The interaction coefficient between O and Y in liquid iron has been calculated by [1973Buz] 

from solubility measurements and found e O (Y) =(∂ log10 f O / ∂ mass% Y) = – 0.46 at 1600˚C 

where f O = (mass% O in pure Fe / mass% O in the alloy). Such a value, very negative, means 

that Y in liquid iron increases the oxygen solubility. The interaction coefficient, evaluated later 

by [1985Tin] and reproduced in [1987Lon], two order of magnitude higher, is not credible. An 

evaluation by [1995Ish] gives a result one order of magnitude higher. On the other hand, as Y 

presents one of the greatest affinity for oxygen, the increase of the oxygen solubility in liquid 

iron is quickly limited by the precipitation of Y 2O 3, whence a difficulty to evaluate the slope of 

the curve f O vs {mass% Y}, which explains the discrepancy observed between the various 

experimental results. The solubility product of Y 2O 3 in liquid Fe is given in Table 3. 

The thermodynamic quantities of formation of τ 1,YFeO 3, τ 2,YFe 2O 3.9 and τ 3,Y 3Fe 5O 12 

from Fe, Y 2O 3 and O 2 are given at 1200˚C in Table 3. The reactions are expressed for 1 mole 

O2, which allows the comparison of the oxygen pressures at equilibria (Fe + Y2O3 + YFeO3), 

(Fe + Y2O3 + YFe2O3.9) and (Fe + Y2O3 +Y3Fe5O12). For the sake of comparison, the oxygen 

pressures at equilibria (Fe + FeO) and (FeO + Fe 3O 4) at 1200˚C are 1.20 · 10 –7 and 7.20 · 10 –5 

Pa, respectively. As a consequence, only τ 2,YFe 2O 3.9 may be in equilibrium with Fe and FeO at 

1200˚C. τ 1,YFeO 3 may be in equilibrium with Fe, FeO and Fe 3O 4 whereas τ 3,Y 3Fe 5O 12 may be 

in equilibrium with Fe 3O 4 and Fe 2O 3. The equilibria (Fe + Y 2O 3 +YFeO 3) and (Fe + Y 2O 3 + 

Y 3Fe 5O 12) are metastable at 1200˚C. An investigation of the (Fe + Y 2O 3 +YFeO 3) equilibrium 

by [1977Tre, 1979Pie, 1985Sko] in a wider temperature range (900-1250˚C) shows that this 

equilibrium is stable below 1010˚C, temperature of formation of τ2,YFe2O4. An extrapolation 

of the oxygen pressure measured towards higher temperature shows that, at 1110˚C, the 

oxygen pressure is the same for the equilibria (Fe + Y 2O 3 + YFeO 3) and (Fe + FeO), which 

means that, above 1110˚C, YFeO 3 cannot be in equilibrium with Fe, in agreement with 

the observation of [1975Kim] at 1200˚C. A further extension of the temperature range 

(900-1250˚C) investigated by [1978Pie, 1979Pie] shows that the invariant equilibrium is at 

1078˚C, temperature accepted in this report. The τ 2,YFe 2O 4 was shown to be stable only 

above 1010˚C [1979Pie]. However, [2004Kit] by investigating the Fe-Fe 2O 3-Y 2O 3 equilibria at 

1100˚C under CO2-H2 atmospheres did not observe the formation of τ2 and concluded to its 

instability. It is probable that the narrowness of the stability domain of τ2 at 1100˚C prevents 

its observation. The thermodynamic properties of the ferrites τ 1, τ 2 and τ 3, from [1979Pie, 

1988Pie] are given in Table 4. A general review of the thermodynamic properties of the rare 

earth and iron mixed oxides was presented by [1978Kat]. The stabilities of rare earth and iron 

mixed oxides are compared in [1983Kim]. A general trend is the increase of stability with the 

size of the rare earth ion, which puts iron and yttrium mixed oxides amongst the less stable of 

the iron and rare earth mixed oxides. This trend has been modelled by [1984Pie] which 

proposes empirical expressions of the thermodynamic quantities taking into account the ionic 

radius of the rare earth ions. 


Fe–O–Y 23 

3 

The main experimental works regarding properties are summarized in Table 5. Y may be used 

as deoxidizer in steelmaking. Although it is known as one the best deoxidizer, its use is limited 

by its price. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_23 

ß Springer 2009

4 23 

Fe–O–Y 

τ 1,YFeO 3 has been proposed for a number of applications from catalysis, reflective coatings, 

electrode material to fast ion conductor. It may be synthesized by ceramics methods 

(Fe 2O 3 +Y 2O 3 annealed several days above 1000˚C) but more efficiently at lower temperature 

(2 h at 800˚C) from a fused salts flux YCl 3 + FeCl 3 +Li 2O[1996Par]. 

τ 2,YFe 2O 4 is a ferrimagnetic compound whose Neel temperature is 205 K. Below the Neel 

point, the non stoichiometric ferrite τ2,YFe2O3.9 presents extra reflections in the electron 

diffraction pattern [1980Mat] which may possibly be related to the magnetic behavior known 

as “parasitic ferrimagnetism”. 

τ 3,Y 3Fe 5O 12, a ferrimagnetic garnet (YIG) whose Neel temperature is 275˚C, has led to very 

intensive studies on the crystallographic, magnetic and electrical properties. It is very effective 

as microwave filter, as well as transducer and transmitter of acoustic energy. YIG is also of 

interest because its ferrimagnetic properties are tunable by partial substitution of non magnetic 

ions for magnetic ones at different sites. It may be synthesized from homogenized 

mixtures of hematite and yttria, but the garnet formation starts above 1000˚C and is complete 

at 1400˚C [2000Pet]. It has been prepared by combustion synthesis [2000Kuz] from a mixture 

(Y 2O 3 +Fe 2O 3 + Fe + NaClO 4) followed by an annealing for 4 h at 1450˚C or grown by laser 

heating [2003Che]. Nanoparticles have also been obtained by a sol-gel combustion synthesis 

(metal nitrates + citric acid) process [2007Hos]. TIG crystals are never grown from the melt, 

even when undercooled at temperatures lower than 1582˚C, the peritectic temperature of the 

Fe 2O 3-YIG system [2002Nag]. The first phase to precipitate is always the pseudo-perowskite 

YFeO 3. The formation of YIG from the melt needs hyperquenching. Single crystals are easily 

grown in a PbO flux [1958Nie], the most convenient composition for the bath being 52.5 PbO, 

44 Fe2O3, 3.5 Y2O3 (in mol%). 

τ 4,Y 12Fe 32O 2 is ferromagnetic [1976Dar] with a Curie temperature at 182 K; its saturation 

magnetization at 4.2 K is 32.4 B per unit formula. τ 4 is sometimes encountered as a by product 

in the preparation of τ 3,Y 3Fe 5O 12 [2000Tak]. 

τ 5,YFe 3+xO 1.5(4+x) is a paramagnetic compound [2004Sug2]. 

Miscellaneous 

The formation mechanism of YIG from its oxides has been investigated by [2000Pet]. It may 

be described by a two-step process: 

3Y 2O 3 +5Fe 2O 3 Ð 6YFeO 3 +2Fe 2O 3 Ð 2Y 3Fe 5O 12 

The orthoferrite formation starts at 816 ± 25˚C whereas the garnet formation started at 

1011 ± 25˚C. 

The YIG has also been prepared in 10 min by microwave heating (2.45 GHz) of a mixture 

Y2O3 +Fe3O4 in the ratio Y/Fe = 3/5 under air atmosphere [1997Ost, 2001Pee]. Fe3O4 is used 

instead of Fe2O3 because hematite is a poor microwave absorber. During the synthesis, 

orthoferrite YFeO 3 appears always as an intermediate compound and even YFe 2O 4 may be 

observed. 

The temperature dependence of electrical conductivity and Seebeck coefficient was 

measured on YIG single crystals for various orientations and different degrees of perfection 

[2003Lom]. The electrical properties of YIG are completely determined by the mechanism of 



MSIT 1

scattering of charge carriers and by their energy spectrum. The intensity ratio of coherent and 

incoherent X-ray scattering characterizes the fraction of conduction electrons in a given 

sample. 

. Table 1 

Investigations of the Fe-O-Y Phase Relations, Structures and Thermodynamics 


[1958Nie] Thermal analysis, crystal growth of 

Y3Fe5O12 in a PbO flux 

[1961Hoo] XRD, thermogravimetry, thermal analysis 

(water quenching) 


Range Studied 

1400-1750˚C, the Fe 2O 3-YFeO 3 phase 

diagram 

1150-1550˚C, Fe 2O 3-YFeO 3-Fe 3O 4 under 

air 

[1962Hoo] Thermal analysis, liquidus determination 1400-1600˚C, Fe2O3-YFeO3-FeO under 

O2, air and CO2 atmospheres 

[1963Ber] Differential thermal analysis < 1500˚C, Y3Fe5O12, under air 

[1975Kim] XRD, chemical analysis, emf 

measurements 

[1977Tre] emf measurements (Y2O3 stabilized ZrO2 as solid electrolyte) 

[1978Pie] emf measurements (CaO stabilized ZrO2 as solid electrolyte) 

[1979Pie] emf measurements (CaO stabilized ZrO2 as solid electrolyte) 

[1980Vor] XRD, microscopy, Seebeck coefficient 

measurements 

1200˚C, Fe-Fe 2O 3-Y 2O 3 diagram, Δ fG˚ 

(YFe 2O 3.9, YFeO 3,Y 3Fe 5O 12) 

900-1100˚C, p O2 at equilibrium (Fe + 

Y 2O 3 + YFeO 3) 

900-1250˚C, Δ fG˚(YFeO 3 and Y 3Fe 5O 12) 

900-1250˚C, Δ fG˚(YFeO 3,Y 3Fe 5O 12 and 

YFe 2O 4) 

800-1400˚C, Y 3Fe 5O 12, departure to 

stoichiometry 

[1983Fet] XRD, thermogravimetry 1000˚C, Y3Fe5O12, reduction under 

H2-H2O atmospheres 

[1985Sko] EMF measurements (CaF2+YF3 or 

CaF2+YOF as solid electrolyte) 

900-1150˚C, ΔfG˚(YFeO3 and Y3Fe5O12) 

[1985Tin, 

1987Lon] 

XRD, solubility measurements in (Fe,Y) 

liquid alloys 

[1995Ish] XRD, solubility measurements in (Fe,Y) 

liquid alloys 

Fe–O–Y 23 

1575-1625˚C, < 0.2 mass% Y, 

< 0.2 mass% O 

1600-1700˚C, < 0.11 mass% Y, 

< 0.2 mass% O 

[2004Kit] XRD, thermogravimetry 1100˚C, Fe-Fe2O3-Y2O3 diagram, CO2-H2 

and CO 2-O 2 atmospheres 



MSIT 1 

5 

DOI: 10.1007/978-3-540-70890-2_23 

ß Springer 2009

6 23 

Fe–O–Y 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


(αδFe) cI2 

(δFe) Im3m a = 293.15 pure Fe at 1394˚C 

1538 - 1394 W 

a = 286.65 

(αFe) (Ferrite) 

< 912 

pure Fe at 25˚C [Mas2, V-C2] 

(εFe) hP2 a = 246.8 at 25˚C, > 13 GPa 

P63/mmc Mg 

c = 396.0 [Mas2] 

(γFe) (Austenite) cF4 a = 364.67 at 915˚C [V-C2, Mas2] 

1394 - 912 Fm3m 

Cu 

(βY) cI2 a = 407 dissolves up to 30.4 at.% O at 1560˚C 

1522 - 1478 Im3m 

W 

[1990Car, 1992Zha] 

(αY) hP2 a = 364.82 Dissolves up to 14.3 at.% O at 1180˚C 

< 1478 P63/mmc Mg 

c = 573.18 [1990Car, 1992Zha] 

YFe2 cF24 a = 735.6 [Mas2] cubic Laves phase 

≲ 1125 Fd3m 

MgCu2 YFe3 hR36 a = 513.3 [1989Rag] 

≲ 1330 R3m 

PuNi3 c = 2460.0 

Y6Fe23 cF116 a = 1212.0 [1989Rag] 

≲ 1300 Fm3m 

Th6Mn23 βY2Fe17 hP38 a = 846.3 [1989Rag, 1992Zha] 

≲ 1400 P63/mmc Th2Ni17 c = 828.2 

αY2Fe17 hR57 a = 846.0 [1989Rag, 1992Zha] 

R3m 

Th2Zn17 c = 1241.0 

Fe1–xO (Wüstite) cF8 a = 431.0 x = 0.05 

1422 - 569 Fm3m 

NaCl 

a = 429.3 x=0.12 [1989Rag] 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Fe–O–Y 23 

Lattice 

Parameters 


Fe3O4 oP56 a = 1186.8 [V-C2, 1989Rag] 

< 580 Pbcm b = 1185.1 

Fe3O4 c=1675.2 

βFe3O4 (Magnetite) cF56 inverse spinel 

1597 - 580 Fd3m a = 854.5 at 1000˚C 

MgAl2O4 a = 839.6 at 25˚C 

αFe2O3 (Hematite) hR30 a = 503.42 [1989Rag] 

< 1457 R3c 

αAl2O3 (Corundum) 

c = 1374.83 

βFe2O3 cI80 a = 939.3 metastable phase 

Ia3 

βMn2O3 

(Bixbyite) 

[V-C2, 1989Rag] 

γFe2O3 (Maghemite) cF56 

Fd3m 

MgAl2O4 a = 834 metastable phase [1989Rag] 

βY2O3 hP* a = 381.3 at 2380˚C [1990Car] 

2430 - 2325 P3m1 c=609 

γY2O3 mC* a = 1391 high pressure phase 

C2/m b = 348.3 

c=859.3 

(> 250 MPa at 1000˚C) [1990Car] 

αY2O3 (Yttria) cI80 a = 1060.73 59.3 to 60 at.% O [1990Car] 

< 2325 Ia3 

βMn2O3 

* τ1, YFeO3 oP20 a = 528.19 ± 0.02 [1965Cop] Distorted perowskite 

< 1720 Pbmn b = 559.57 ± 0.05 

c = 760.46 ± 0.04 

structure 

cI* a = 1059.6 [1957Cur] (Metastable?) 

* τ2, YFe2O4 hR* a = 609.0 ± 0.4 [1975Kim]. Probably YFe2O4–x R3m c = 2478.8 ± 0.4 (x < 0.1) 

* τ3,Y3Fe5O12 (Yttrium cI160 

quenched from 1400˚C 

Iron Garnet) 

Ia3d 

< 1555 (under air) a = 1237.4 37 mol% Y2O3 a = 1237.8 37.5 mol% Y2O3 [1961Hoo] 



MSIT 1 

7 

DOI: 10.1007/978-3-540-70890-2_23 

ß Springer 2009

8 23 

Fe–O–Y 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


* τ4,Y12Fe32Ox cI46 x



(4/3) Fe + (2/5) Y 2O 3 +O 2 Ð (4/15) 

Y 3Fe 5O 12 

Temperature 

[˚C] 

Quantity, per mol of O 2 

[J, mol, K] 

Comments 

1200 Δ fG˚ = – 322400 ± 600 [1975Kim] 

pO2 = 3.69 · 10 –7 900 - 1250 

Pa 

ΔfG˚ = – 554200 + 156.0 T 

pO2 = 3.13 · 10 

[1979Pie] 

–7 Pa at 

1200˚C 

Y2O3 Ð 2 {Y} + 3 {O} (in liquid Fe) 1575 - 1625 ΔrG˚ = 1793000 – 658.0 T 

(Standard state: 1 mass% in 

Fe) 

[1985Tin] 

{mass% Y} 2 {mass% O} 3 

1600 - 1700 4.19 – (18810 / T) [1995Ish] 

. Table 4 

Thermodynamic Properties of Single Phases 

Phase 


[˚C] 

Fe–O–Y 23 

Property, per mole of atoms 

[J, mol, K] Comments 

(1/5)YFeO3 25 ΔfH ˚ = – 273200 ± 200 

ΔfS ˚ = – 50.5 ± 1.0 

[1979Pie] 

S˚ = 24.902 [1988Pie] 

900-1250 Cp = 21.072 + 3.764 · 10 –3 T – 1.996 · 10 5 T –2 

(1/7) YFe2O4 1010-1250 ΔfH ˚ = – 230800 ± 800 

ΔfS ˚ = – 43.8 ± 2.0 

[1979Pie] 

(1/20) Y3Fe5O12 25 ΔfH ˚ = – 245600 ± 150 

ΔfS ˚ = – 49.9 ± 0.60 

[1979Pie] 

S˚ = 23.214 [1988Pie] 

900-1250 Cp = 22.749 + 2.858 · 10 –3 T – 1.511 · 10 5 T –2 



MSIT 1 

9 

DOI: 10.1007/978-3-540-70890-2_23 

ß Springer 2009

10 23 

Fe–O–Y 

. Table 5 

Investigations of the Fe-O-Y Materials Properties 


[1957Cur] XRD, powder diffraction τ1,YFeO3, crystal structure 

[1957Gel] XRD, single crystal τ3,Y3Fe5O12, crystal structure 

[1965Cop] XRD, powder diffraction τ1,YFeO3, crystal structure 

[1976Dar] XRD, powder diffraction τ4,Y12Fe32O2, crystal structure 

[1980Mat] Electron diffraction τ2,YFe2O4, parasitic ferrimagnetism 

[1988Pie] CVD, transport by Cl or CCl4 at 800- τ1,YFeO3 and τ3,Y3Fe5O12, single crystal 

1000˚C 

growth 

[1992Boc] XRD, XPS τ1,YFeO3, electronic structure 

[1996Par] XRD, SEM, energy dispersive analysis τ1,YFeO3 synthesis by mixture YCl3 + FeCl3 + 

by X-Rays (EDAX), Fourier transform IR 

(FT-IR) 

Li2O (2 h at 800˚C) 

[1997Ost] XRD, magnetism, monomodal 

microwave oven at 2.45 GHz 

[1998Niu] High temperature XRD, 

thermogravimetry 

[1999Cau, 

2001Cau] 

High temperature XRD, 


[1999Li] High temperature XRD, 


[2000Kuz] XRD, SEM, EDAX, IR and Mössbauer 

spectrometry 

[2000Pet] High temperature XRD, Rietveld 

analysis in situ 

[2000Tak] XRD, TEM, SAES (Selected Area 

Electron Diffraction) 

[2001Pee] Multimodal microwave oven at 

2.45 GHz 

< 500˚C, synthesis of Y 3Fe 5O 12, YFeO 3 and 

YFe 2O 4 from oxides 

600-700˚C, 15 and 30 mass% Y in Fe under 

H 2-CO 2 atmospheres 

700˚C, Y-doped and undoped Fe under 

0.04 Pa of O 2 pressure 

700-800˚C, 15 and 30 mass% Y in Fe under 

0.1 MPa of O2 pressure 

τ 3,Y 3Fe 5O 12, combustion synthesis from Y 2O 3 

+Fe 2O 3 + Fe + NaClO 4 then annealing 4 h at 

1450˚C 

< 1400˚C, formation mechanism of Y 3Fe 5O 12 

from 3 Y 2O 3 +5Fe 2O 3 

Nanocrystalline Y 3Fe 5O 12 prepared by the 

alkoxide method 

900-1300˚C, synthesis of Y 3Fe 5O 12 from Y 2O 3 

+Fe 3O 4 under air 

[2002Nag] XRD, SEM, micrography Crystallization from undercooled Y 3Fe 5O 12 

melts below 1582˚C 

[2003Che] XRD, SQUID (Superconducting 

Quantum Interference Device) 

[2003Lom] Resistivity, thermoelectric power, 

X-ray scattering 

Composition of Y 3Fe 5O 12 obtained by Laser 

Heated Pedestal Growth 

200-410˚C, Y 3Fe 5O 12 single crystal 



MSIT 1



[2004Sug1, 

2004Sug2] 

XRD, TEM, Mössbauer, saturation 

magnetization 

[2004Wu] XRD, SEM, TEM, FT-IR, Raman 

spectroscopy, DSC, TGA 

Fe–O–Y 23 

τ 5,YFe 3+xO 1.5(4+x), prepared by rf Ar-O 2 

thermal plasma 

YFeO 3 nano prepared by self-propagating 

combustion synthesis 

11 

[2007Hos] XRD, SEM, DTA/TGA Y 3Fe 5O 12, nanoparticles prepared by a sol-gel 

autocombustion process 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_23 

ß Springer 2009

12 23 

Fe–O–Y 

. Fig. 1 

Fe-O-Y. The Y 2O 3-Fe 2O 3 quasibinary system under air atmosphere 



MSIT 1

. Fig. 2 

Fe-O-Y. Liquidus surface projection 



MSIT 1 

Fe–O–Y 23 

13 

DOI: 10.1007/978-3-540-70890-2_23 

ß Springer 2009

14 23 

Fe–O–Y 

. Fig. 3 

Fe-O-Y. Phase equilibria at 1200˚C 



MSIT 1

. Fig. 4 

Fe-O-Y. Phase equilibria at 1000˚C 



MSIT 1 

Fe–O–Y 23 

15 

DOI: 10.1007/978-3-540-70890-2_23 

ß Springer 2009

16 23 

Fe–O–Y 

References 

[1945Dar] Darken, L.S., Gurry, G.W., “The System Iron-Oxygen. I- The Wuestite Field and Related Equilibria”, 

J. Am. Chem. Soc., 67, 1398–1412 (1945) (Experimental, Phase Diagram, Thermodyn., *, 26) 

[1946Dar] Darken, L.S., Gurry, G.W., “The System Iron-Oxygen. II- Equilibria and Thermodynamics of Liquid 

Oxides and Other Phases”, J. Am. Chem. Soc., 68, 798–816 (1946) (Experimental, Phase Diagram, 

Thermodyn., *, 24) 

[1957Cur] Curtis, C.E., “Properties of Yttrium Oxide Ceramics”, J. Am. Ceram. Soc., 40(8), 274–278 (1957) (Crys. 


[1957Gel] Geller, S., Gilleo, M.A., “The Crystal Structure and Ferrimagnetism of Yttrium-Iron Garnet, 

Y 3Fe 2(FeO 4) 3”, J. Phys. Chem. Solids, 3, 30–36 (1957) (Crys. Structure, Experimental, 28) 

[1958Nie] Nielsen, J.W., Dearborn, E.F., “The Growth of Single Crystals of Magnetic Garnets”, J. Phys. Chem. 

Solids, 5, 202–207 (1958) (Phase Diagram, Phase Relations, Experimental, 8) 

[1961Hoo] Van Hook, H.J., “Phase Relations in the System Fe 2O 3-Fe 3O 4-YFeO 3 in Air”, J. Am. Ceram. Soc., 44(5), 

208–214 (1961) (Experimental, Phase Diagram, 6) 

[1962Hoo] Van Hook, H.J., “Phase Relations in the Ternary Systems Fe 2O 3-FeO-YFeO 3”, J. Am. Ceram. Soc., 45(4), 

162–165 (1962) (Experimental, Phase Diagram, 9) 

[1963Ber] Beretka, J., “Differential Thermal Analysis of Yttrium Iron Garnet”, J. Phys. Chem. Solids, 24(1), 169–171 


[1965Cop] Coppens, P., Eibschutz, M., “Determination of the Crystal Structure of Yttrium Orthoferrite and 

Refinement of Gadolinium Orthoferrite”, Acta Crystallogr., 19, 524–531 (1965) (Crys. Structure, 



Iron at 1600˚C”, Int. Symp. Metall. Chem. - Appl. Ferrous Metall., Sheffield, July 1971, Iron and Steel Inst, 

London, 173–177 (1973) (Phase Relations, Thermodyn., Review, 8) 

[1975Lev] Levin, E.M., McMurdie, H.F., Phase Diagrams for Ceramists, Am. Ceram. Soc. Vol. 3, p. 44, Fig. 4212 

(1975), as quoted in Cassedanne, J., Compt. Rend. Acad. Sci., Paris, 252, 3262 (1961) 

[1975Kim] Kimizuka, N., Katsura, T., “Standard Free Energy of Formation of YFeO 3,Y 3Fe 5O 12, and a New 

Compound YFe 2O 4 in the Fe-Fe 2O 3-Y 2O 3 System at 1200˚C”, J. Solid State Chem., 13, 176–181 (1975) 

(Experimental, Thermodyn., Phase Diagram, 8) 

[1976Dar] Dariel, M.P., Pickus, M.R., “Structural and Magnetic Study of Some Oxygen Stabilised Rare-Earth-Iron 

Intermetallic Compounds”, J. Less-Common Met., 50, 125–137 (1976) (Crys. Structure, Experimental, 

18) 

[1977Tre] Tretyakov, Yu.D., Kaul, A.R., Portnoy, V.K., “Formation of Rare Earth and Yttrium Orthoferrites: 

A Thermodynamic Study”, High Temp. Sci., 9, 61–70 (1977) (Experimental, Phase Relations, Thermodyn., 

19) 

[1978Kat] Katsura, T., Sekine, K., Kitayama, K., Sugihara, T., Kimizuka, N., “Thermodynamic Properties of 

Fe-Lanthanoid-O Compounds at High Temperatures”, J. Solid State Chem., 23, 43–57 (1978) (Phase 

Diagrams, Thermodyn., Review, 24) 

[1978Pie] Piekarczyk, W., Weppner, W., Rabenau, A., “Dissociation Pressure and Gibbs Energy of Formation of 

Y 2Fe 5O 12 and YFeO 3”, Mater. Res. Bull., 13, 1077–1083 (1978) (Experimental, Thermodyn., 11) 

[1979Pie] Piekarczyk, W., Weppner, W., Rabenau, A., “Solid State Electrochemical Study of Phase Equilibria and 

Thermodynamics of the Ternary System Y-Fe-O at Elevated Temperatures”, Z. Naturforsch. A, 34(4), 

430–436 (1979) (Experimental, Phase Diagram, Thermodyn., 23) 

[1980Mat] Matsui, Y., “Extra Electron Reflections Observed in YFe 2O 4, YbFe 2O 4,Yb 2Fe 3O 7 and Yb 3Fe 4O 10”, 

J. Appl. Crystallogr., 13, 395–397 (1980) (Crys. Structure, Experimental, 8) 

[1980Vor] Vorobev, Yu.P., Dragoshanskaya, T.I., Matskevich, S.L., Men, A.N., “Determination of Departure of 

Y 3Fe 5O 12, Gd 3Fe 5O 12 and Y 1.5Gd 1.5Fe 5O 12 from Stoichiometry at 800-1400˚C”, Inorg. Mater., 16(6), 

754–758 (1980), translated from Izv. Akad.. Nauk SSSR, Neorgan. Mater., 16(6), 1083–1087 (1980) (Crys. 


[1983Fet] Fetisov, V.B., Dvinina, M.A., Vorobev, Yu.P., Sapozhnikova, T.V., Shapovalov, A.G., Pankov, Yu.V., 

Sovkov, V.E., Men, A.N., “Phase Equilibria in the Y-Fe-O System at 1270K”, Inorg. Mater., 19(11), 

1650–1652 (1983), translated from Izv. Akad. Nauk SSSR, Neorgan. Mater., 19(11), 1871–1874 (1983) 

(Phase Relations, Experimental, 12) 



MSIT 1

Fe–O–Y 23 

17 

[1983Kim] Kimizuka, N., Yamamoto, A., Ohashi, H., Sugihara, T., Sekine, T., “The Stability of the Phases in the 

Ln 2O 3-FeO-Fe 2O 3 Systems which are Stable at Elevated Temperatures (Ln: Lanthanide Elements and 

Y)”, J. Solid State Chem., 49, 65–76 (1983) (Review, Thermodyn., 30) 

[1984Pie] Piekarczyk, W., Rabenau, A., Weppner, W., “Relations between the Thermodynamic Potentials for the 

Formation of Yttrium and Rare Earth Iron Perovskites and Garnets and the Ionic Radii of Yttrium and 

the Rare Earth Elements”, (in German), Z. Anorg. Allg. Chem., 516, 153–158 (1984) (Review, Calculation, 


[1985Sko] Skolis, Yu.Ya., Kitsenko, S.V., Levitskii, V.A., “Measurement of the Thermodynamic Properties of 

Yttrium Ferrites by the E.m.f. Method with a Solid Fluoride-ion Electrolyte”, Russ. J. Phys. Chem., 59(9), 

1403–1404 (1985), translated from Zh. Fiz. Khim., 59(9), 2356–2358 (1985) (Experimental, Thermodyn., 

9) 

[1985Tin] Ting, D., Longmei, W., “Thermodynamics of Fe-Y-S, Fe-Y-O and Fe-Y-S-O Metallic Solutions”, J. Less- 

Common Met., 110, 179–185 (1985) (Experimental, Phase Relations, Thermodyn., 10) 

[1987Lon] Longmei, W., Ting, D., Kexiang, Y., “A Study of Thermodynamics and Phase Equilibria in Order to 

Predict the Behavior of Yttrium in Iron and Steel”, Inorg. Chim. Acta, 140(1-2), 189–191 (1987) 

(Experimental, Phase Relations, Thermodyn., 8) 

[1988Pie] Piekarczyk, W., “Thermodynamic Model of Chemical Vapour Transport and its Application to some 

Ternary Compounds”, J. Cryst. Growth, 89, 267–286 (1988) (Experimental, Review, Calculation, Thermodyn., 

27) 

[1989Rag] Raghavan, V., “The Fe-O-Y (Iron-Oxygen-Yttrium) System”, Phase Diagrams of Ternary Iron Alloys, Ind. 

Inst. Metals, Calcutta, 5, 355–365 (1989) (Phase Diagram, Crys. Structure, Review, 22) 

[1990Car] Carlson, O.N., “The O-Y (Oxygen-Yttrium) System”, Bull. Alloy Phase Diagrams, 11(1), 61–66, (1990) 

(Phase Diagram, Crys. Structure, Thermodyn., Calculation, 28) 


Diagram, Thermodyn., Assessment, Calculation, 53) 

[1992Boc] Bocquet, A.E., Fujimori, A., Mizokawa, T., Saitoh, T., Namatame, H., Suga, S., Kimizuka, N., Takeda, Y., 

Takano, M., “Electronic Structure of SrFe 4+ O 3 and Related Fe Perovskite Oxides”, Phys. Rev. B, 45(4), 

1561–1570 (1992) (Experimental, Electronic Structure, 35) 

[1992Zha] Zhang, W., Liu, G., Han, K., “The Fe-Y (Iron-Yttrium) System”, J. Phase Equilib., 13(3), 304–308 (1992) 

(Phase Diagram, Crys. Structure, Review, 29) 

[1995Ish] Ishii, F., Ban-ya, S., “Equilibrium between Yttrium and Oxygen in Liquid Iron and Nickel”, ISIJ Int., 

35(3), 280–285 (1995), translated from Tetsu to Hagane, 80(5), 359–364 (1994) (Phase Relations, 

Thermodyn., Experimental, 29) 

[1995Kow] Kowalski, M., Spencer, P.J., “Thermodynamic Revaluation of the Cr-O, Fe-O and Ni-O Systems: 

Remodelling the Liquid, BCC and FCC Phases”, Calphad, 19(3), 229–243 (1995) (Assessment, Phase 

Diagram, Thermodyn., Review, 47) 

[1996Par] Parkin, I.P., Komarov, A.V., Fang, Q., “Alternative Solid State Routes to Mixed Metal Oxides (LnCrO3, 

LnFeO 3)”, Polyhedron, 15(18), 3117–3121 (1996) (Crys. Structure, Phase Relations, Experimental, 10) 

[1997Ost] Ostorero, J., Gasgnier, M., Petit, A., “Yttrium Iron Garnet and Y, Fe Oxides Synthesized by Microwave 

Monomode Energy Transfert”, J. Alloys Compd., 262/263, 275–280 (1997) (Crys. Structure, Phase 


[1998Niu] Niu, Y., Yan, R.Y., Fu, G.Y., Wu, W.T., Gesmundo, F., “The Oxidation of two Fe-Y Alloys under Low 

Oxygen Pressures at 600-800˚C”, Oxid. Met., 49, 91–114 (1999) (Experimental, Phase Relations, 

Kinetics, 26) 

[1999Cau] Caudron, E., Buscail, H., Riffard, F., “Initial Oxidation Stages of Yttrium-Implanted Pure Iron at 700˚C 

by In-situ High Temperature X-Ray Diffraction”, Eur. Phys. J. - Applied Phys., 8(3), 233–240 (1999) 

(Experimental, Phase Relations, Kinetics, 38) 

[1999Li] Li, Y.S., Niu, Y., Gesmundo, F., “High Temperature Scaling of Binary Fe-Y Alloys in Pure Oxygen”, High 

Temp. Mater. Proc., 18(3), 185–195 (1999) (Experimental, Phase Relations, Kinetics, 29) 

[2000Kuz] Kuznetsov, M.V., Pankhurst, Q.A., Parkin, I.P., Affleck, L., Morozov, Y.G., “Self-Propagating High 

Temperature Synthesis of Yttrium Iron Chromium Garnets Y 3Fe 5–xCr xO 12 (x < 0 < 0.6)”, J. Mater. 

Chem., 10, 755–760 (2000) (Crys. Structure, Phase Relations, Experimental, 30) 

[2000Pet] Petras, L., Preisinger, A., “Reaction Kinetics of Yttrium Iron Garnet Formation in Air up to 1400˚C”, 

Mater. Sci. Forum, 321–324, 368–373 (2000) (Experimental, Phase Relations, Kinetics, 4) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_23 

ß Springer 2009

18 23 

Fe–O–Y 

[2000Tak] Taketomi, S., Sai, Z.R., Ohuchi, F.S., “Electron Diffraction of Yttrium Iron Oxides Nanocrystals 

Prepared by the Alkoxide Method”, J. Magn. Magn. Mater., 217, 5–13 (2000) (Experimental, Phase 

Relations, Morphology, Nano, 22) 

[2001Cau] Caudron, E., Buscail, H., “Initial Stages of Oxidation of Yttrium-Implanted Pure Iron and Various 

Steels at 700˚C under Low Oxygen Partial Pressure”, Corros. Sci., 43(8), 1477–1495 (2001) (Experimental, 

Phase Relations, Kinetics, 39) 

[2001Pee] Peelamedu, R.D., Roy, R., Agrawal, D.K., “Reaction Kinetics and Anisothermal Effects in Microwave 

Fields: System Y 2O 3-Fe 3O 4”, J. Mater. Res., 16(10), 2770–2772 (2001) (Experimental, Phase Relations, 

Kinetics, 13) 

[2002Nag] Nagashio, K., Kuribayashi, K., “Phase Selection in the Undercooled Peritectic Y 3Fe 5O 12 Melt”, Acta 

Mater., 50, 1973–1981 (2002) (Experimental, Phase Relations, Transport Phenomena, 27) 

[2003Che] Chen, C., Hu, C.C., “Quantitative Analysis of YIG, YFeO 3 and Fe 3O 4 in LHPG-Grown YIG Rods”, 

J. Cryst. Growth, 249, 245–250 (2003) (Crys. Structure, Phase Relations, Magn. Prop., 12) 

[2003Lom] Lomako, I.D., Pavlov, V.I., Shishkin, N.Ya., “Transport Properties of Y 3Fe 5O 12 Garnet Crystals”, 

Crystallography Reports, 48(1), 116–123 (2003), translated from Kristallografiya, 48(1), 121–129 

(2003), (Experimental, Electric Prop., Transport Phenomena, 22) 

[2004Kit] Kitayama, K., Sakaguchi, M., Takahara, Y., Endo, H., Ueki, H., “Phase Equilibrium in the System 

Y-Fe-O at 1100˚C”, J. Solid State Chem., 177(6), 1933–1938 (2004) (Experimental, Phase Diagram, 


[2004Li] Li, C., Soh, K.C.K., Wu, P., “Formability of ABO 3 Perovskites”, J. Alloys Compd., 372, 40–48 (2004) 

(Crys. Structure, Theory, 28) 

[2004Sug1] Sugasava, M., Kikukawa, N., Nagano, Y., Kayano, N., Kimura, T., “Characterisation of the Y-Fe-O 

Ultrafine Particles Containing a New Compound YFe 3+xO 1.5(4+x) Sythesized by rf Thermal Plasmas”, 

Ceramic Intl., 30(4), 515–523 (2004) (Crys. Structure, Magn. Prop., Experimental, 13) 

[2004Sug2] Sugasava, M., Kikukawa, N., Nagano, Y., Kayano, N., Kimura, T., “Magneic Properties of Y-Fe-O 

Ultrafine Particles YFe 3+xO 1.5(4+x) Sythesized by rf Thermal Plasma”, Ceramic Intl., 30(8), 2191–2201 

(2004) (Crys. Structure, Magn. Prop., M‘ssbauer, Experimental, 16) 

[2004Wu] Wu, L., Yu, J.C., Zhang, L., Wang, X., Li, S., “Selective Self-propagating Combustion Synthesis of 

Hexagonal and Orthorhombic Nanocrystalline Yttrium Iron Oxide”, J. Solid State Chem., 177(10), 

3666–3674 (2004) (Crys. Structure, Experimental, Magn. Prop., Morphology, Nano, Phase Relations, 

43) 

[2007Hos] Hosseini Vajargah, S., Madaah Hosseini, H.R., Nemati, Z.A., “Preparation and Characterization of 

Yttrium Iron Garnet (YIG) Nanocrystalline Powders by Auto-Combustion of Nitrate-Citrate Gel”, 

J. Alloys Compd., 430(1-2), 339–343 (2007) (Crys. Structure, Experimental, Nano, 18) 


(1990) 





MSIT 1

Iron – Oxygen – Zirconium 


Olga Fabrichnaya 

Introduction 

Fe–O–Zr 24 

1 

The ZrO 2 and FeO are the major components in systems significant for understanding 

whether refractories would react with metallurgical slag and whether the melt in the active 

zone of a nuclear reactor would react with its housing material and with a device designed to 

keep the melt in active zone of a reactor in case of severe nuclear accident. The phase relations 

in the Zr-Fe-O system are also of interest because of deoxidation and inclusion shape control 

in steels. Stabilized ZrO 2 are widely used as oxygen sensors [2001Cao]. Fe 2O 3 stabilization of 

ZrO 2 decreases operating temperature down to 320˚C. The ZrO 2-Fe 2O 3 samples prepared by 

co-precipitation followed by calcination revealed catalytic activity for different organic chemistry 

reactions [1981Jin, 1993Wu]. 

The phase relations in the FeO-ZrO 2 system were experimentally studied in an inert 

atmosphere by [1957Fis]. Recently the phase relations in this system were studied by 

[2006Bec] and [2006Bes] under an inert atmosphere and the eutectic temperature and 

composition were refined. [1967Jon] presented a phase diagram of the ZrO 2-Fe 3O 4 system. 

[1975Kat] used thermogravimetric analysis in oxygen controlled atmosphere and presented 

the isothermal section of the ZrO 2-FeO-Fe 2O 3 system at 1200˚C. [1987Kim] and [1988Kim] 

studied the ZrO2-FeO-Fe2O3 system using thermogravimetry at air condition and partial 

oxygen pressure of 2.1·10 2 Pa. 

[2002Pet] studied the ZrO 2-FeO-Fe 2O 3 system at air conditions in the temperature range 

of 1870-2230˚C and found liquid immiscibility in the composition range 34-82 mass% ZrO 2. 

The liquidus surface and phase diagram of the ZrO 2-FeO 1.357 join were calculated by [2002Pet] 

using regular solution model. 

The solubility of oxygen in Fe-Zr melts was experimentally studied by equilibration 

technique in [1965Buz, 1973Buz, 1974Fru, 1976Jan]. Minimum solubility of oxygen (0.0008 

mass% O) was found by [1974Fru] at 0.08 mass% Zr and 1680˚C. Oxygen activity in Fe-Zr 

melts was measured by emf method in [1973Tep, 1976Jan]. 

Investigation of thermal stability and properties of the ZrO 2-Fe 2O 3 solid solutions produced 

by high-energy ball milling at room temperature was performed by [1996Ton, 2000Cao, 

2001Cao, 2002Cao, 2006Fig]. 

Co-precipitation method was used in several studies [1977Heu, 1997Nar, 1999Ste, 

2000Laj, 2000Ste, 2001Ste] to produce an amorphous phase in the ZrO 2-Fe 2O 3 system. The 

microstructures and phase development were observed for different temperatures and times of 

heat treatment. It was shown that in this system metastable phases were formed first, which 

transform to the stable phases during heat treatment. 

An evaluation of the experimental data for the Fe-O-Zr system was performed by 

[1989Rag1] and the isothermal section at 1000˚C was constructed as well as the solubility 

curves of oxygen at 1680 and 1800˚C based on the available experimental data of [1974Fru, 

1967Buz]. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_24 

ß Springer 2009

2 24 

Fe–O–Zr 

Wagner’s formalism was used in studies of [1965Buz, 1967Buz, 1973Buz, 1974Fru, 

1976Jan, 1986Gho] to calculate interaction parameters and deoxidation constant. 

[2004Hua] made a Calphad-type assessment for the Fe-O-Zr system using ionic model for 

the liquid description. However experimental data on the Fe solubility in βZrO 2 and γZrO 2 

were not taken into account as well as Zr solubility in hematite and magnetite phases. The 

derived database was used to calculate solubility of oxygen in Fe-Zr melt. [2004Jun] used 

associate model to calculate solubility curves at 1600 and 1680˚C as well as activity of oxygen 

in Fe-Zr melt. 

Experimental studies and modelling in the Fe-O-Zr system are summarized in Table 1. 


The Fe-Zr binary system is accepted from the experimental study of [2002Ste]. In this study it 

was shown that the Fe23Zr6 phase shown by [Mas2] is oxygen stabilized and is not an 

equilibrium phase. According to [2002Ste] the Zr 2Fe phase is stable in a quite narrow 

temperature range of 780-951˚C, while according to [Mas2] it is stable below 974˚C. The 

phase diagram of the Fe-O system is accepted from [1991Sun]. The thermodynamic assessment 

of [1991Sun] gives results very close to [Mas2]. The phase diagram of the Zr-O system is 

accepted from a thermodynamic assessment of Wang et al. [2004Wan, 2006Wan] which is in 

good agreement with [Mas2]. 


The crystallographic data for solid phases are listed in Table 2. Polymorphic modifications of 

ZrO 2 dissolve some amount of FeO [2006Bes]. The cubic phase γZrO 2 with the fluorite 

structure dissolves up to 13 mol% FeO at T~1800˚C and the tetragonal phase βZrO 2 up to 

2.2 mol% at 1332˚C. According to [1957Fis] the FeO solubility in the tetragonal phase is 

higher (6.7 and 5 mol% FeO at 1450 and 1800˚C, respectively). It should be mentioned that a 

tetragonal phase t’ obtained by fast quenching from high temperature forms by diffusionless 

mechanism and differs in the unit cell parameters from the tetragonal phase obtained by slow 

cooling (equilibrium phase). For the t’ phase the c/a ratio is slightly above 1. Probably, in fact, 

[2006Bes] obtained the t’ phase, therefore the unit cell parameters were different from βZrO 2. 

The monoclinic phase αZrO 2 does not dissolve any detectable amount of FeO. Fe xOwüstite 

does not dissolve any detectable amount of ZrO 2 [1989Rag1]. According to [1975Kat] 

magnetite Fe 3O 4+x dissolves ~2.7 mol% of ZrO 2. Kiminami [1987Kim, 1988Kim] reported 

data on the reaction of decomposition of magnetite to hematite. The temperature of this 

reaction increases from 1300 to 1437˚C with an increase of the partial pressure of oxygen 

from 2·10 2 to 2·10 4 Pa accompanied by an increase of the solubility of ZrO 2 in Fe 2O 3 from 2 to 

6 mol% and decrease of the solubility of Fe 2O 3 in ZrO 2 from 8 to 3 mol% of Fe 2O 3. The results 

of [1967Jon] on the solubility of ZrO 2 in hematite and magnetite and solubility of Fe 3O 4 in 

ZrO 2 are in reasonable agreement with [1987Kim]. [2002Pet] found the maximal solubility of 

FeO 1.357 in the monoclinic ZrO 2 as high as 6.6 mass% and maximal solubility of ZrO 2 in Fe 3O 4 

as high as 2.5 mass%. The iron oxide solubility in monoclinic ZrO 2 seems to be too high and 

probably refers to another modification of ZrO2. 



MSIT 1

[2002Kov] reported solid solutions Zr 3FeO x of the BRe 3 type forming at 800˚C in the range 

of x = 0-1. 

[1960Nev] found a Ti 2Ni type cubic ternary compound τ 1 with a small homogeneity range 

(Zr 2Fe) 1–xO x stable at 1000˚C. The maximal concentration of oxygen in this compound was 

around 10 mol%. The same structure TiNi 2 was reported by [1967Hol] and by [1998Zav] after 

annealing at 800-1000˚C in the purified Ar. The composition of the τ 1 phase determined by 

[1998Zav] (Zr4Fe2O0.6) was close to the data of [1967Hol] (Zr6Fe3O) and [1960Nev]. A cubic 

ternary compound of ZrFe2.67O0.67 was mentioned by [1989Rag1] by mistake referring 

[1984Pap]. The compound studied by [1984Pap] is oxifluoride and it is not relevant to the 

Fe-O-Zr system. [2001Wu] reported on the synthesis of iron zirconate by aging at 850˚C of 

sintered mixture of ZrO 2 and αFe 2O 3. This phase with the Zr/Fe ratio of approximately 1 has 

the monoclinic crystallographic symmetry and it is most probably metastable. 


[1957Fis] experimentally studied the phase relations in the FeO-ZrO 2 system. It is a simple 

eutectic system with no significant solubility of ZrO 2 in FeO and small solubility of iron oxide 

in ZrO 2. Later this system was studies by [2006Bec, 2006Bes]. The position of the eutectic 

point was refined at 1332˚C and 10.3 mol% ZrO 2. The maximal solubility of FeO in the 

tetragonal ZrO2 (βZrO2) was determined as 2.2 mol% FeO at 1332˚C. The obtained temperature 

is in agreement with [1957Fis], while eutectic composition (ZrO 2 content) is higher than 

one obtained by [1957Fis]. The position of the metatectic reaction γZrO 2 Ð βZrO 2+L was 

approximately determined by [2006Bes] at the temperature of 1800˚C or below with the 

maximal solubility of FeO in the cubic ZrO 2 (γZrO 2) ~13 mol%. The experimental phase 

diagram of the ZrO 2-FeO system from the work of [2006Bes] is presented in Fig. 1. Strictly 

speaking this system is not quasibinary because metallic Fe was in equilibrium with FeO. 

The ZrO 2-Fe 2O 3 system was extensively studied in many works [1977Heu, 1996Pop, 

1997Nar, 1999Ste, 2000Ste, 2001Ste], but many of them dealt with metastable phase formations 

at low temperature (500-900˚C). An equilibrium study was performed at 1100˚C by 

[1996Pop] and the maximal mutual solubility of ZrO 2 and Fe 2O 3 was determined by XRD. It 

was up to 2 mol% of Fe 2O 3 in the monoclinic ZrO 2 (αZrO 2) and 1 mol% of ZrO 2 in αFe 2O 3. 

For the composition range between 2 and 99 mol% Fe 2O 3 two solid solution phases αZrO 2 

and αFe 2O 3 were found in equilibrium. 


The data on the invariant reactions obtained by [2006Bes] and [1967Jon] are presented 

in Table 3. [1991Zhu] studied a eutectoid reaction in the Zr-Fe-O (0.98 mass% Fe, 

0.21 mass% O) alloy using DTA, but these data are not accepted in the present evaluation 

due to difference in the transformation temperatures in pure Zr and Fe-Zr system. 



3 

The liquidus surface in the ZrO 2-FeO-Fe 2O 3 was calculated by [2002Pet]. However, the 

thermodynamic data were not presented by [2002Pet] and polymorphic transformations in 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_24 

ß Springer 2009

4 24 

Fe–O–Zr 

ZrO 2 were not taken into account. The ZrO 2 phase with the hexagonal structure found by 

[2002Pet] seems to be erroneous. The monovariant line FeO+Fe 3O 4+L was missing. Therefore 

the calculated liquidus surface and invariant reactions from [2002Pet] are not presented in this 

evaluation. According to the calculations of [2002Pet] there is a quite large liquid miscibility 

gap starting in the ZrO 2-Fe 2O 3 system extending into the ternary system up to 40 mass% of 

FeO. The presence of the miscibility gap was also confirmed by the experimental studies 

performed in [2002Pet]. However, it should be mentioned that the miscibility gap was not 

indicated in other ZrO 2 based systems (see [2005ACS]). It is not clear why the miscibility gap 

appears only in the ZrO 2-Fe 2O 3 system, but not in the ZrO 2-Al 2O 3. It should be also 

mentioned that the samples investigated by [2002Pet] contained a remarkable amount of 

impurities. 


The isothermal section of the Fe-O-Zr system at 1000˚C presented in Fig. 2 is from the 

evaluation of [1989Rag1] who took into account data of [1960Nev] and data of [1975Kat] 

obtained at 1200˚C with the corrected solubility of Zr in magnetite ~0.3 at.% at 1000˚C instead 

of 0.8 at.% at 1200˚C. Some corrections were made in Fig. 2 according to the accepted binary 

Fe-Zr system. The isothermal section in the ZrO 2-FeO-Fe 2O 3 system at 1200˚C from 

[1975Kat] is shown in Fig. 3. The solubility of FeO in ZrO 2 and ZrO 2 in Fe 2O 3 was not 

determined. The isothermal section at 1437˚C at air oxygen partial pressure from [1987Kim] 

and at T ≤1380˚C at p(O2) = 2.1·10 2 Pa from [1988Kim] are presented in Figs. 4a and 4b. 


The system Fe 3O 4-ZrO 2 was studied by [1967Jon]. Two invariant reactions an eutectic and a 

peritectic were found at 1525 and 1434˚C, respectively. The phase diagram from [1967Jon] is 

presented in Fig. 5. At high temperatures the phase diagram is shown tentatively and the 

cubic-tetragonal transformation was not presented. As mentioned in the section of Solid 

Phases, according to [1967Jon], the ZrO 2 phase dissolved ~6 mol% of Fe 3O 4 and the Fe 3O 4 

and Fe 2O 3 phases dissolve limited amount of ZrO 2. However, it was not indicated which ZrO 2 

modification participate in the equilibrium. The data of [1987Kim] indicated that the 

solubility of ZrO 2 in Fe 2O 3 increases the temperature of decomposition of hematite to 

magnetite and oxygen from 1380 to 1437˚C in air condition, that is in agreement with 

[1967Jon] within uncertainty limits. [1988Kim] studied a reaction of the hematite decomposition 

at lower partial pressure of oxygen (p(O2)=2.1·10 2 Pa) than in [1987Kim] and it was 

found that due to the solubility of ZrO2 in hematite the temperature of its decomposition 

increased from 1265˚C in pure Fe-O system to 1300˚C in the ZrO 2 containing system. 


The effect of Zr in liquid iron on oxygen activity along liquid/ZrO 2 equilibrium was experimentally 

studied by emf method in [1973Tep] and [1976Jan]. The experimentally determined 

oxygen content in the Fe-Zr melts by [1976Jan] was higher than the calculated from the 



MSIT 1

activity data using Wagner’s formalism. The calculation of [2004Jun] based on the associate 

model reproduce experimental data on oxygen activity very well. The calculated activities of 

oxygen in the Fe-Zr liquid alloys at 1550-1650˚C from [2004Jun] are presented in Fig. 6. The 

calculated oxygen solubility at 1600 and 1680˚C in the composition range 0.1-1.5 mass% Zr by 

[2004Jun] is in reasonable agreement with the experimental data of [1976Jan] and [1974Fru], 

respectively. However, at lower Zr content the calculated solubility is lower than that measured 

experimentally. It should be mentioned that there is a large scatter in the experimental data on 

the solubility of oxygen in [1965Buz] and [1976Jan]. 

The calculated activity and solubility of oxygen in molten Fe based on partially ionic 

liquid model by [2004Hua] seems to be inconsistent with experimental data. The calculated 

O solubility [2004Hua] is one order of magnitude lower than the experimental data and 

the calculated minimum of oxygen solubility is at much higher Zr content. This implies 

that the measured O-Zr interaction is much stronger that predicted by the modelling of 

[2004Hua]. 

Fruehan [1974Fru] applied Wagner’s formalism for dilute solutions to derive e Zr O =–3 

and K O Zr = 3.5·10 –8 using his own experimental data on oxygen solubility in Fe-Zr melt. 

[1986Gho] treated experimental data of [1974Fru] using Wagner’s formalism to calculate 

first and second order interaction parameters as well as deoxidation constant at 1680˚C. 



5 

ZrO2 based oxygen gas sensors have wide applications [2000Tan, 2001Cao, 2002Cao]. 

[2000Tan] prepared nanostructured non-equilibrium solid solution in the ZrO2-Fe2O3 system 

by high-energy ball milling and annealing at 400-650˚C and studied gas sensing properties. 

According to [2001Cao] the ZrO 2-Fe 2O 3 oxygen sensors obtained by ball milling, annealed at 

400-800˚C have low operating temperature of 350˚C. [2000Cao] studied oxygen sensitivity 

and electric conductivity of 0.8ZrO 2-0.2Fe 2O 3 mixtures depending on time of annealing. 

[2001Cao] studied oxygen sensitivity for different annealing temperatures depending on 

time of annealing. Additionally, the effect of composition, annealing temperature and milling 

time on sensitivity were studied. Also the response time for the composition of 0.8ZrO2- 

0.2Fe2O3 annealed at 600˚C was quite good for such a low operating temperature as 320˚C. 

[2002Cao] used XPS spectra to estimate oxygen vacancy concentration in ZrO 2-Fe 2O 3 solid 

solutions obtained by high energy ball milling. 

Thin films in the ZrO 2-Fe 2O 3 system were annealed in two stages at 77 and 97-997˚C and 

optical properties of these films were studied by [2002Koz]. A decomposition of the solid 

solution and the formation of Fe 2O 3 was observed with increasing of the annealing temperature 

from 427-727˚C. This was accompanied by increase of light absorbtion in the visible 

region. The thin films are dielectric with high refractive indexes. They absorb radiation in 

210-340 nm and 500-800 nm, the latter can be referred to high energy-gap semiconductors. 

[1998Zav] studied hydrogenation of Zr 4Fe 2O 0.6 composition and magnetic properties of 

this compound and products of hydrogenation. 

[1992Lou] performed thermoelectric-power and resistivity measurements to study precipitation 

kinetics of the Fe-O-Zr alloys between 450 and 600˚C. The correlation between 

these two properties was shown due to the precipitation. The solubility of Fe in Zr alloys 

between 450 and 550˚C depended on the presence of oxygen. Experimental studies of material 

properties are presented in Table 4. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_24 

ß Springer 2009

6 24 

Fe–O–Zr 

Miscellaneous 

There are several papers devoted to microstructure and phase development during heat 

treatment of amorphous precursors obtained by co-precipitation method in the ZrO 2-Fe 2O 3 

system [1977Heu, 1997Nar, 1999Ste, 2000Ste, 2001Ste]. [1977Heu] indicated that in the 

ZrO2-Fe2O3 system a metastable cubic phase crystallized first then transformed to a stable 

phase assemblage by heat treatment. Similar observation was made by [1997Nar]. [1997Nar] 

also indicated an amorphous phase first crystallized as a single-phase solid solution appeared 

as cubic by XRD and tetragonal by electron diffraction. At higher temperatures this phase 

transforms to the tetragonal phase and γFe 2O 3 (observed only by TEM), which transformed to 

αFe 2O 3 at even higher temperatures. Thermal stability of the ZrO 2-Fe 2O 3 amorphous precursors 

obtained by co-precipitation from aqueous solutions were studied after calcination at 

500-1100˚C by XRD, Raman and Mössbauer spectroscopy by [1999Ste, 2000Ste, 2001Ste]. 

[2000Ste] additionally studied thermal stability under low pressure (4·10 –3 Pa). Amorphous 

samples were studied by thermal analysis and gravimetry. It was found that incorporation of 

Fe +3 stabilized cubic polymorph of ZrO 2 occurring at Fe 2O 3 content ≥10 mol%. The presence 

of Fe 2O 3 above solubility limit caused transformation to monoclinic ZrO 2. Terminal solubility 

limit of Fe 2O 3 in the ZrO 2 decreased with temperature increase from 33 mol% at 600˚C to 2% 

at 1100˚C. Mössbauer spectroscopy indicated incorporation of Zr +4 into αFe 2O 3 structure 

decreasing with temperature increase. A comparison of the results obtained at atmospheric 

pressure and at low pressure showed that Fe +3 destabilized cubic ZrO 2 at low pressure 

[2001Ste]. Also, it was found by [2001Ste] that the solubility of Fe2O3 in ZrO2 was higher at 

low pressure. The effect of pressure was attributed to the influence of oxygen vacancies 

introduced during calcination at low pressure. Nanocrystallized cubic Fe-stabilized zirconia 

were prepared by co-precipitation method and heat treated at different temperatures between 

400 and 900˚C in [2000Laj]. It transformed to the tetragonal phase at the temperatures above 

800˚C and then to the monoclinic phase at 900˚C. An addition of 30 mol% of Fe +3 stabilized 

cubic phase above 800˚C in Ar. Higher Fe 2O 3 content resulted in phase separation of hematite. 

The greatest thermal stability was found at 20 mol% of Fe +3 . Particle size was a primary factor 

determining cubic-tetragonal transformation. 

The mixtures of ZrO2-Fe2O3 (16.7 mass% Fe2O3) obtained by high energy ball milling at 

room temperature were investigated by XRD and TEM in work of [1996Ton]. It was shown 

that nanocrystalline structure was forming during milling that enables the formation of the 

tetragonal phase. TEM study showed that grains were slading and overlapping each other. The 

obtained patterns could be ascribed to tetragonal or cubic phases. Cao et al. [2000Cao, 

2001Cao, 2002Cao] studied thermal stability, electric conductivity and gas sensitivity of 

powders obtained by ball milling at room temperature. [2000Cao] showed using XRD, DTA 

and TEM that after 60 h of milling monoclinic ZrO2 transformed to Fe +3 stabilized cubic 

structure which forms to amorphous-like conglomerates at 120 hours of milling. After heat 

treatment at 650˚C the Fe +3 expelled from the metastable cubic phase forming αFe 2O 3 

[2000Cao]. [2002Cao] obtained XPS spectra and calculated oxygen vacancy concentration. 

Thermal stability of the ZrO 2-15 mol% Fe 2O 3 solid solutions obtained by ball milling at 

room temperature was studies by [2006Fig] using Mössbauer spectroscopy, XRD and DTA. 

It was shown that all Fe 2O 3 was incorporated in cubic ZrO 2 structure by ball milling, 

producing very disrupted solid solution which crystallized in cubic form after annealing at 

620˚C. After annealing at 900˚C cubic solid solution decomposed to hematite and tetragonal 

solid solution. Annealing at 1100˚C results in the formation of the monoclinic ZrO2 phase. 



MSIT 1

The temperature of 900˚C is indicated as a limit of the stability of the tetragonal metastable 

solid solution. 

[2005Str] studied interaction of stabilized ZrO 2 solutions with Fe 2O 3 at 1750˚C. It was 

found that only MgO stabilized cubic zirconia reacted with Fe 2O 3 forming MgFe 2O 4 spinel, 

while Ca, Y and Nd stabilized ZrO 2 resisted decomposition by Fe 2O 3 attack. Some dissolution 

of Fe 2O 3 in cubic structure was indicated. 

Influence of Fe2O3 on martensitic transformation of tetragonal to monoclinic phase in the 

ZrO2 was studied in works of [1990Kim] and [1999Boh]. 

Supersaturation phenomenon when deoxidation products precipitate from liquid was 

studied in Fe-0.04 mass% Zr alloy by [1997Li] by EMF technique in Ar-20 vol% H 2 atmosphere. 

Supersaturation ratio (a Zr·a 2 O)ss/(a Zr·a 2 O)eq was found to be equal to 1.3. 

. Table 1 

Investigations of the Fe-O-Zr Phase Relations, Structures and Thermodynamics 


[1957Fis] Equilibrium study, thermal analysis, XRD, 

optical microscopy 

[1960Nev] Arc melting, annealing in vacuum, 

metallography, XRD 

[1965Buz], 

[1967Buz] 

Equilibrium studies, thermodynamic 

calculations 

[1967Jon] Vertical tube furnace with quenching, 

optical microscopy and XRD 

[1973Buz] Equilibrium studies, thermodynamic 

calculations 


Range Studied 

1300-1800˚C in air, ZrO 2-FeO 

1000˚C, vacuum 5·10 –5 mm Hg, x < 0.1 

1800˚C, Fe-Zr 0.15-1.5 mass% Zr 

1250-1600˚C, p(O 2) = 2.1·10 –2 Pa, ZrO 2- 

Fe 3O 4 

1600˚C Ar, Fe-Zr 0.01-1.85 mass% Zr 

[1973Tep] EMF, chemical analysis 1550, 1600 and 1650˚C, 

0.001-0.3 mass% Zr 

[1974Fru] Equilibrium studies in He atmosphere ZrO2 crucibles 

1680˚C, Fe-Zr alloys 0.05-1 mass% Zr 

[1975Kat] Thermogravimetry (TGA), equilibration 

with gas mixture CO 2/H 2, oxygen control 

by gas sensors 

1200˚C, p(O 2)=10 –3.76 -10 –12.82 atm, 

ZrO 2-FeO-Fe 2O 3 

[1976Jan] Equilibrium studies, chemical analysis, EMF 1600˚C, Fe-Zr alloys 0.0009-1.7 mass% 

Zr 

[1977Heu] Co-precipitation, XRD, DTA, dilatometry, IRspectrometry 


400-1200˚C, ZrO 2-Fe 2O 3 (0-90 mol% 

Fe 2O 3) 

[1986Gho] Thermodynamic calculations 1680˚C, Fe-Zr (up to 1 mass% Zr) 

[1987Kim] TGA p(O2) = 2.1·10 –2 Pa, T up to 1500˚C 

ZrO2-FeO-Fe2O3 [1988Kim] TGA p(O2) = 2.1·10 –4 Pa, T up to 1380˚C 

ZrO2-FeO-Fe2O3 



MSIT 1 

7 

DOI: 10.1007/978-3-540-70890-2_24 

ß Springer 2009

8 24 

Fe–O–Zr 




Range Studied 

[1990Kim] HT-XRD, DTA Up to 1400˚C, ZrO2-Fe2O3 (0-98 mol% 

Fe2O3) [1991Zhu] DTA in Ar 792-856˚C, Zr-0.98Fe-0.21O (mass%) 

[1996Pop] Co-precipitation, XRD, Mössbauer 

spectroscopy 

1100˚C, ZrO2-Fe2O3 [1996Ton] High-energy ball milling, XRD, TEM ZrO2-Fe2O3 (16.7 mass% Fe2O3) [1997Li] EMF in Ar-20 vol% H2 1600˚C, supersaturation during 

deoxidation and ZrO2 precipitation of 

Fe-0.04 mass% Zr liquid alloy 

[1997Nar] Co-precipitation, XRD, TEM/EDX, SEM 500-1300˚C, ZrO2-Fe2O3 (10-40 mol% 

Fe2O3) [1998Zav] Arc-melting in Ar, XRD, Mössbauer 

spectroscopy 

800 and 1000˚C annealing, Zr4Fe2O0.6 

[1998Zio] X-ray radial electronic density distribution 

spectra 

Co-precipitation, calcination at 110 

and 400˚C, ZrO2-Fe2O3 (Zr:Fe = 

0.907:0.093) 

[1999Boh] XRD, SEM/EDX 840-950˚C, ZrO 2-Fe 2O 3 (50 mass%) 

[2000Laj] XRD, HT-XRD, electron paramagnetic 

resonance spectra 

Co-precipitation, 400-900˚C heat 

treatment, ZrO 2-Fe 2O 3 (5-40 mol% 

FeO 1.5) 

[2000Cao] High-energy ball milling, XRD, TEM, DTA 200-1000˚C, 0.8ZrO2-0.2αFe2O3 

[2000Tan] High-energy ball milling, XRD Annealing 400-650˚C, ZrO 2-Fe 2O 3 with 

0-20 mol% ZrO 2 

[1999Ste], 

[2000Ste], 

[2001Ste] 

Co-presipitation and calcination of 

amorphos samples, XRD, Raman, DTA, TGA, 


600-1100˚C calcination, ZrO 2-Fe 2O 3 

(0-50 mol% Fe 2O 3) 

[2001Cao] High-energy ball milling, XRD, TEM ZrO 2-Fe 2O 3 with 5-25 mol% Fe 2O 3 

[2001Wu] XRD, analytical electron microscopy, EDX Sintering of oxide mixture at 1200˚C 

and aging at 850˚C, Fe/Zr ≈ 1 

[2002Cao] High-energy ball milling, XPS ZrO2-Fe2O3 with 5-30 mol% Fe2O3 [2002Kov] XRD Annealing at 800˚C, Zr 3FeO x (x = 0, 0.2, 

0.4, 0.6, 0.8, 1) 

[2002Pet] Induction melting, XRD, microprobe 

analysis, SEM, calculation 

Air condition, 1870-2230˚C, ZrO 2-FeO- 

Fe 2O 3 

[2004Hua] CALPHAD, ionic liquid model 1600, 1680˚C, Zr-Fe-O 

[2004Jun] CALPHAD, associate model 1600, 1680˚C, Zr-Fe-O 



MSIT 1



[2006Bec] 

[2006Bes] 

DSC, chemical analysis, visual polythermal 

analysis in induction melting in cold 

crucible or Galakhov furnace, XRD, SEM/ 

EDX 

[2006Fig] High energy ball milling, Mössbauer 

spectra, Perturbed Angular Correlation 

spectra, XRD, DTA 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 



Range Studied 

1100-2710˚C, inert atm. Ar/He, ZrO 2- 

FeO 

25˚C, 250-1100˚C (annealing 

temperature), Zr 0.7Fe 0.3O 1.85 

Lattice 

Parameters 


(δFe) cI2 a = 293.15 pure Fe at 1390˚C [Mas2] 

1538 - 1394 Im3m 

W 


1394 - 912 Fm3m 

Cu 


< 912 Im3m 

W 


P63/mmc Mg 

c = 396.0 

(βZr) cI2 a = 352.4 up to 4 at.% Fe 

1855 - 775 Im3m 

W 

a = 360.9 805˚C 100% Zr [1989She] 

(αZr) hP2 a = 323.17 at 25˚C 100% Zr [1989She] 

< 863 P63/mmc Mg 

c = 514.7 

αFe2O3 hR30 ~60 at.% O, ~6 mol% ZrO2 at 1437˚C 

< 1457 R3c 

[1987Kim] 

Al2O3 a = 503.42 ± 0.03 

c = 1374.83 ± 0.04 

[V-C2] 

γFe2O3 cF56 a = 834 [1989Rag2] 

Fd3m 

MgAl2O4 metastable 



MSIT 1 

9 

DOI: 10.1007/978-3-540-70890-2_24 

ß Springer 2009

10 24 

Fe–O–Zr 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 

Lattice 

Parameters 


FexO cF8 wustite, 0.845 ≤ x ≤ 0.961 

1424 - 570 Fm3m 

NaCl 

a = 435.35 at 1000˚C [V-C2] 

Fe3O4+y cF56 

Fe3O4 Fd3m magnetite 

< 1596 MgAl2O4 57.1 to 58.0 at.% O, ~6 mol% ZrO2 a = 841.1 at 1437˚C [1987Kim] 

at 200˚C [V-C2] 

ZrFe2 cF24 a = 702 to 709 27.5 to 34.4 at.% Zr [2002Ste] 

(h1) Fd3m C15 structure 

< 1673 MgCu2 

λZrFe2 hP24 a = 495 26.5 to 27 at.% Zr [2002Ste] 

(h2) P63/mmc c = 1614 C36 structure 

1345 - 1240 MgNi2 

Zr2Fe tI12, 66.7 to 67.2 at.% Zr, C16 structure 

951 - 780 I4/mmc a = 638 [2002Ste] 

CuAl2 c = 560 

Zr3FeOx oC16 solid solution 0 ≤ x ≤ 1[2002Kov] 

Cmcm a = 332.28 x =1 

BRe3 b = 1111.37 

c = 872.3 

Zr3Fe 74.8 to 75.4 at.% Zr [2002Ste] 

≤ 851 a = 332 

b = 1100 

c = 882 

x =0[2002Ste] 

Zr6Fe23 cF116 a = 1172 metastable, stabilized by oxygen 

Fm3m 

Th6Mn23 [2002Ste] 

γZrO2 cF12 [1989Rag1], [2006Wan] 

2710 - 2311 Fm3m 13 mol% FeO at 1800˚C 

CaF2 a = 509 pure ZrO2 [V-C2] 

a = 508.5 11.3 mol% FeO [2006Bes] 

βZrO2 tP6 up to 2.2 mol% FeO at 1332˚C 

2311 - 1094 P42/nmc [2006Bes] 

ZrO2 a = 360.55 

c = 517.97 

pure ZrO2 [V-C2] 

t’ (?) a = 507 

c = 517 

2.2 mol% FeO [2006Bes] 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space Group/ 

Prototype 

Lattice 

Parameters 


αZrO2 mP12 a = 514.15 baddeleyite pure ZrO2 [V-C2] 

≤1094 P21/c b = 520.56 

ZrO2 c = 531.28 

β = 99.30 

τ1 (Zr2Fe) 1–xOx cF96 a = 1218.9 60.2-65.6 at.% Zr, 3.1-8.6 at.% O 

Fd3m 

[1960Nev] 

NiTi2 a = 1221 x = 0 metastable [2002Ste] 

. Table 3 




Fe O Zr 

γZrO2 Ð βZrO2+L ~1800 p γZrO2 4.53 65.16 30.31 

βZrO2 0.67 66.44 32.89 

L 36.36 54.54 9.09 

L Ð βZrO2+FexO 1332 e L 42.65 52.45 4.9 

βZrO2 0.74 66.42 32.84 

FexO 49.7 51.30 0 

L Ð Fe3O4+y+ZrO2 1525 e L 38.71 58.06 3.23 

Fe2O3 Ð Fe3O4+y +O2 (ZrO2) 1434 d Fe2O3 38.52 60.25 1.23 

Fe3O4+y 42.49 57.22 0.29 

βZrO2 5.56 65.43 29.01 

. Table 4 

Investigations of the Fe-O-Zr Materials Properties 


[1992Lou] Voltage between sample and metallic reference 

blocks at T and T+ΔT temperature, voltage and 

electric current measurements 

[1998Zav] Mössbauer spectroscopy, magnetic susceptibility 

measurements 



MSIT 1 


Thermal electric power and 

resistivity of Zr-Fe-O alloys 

Magnetic properties 

11 

DOI: 10.1007/978-3-540-70890-2_24 

ß Springer 2009

12 24 

Fe–O–Zr 



[2000Cao] Gas sensing measurement system Oxygen gas sensitivity, electric 

conductivity 

[2001Cao] Gas sensing measurement system Oxygen gas sensitivity, response 

time 

[2002Cao] Gas sensing measurement system, XPS Oxygen gas sensitivity and 

concentration of oxygen 

vacancies 

[2002Koz] Spectrophotometry and elipsometry Optical properties of thin films 

[2002Sei] Transmission Mössbauer spectroscopy Magnetic properties 



MSIT 1

. Fig. 1 

Fe-O-Zr. Phase diagram of the FeO-ZrO 2 system 



MSIT 1 


13 

DOI: 10.1007/978-3-540-70890-2_24 

ß Springer 2009

14 24 

Fe–O–Zr 

. Fig. 2 

Fe-O-Zr. Isothermal section at 1000˚C 



MSIT 1


. Fig. 3 

Fe-O-Zr. Isothermal section of the ZrO 2-FeO-Fe 2O 3 system at 1200˚C together with isobars 



MSIT 1 

15 

DOI: 10.1007/978-3-540-70890-2_24 

ß Springer 2009

16 24 

Fe–O–Zr 

. Fig. 4a 

Fe-O-Zr. Isothermal section of the ZrO 2-FeO-Fe 2O 3 system at 1437˚C and p(O 2) = 2.1·10 4 Pa 



MSIT 1


17 

. Fig. 4b 

Fe-O-Zr. Isothermal section of the ZrO 2-FeO-Fe 2O 3 system at T ≤ 1380˚C and p(O 2) = 2.1·10 2 Pa 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_24 

ß Springer 2009

18 24 

Fe–O–Zr 

. Fig. 5 

Fe-O-Zr. Phase diagram for the Fe 3O 4-ZrO 2 system from [1967Jon] in air. The β Ð γ 

transformation in ZrO 2 is accepted according to [2006Wan], the γ Ð β+L transition is tentatively 

shown by a dashed line 



MSIT 1


. Fig. 6 

Fe-O-Zr. Calculated oxygen activity in liquid Fe-O-Zr alloys in equilibrium with solid ZrO 2 at 

1550-1650˚C 



MSIT 1 

19 

DOI: 10.1007/978-3-540-70890-2_24 

ß Springer 2009

20 24 

Fe–O–Zr 

References 

[1957Fis] Fischer, W.A., Hoffmann, A., “Equilibrium Studies in the System FeO-ZrO 2” (in German), Arch. 

Eisenhuettenwes., 28(11), 739–743 (1957) (Experimental, Phase Relations, #, 23) 

[1960Nev] Nevitt, M.V., Downey, J.W., Morris, R.A., “A Further Study of Ti2Ni-Type Phases Containing Titanium, 

Zirconium or Hafnium”, Trans. Met. Soc. AIME, 218, 1019–1023 (1960) (Crys. Structure, Experimental, 

Phase Diagram, #, 7) 

[1965Buz] Buzek, Z., “The Effect of Aluminium, Titanium, Zirconium, and Cerium on the Solubility of Oxygen in 

Liquid Iron at 1800˚C”, Sb. Ved. Pr. Vys. Sk. Banske Ostrave, Rada Hutn., 11, 395–400 (1965) (Experimental, 


[1967Buz] Buzek, Z., Schindlerova, V., Macoszek, M., “The Influence of Cr, Mn, V, Si, Ti, Al, Zr, Ce and Ca on 

the Activity and Solubility of Oxygen in Liquid Iron”, Sb. Ved. Pr. Vys. Sk. Banske Ostrave, Rada Hutn., 

13(2-3), 175–193 (1967) (Experimental, Phase Relations, 26) 

[1967Hol] Holleck, H., Thuemmler, F., “Investigations on the Formation of Metalloid-Stabilised Zr-Rich 

Transition” (in German), J. Nucl. Mater., 23, 88–94 (1967) (Crys. Structure, Experimental, 12) 

[1967Jon] Jones, T.S., Kimura, S., Muan, A., “Phase Relations in the System FeO-Fe 2O 3-ZrO 2-SiO 2”, J. Amer. 

Ceram. Soc., 50(3), 137–142 (1967) (Experimental, Phase Diagram, Phase Relations, #, 16) 

[1973Tep] Teplitsky, E.B., Vladimirov, L.P., “Thermodynamics of Steel Killing by Zirconium” (in Russian), Izv. 

Vyss. Uchebn. Zaved., Chern. Metall., (3), 5–7 (1973) (Experimental, Thermodyn., 6) 


Iron at 1600˚C” in “Metall. Chem. - Appl. Ferrous Metall.”, Int. Symp., Sheffield, July 1971, Iron Steel 

Inst., London, 173–177 (1973) (Crys. Structure, Experimental, Review, 8) 

[1974Fru] Fruehan, R.J., “The Effect of Zr, Ce, and La on the Solubility of Oxygen in Liquid Fe”, Metall. Trans., 5, 


[1975Kat] Katsura, T., Wakihara, M., Hara, S.I., Sugihara, T., “Some Thermodynamic Properties in Spinel Solid 

Solutions with the Fe 3O 4 Component”, J. Solid State Chem., 13(1-2), 107–113 (1975) (Calculation, 

Experimental, Phase Diagram, Phase Relations, Thermodyn., #, 11) 

[1976Jan] Janke, D., Fischer, W.A., “Deoxidation Equilibria of Ti, Al and Zr in Fe Melts at 1600˚C” (in German), 

Arch. Eisenhuettenwes., 47(4), 195–198 (1976) (Experimental, Phase Relations, 30) 

[1977Heu] Heughebaert-Therasse, M., “Study Contribution to the Evolution and Sintering of Several Oxides 

Stabilized Zirconia, at Temperatures below 1300˚C” (in French), Ann. Chim., 2, 229–243 (1977) (Crys. 

Structure, Phase Diagram, Phase Relations, 38) 

[1981Jin] Jin, T., Hattori, H., Tanabe, K., “Formation of Butane from Butanol Catalyzed by Fe 2O 3,Fe 2O 3-ZrO 2, 

and Fe 2O 3-ZnO”, Chem. Lett., 10(11), 1533–1534 (1981) (Experimental, Catalysis, 2) 

[1984Pap] Papiernik, R., Frit, B., “Crystal Structure of Cubic Phase Disordered Anion Excess ZrFe 2.67 Related to 

the ReO 3” (in French), Mater. Res. Bull., 19(4), 509–516 (1984) (Crys. Structure, Experimental, 20) 

[1986Gho] Ghosh, A., Murthy, G.V.R., “An Assessment of Thermodynamic Parameters for Deoxidation of Molten 

Iron by Cr, V, Al, Zr and Ti”, Trans. Iron Steel Inst. Jpn., 26(7), 629–637 (1986) (Assessment, Phase 

Diagram, Thermodyn., Phase Relations, 41) 

[1987Kim] Kiminami, R.H.G.A., “Study of the ZrO 2-FeO-Fe 2O 3 System by Thermogravimetry at Air-Oxygen 

Partial Pressures and Temperatures up to 1500˚C” (in Portuguese), Ceramica (Sao Paulo), 33(213), 

207–209 (1987) (Experimental) as quoted in [2005ACS] 

[1988Kim] Kiminami, R.H.G.A., “Study of the ZrO 2-FeO-Fe 2O 3 System by Thermogravimetry at Oxygen Partial 

Pressures 2.1·10 2 Pa and Temperatures up to 1380˚C” (in Portuguese), Ceramica (Sao Paulo), 34(223), 

121–123 (1988) (Experimental) as quoted in [2005ACS] 

[1989Rag1] Raghavan, V., “The Fe-O-Zr System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Met., 

Calcutta, 5, 374–379 (1989) (Phase Diagram, Phase Relations, Review, 11) 

[1989Rag2] Raghavan, V., “The Fe-O System”, Phase Diagrams of Ternary Iron Alloys, Indian Inst. Met., Calcutta, 5, 

5–8 (1989) (Phase Diagram, Phase Relations, Crys. Structure, Review, 3) 

[1989She] Sheldon, R.I., Peterson D.E., “The U-Zr (Uranium-Zirconium) System”, Bull. Alloy Phase Diagrams, 10 

(2), 165–171 (1998) (Review, Crys. Structure, Phase Diagram, Phase Relations, Thermodyn., 33) 

[1990Kim] Kiminami, R.H.G., “The Monoclinic-Tetragonal Phase Transformation of Zirconia in the System ZrO 2- 

Fe 2O 3”, J. Mater. Sci. Lett., 9(4), 373–374 (1990) (Experimental, Phase Relations, 9) 

[1991Sun] Sundman, B., “An assessment of the Fe-O system”, J. Phase Equilib., 12(1), 127–140 (1991) (Phase 

Relations, Phase Diagram, Thermodyn., Assessment, 53) 



MSIT 1


21 

[1991Zhu] Zhu, Y.T., Devletian, J.H., “Precise Determination of Isomorphous and Eutectoid Transformation 

Temperatures in Binary and Ternary Zr Alloys”, J. Mater. Sci., 26, 6218–6222 (1991) (Experimental, 


[1992Lou] Loucif, K., Borrelly, R., Merle, P., “Study by Thermoelectric-Power and Resistivity Measurements of the 

Precipitation Kinetics in Zirconium Alloys Between 450˚C and 600˚C”, J. Nucl. Mater., 189(1), 34–45 

(1992) (Electr. Prop., Experimental, Kinetics, Thermodyn., 24) 

[1993Wu] Wu, J.-C., Liu, D.-S., Ko, A.-N., “Dehydrogenation of Ethylbenzene over TiO 2-Fe 2O 3 and ZrO 2-Fe 2O 3 

Mixed Oxide Catalysts”, Catal. Lett., 20(3-4), 191–201 (1993) (Experimental, Phase Relations, Phys. 

Prop., 28) 

[1996Pop] Popovic, S., Grzeta, B., Stefanic, G., Czako-Nagy, I., Music, S., “Structural Properties of the System 

m-ZrO2-α-Fe2O3”, J. Alloys Compd., 241(1-2), 10–15 (1996) (Crys. Structure, Experimental, Phase 


[1996Ton] Tonejc, A.M., Tonejc, A., “Zirconia Solid Solutions ZrO 2-Y 2O 3 (CoO or Fe 2O 3) Obtained by Mechanical 

Alloying”, Mater. Sci. Forum, 225–227(pt.1), 497–502 (1996) (Experimental, Morphology, 10) 

[1997Li] Li, G.Q., Suito, H., “Electrochemical Measurement of Critical Supersaturation in Fe-O-M (M = Al, Si, 

and Zr) and Fe-O-Al-M (M = C, Mn, Cr, Si, and Ti) Melts by Solid Electrolyte Galvanic Cell”, ISIJ Int., 


[1997Nar] Narwankar, P.K., Lange, F.F., Levi, C.G., “Microstructure Evolution of ZrO 2-(Fe 2O 3,Al 2O 3) Materials 

Synthesized with Solution Precursors”, J. Am. Ceram. Soc., 80(7), 1684–1690 (1997) (Experimental, 


[1998Zav] Zavaliy, I.Yu., Riabov, A.B., Yartys, V.A., Wiesinger, G., Michor, H., Hilscher, G., “(Hf,Zr) 2Fe 

and Zr 4Fe 2O 0.6 Compounds and Their Hydrides: Phase Equilibria, Crystal Structure and Magnetic 

Properties”, J. Alloys Compd., 265, 6–14 (1998) (Crys. Structure, Experimental, Magn. Prop., Phase 


[1998Zio] Ziouzin, D.A., Moroz, E.M., Ivanova, A.S., “X-Ray Diffraction Study of Amorphous Zr-Fe-O System”, 

Mater. Sci. Forum, 278–281(2), 826–832 (1998) (Crys. Structure, Experimental, 3) 

[1999Boh] Bohe, A.E., Gamboa, J.J.A., Pasquevich, D.M., “Enhancement of the Martensitic Transformation of 

Tetragonal Zirconia Powder in the Presence of Iron Oxide”, Mater. Sci. Forum, 273, 218–221 (1999) 

(Crys. Structure, Experimental, Morphology, 15) 

[1999Ste] Stefanic, G., Music, S., Popovic, S., Nomura, K., “A Study of the ZrO 2-Fe 2O 3 System by XRD, 57 Fe 

Mössbauer and Vibrational Spectroscopies”, J. Mol. Struct., 480–481, 627–631 (1999) (Electr. Prop., 


[2000Cao] Cao, W., Tan, O.K., Zhu, W., Jiang, B., “Mechanical Alloying and Thermal Decomposition of (ZrO 2) 0.8- 

(α-Fe 2O 3) 0.2 Powder for Gas Sensing Applications”, J. Solid State Chem., 155, 320–325 (2000) (Crys. 

Structure, Electrical Properties, Experimental, Phase Relations, 14) 

[2000Laj] Lajavardi, M., Kenney, D.J., Lin, Sh.H., “Time-Resolved High and Low Temperature Phase Transitions 

of the Nanocrystalline Cubic Phase in the Y2O3-ZrO2 and Fe2O3-ZrO2 System”, J. Chin. Chem. Soc., 47, 


[2000Ste] Stefanic, G., Grzeta, B., Music, S., “Influence of Oxygen on the Thermal Behavior of the ZrO 2-Fe 2O 3 

System”, Mater. Chem. Phys., 65(2), 216–221 (2000) (Crys. Structure, Experimental, Phase Relations, 14) 

[2000Tan] Tan, O.K., Cao, W., Zhu, W., “Alcohol Sensor Based on a Non-Equilibrium Nanostructured xZrO 2- 

(1–x)α-Fe 2O 3 Solid Solution System”, Sens. Act. B (Chemical), 63(1-2), 129–134 (2000) (Crys. Structure, 

Experimental, Nano, Phase Relations, 15) 

[2001Cao] Cao, W., Tan, O.K., Zhu, W., Jiang, B., Gopal Reddy, C.V., “An Amorphous-Like xα-Fe 2O 3-(1–x)ZrO 2 

Solid Solution System for Low Temperature Resistive-Type Oxygen Sensing”, Sens. Act. B, 77(1-2), 


[2001Ste] Stefanic, G., Grzeta, B., Nomura, K., Trojko, R., Music, S., “The Influence of Thermal Treatment on 

Phase Development in ZrO2-Fe2O3 and HfO2-Fe2O3 Systems”, J. Alloys Compd., 327, 151–160 (2001) 


[2001Wu] Wu, M.L., Gan, D., Shen, P., “Precipitation of Iron Zirconate from Zr 4+ -Oversaturated Fe 2O 3–x (I)”, 

Mater. Sci. Eng. A, 297(1-2), 119–123 (2001) (Crys. Structure, Experimental, Morphology, Phase 


[2002Cao] Cao, W., Tan, O.K., Pan, J.S. Zhu, W., Gopal Reddy, C.V., “XPS Characterization of xα-Fe 2O 3-(1–x) 

ZrO 2 for Oxygen Gas Sensing Application”, Mater. Chem. Phys., 75(1-3), 67–70 (2002) (Experimental, 




MSIT 1 

DOI: 10.1007/978-3-540-70890-2_24 

ß Springer 2009

22 24 

Fe–O–Zr 

[2002Kov] Kovalchuk, I.V., Zavaliy, I.Y., “Hydrogenation of Oxygen-Stabilized Zr 3FeO x Phase with Filled Re 3B- 

Type of Structure” in “Crys. Chem.”, VII Int. Conf., Lviv., 133 (2002) (Crys. Structure, Experimental, 4) 

[2002Koz] Kozik, V.V., Shul‘pekov, A.M., Borilo, L.P., “The Structure and Optical Properties of Thin ZrO 2, ZrO 2- 

Y 2O 3, and ZrO 2-Fe 2O 3 Films”, Russ. Phys. J., 45(12), 1228–1230 (2002), translated from Izv. Vyss. Ucheb. 

Zaved., Fiz., 45(12), 77–78 (2002) (Crys. Structure, Experimental, Optical Prop., 3) 

[2002Pet] Petrov, Yu.B., Udalov, Yu.P., Slovak, J., Morozov, Yu.G., “Liquid Immiscibility Phenomena in Melts of 

the ZrO 2-FeO-Fe 2O 3 System”, Glass Phys. Chem., 28(3), 139–146 (2002), translated from Fiz. Khim. 

Stekla, Russia, 28(3), 139–146 (2002) (Experimental, Morphology, Phase Diagram, Phase Relations, 14) 

[2002Sei] Seifu, D., Li, F., “Mössbauer Study of Nano-Crystalline Thin Films of Fe-Zr-O”, Phys. Status Solidi A, 

189(3), 731–734 (2002) (Experimental, Crys. Structure, 3) 



(2002) (Crys. Structure, Experimental, Phase Relations, Phase Diagram, 88) 

[2004Hua] Huang, W., “Oxygen Solubility in Fe-Zr-O Liquid”, Calphad, 28(2), 153–157 (2004) (Calculation, Phase 

Diagram, Phase Relations, Thermodyn., 15) 

[2004Jun] Jung, I.-H., Decterov, S.A., Pelton, A.D., “A Thermodynamic Model for Deoxidation Equilibria in 

Steel”, Metall. Mater. Trans. B, 35b(3), 493–507 (2004) (Calculation, Theory, Thermodyn., 100) 

[2004Wan] Wang, C., Zinkevich, M., Aldinger, F., “On the Thermodynamic Modeling of the Zr-O System”, 

Calphad, 28(3), 281–292 (2004) (Calculation, Phase Diagram, Phase Relations, Thermodyn., 77) 

[2005ACS] American Ceramic Society – NIST “Phase Equilibria Diagrams”, CD-ROM Database, Version 3.1, 

ACerS-NIST (2004-2005) 

[2005Str] Strakhov, V.I., Ivanova, I.V., Arsirii, A.I., Velkova, K., Migal, V.P., Gershkovich, S.I., “Phase 

Transformations in Stabilized ZrO 2-Fe 2O 3 Compositions”, Refract. Indust. Ceram., 46(5), 322–324 


[2006Bec] Bechta, S.V., Krushinov, E.V., Almjashev, V.I., Vitol, S.A., Mezentseva, L.P., Petrov, Yu.B., Lopukh, D.B., 

Khabensky, V.B., Barrachin, M., Hellmann, S., et al, “Phase Diagram of the ZrO 2-FeO System”, J. Nucl. 

Mater., 348(1-2), 114–121 (2006) (Crys. Structure, Experimental, Morphology, Phase Diagram, Phase 

Relations, #, 26) 

[2006Bes] Beshta, S.V., Krushinov, E.V., Al‘myashev, V.I., Vitol‘, S.A., Mezentseva, L.P., Petrov, Yu.B., Lopukh, D. 

B., Khabenskii, V.B., Barrachin, M., Hellmann, S., Gusarov, V.V., “Phase Relations in the ZrO 2-FeO 

System”, Russ. J. Inorg. Chem. (Engl. Transl.), 51(2), 325–331 (2006), translated from Zh. Neorgan. Khim., 

51(2), 367–374 (2006) (Experimental, Morphology, Phase Diagram, Phase Relations, #, 25) 

[2006Fig] Figueroa, S., Desimoni, J., Rivas, P.C., Caracoche, M.C., de Sanctis, O., “Local Structures in the ZrO2- 

15 mol% Fe 2O 3 System Obtained by Ball Milling”, J. Am. Ceram. Soc., 89(12), 3759–3764 (2006) (Crys. 

Structure, Electr. Prop., Experimental, #, 16) 

[2006Wan] Wang, C., Zinkevich, M., Aldinger, F., “The Zirconia - Hafnia: DTA Measurements and 

Thermodynamic Calculations”, J. Am. Ceram. Soc., 89(12) 3751–3758 (2006) (Experimental, Calculation, 

Phase Relations, Thermodyn., 78) 


(1990) 





MSIT 1

Iron – Phosphorus – Silicon 



Introduction 

Phase relations in the Fe-P-Si system are of great interest mainly in two aspects - application of 

phosphorus as dopant in Si-semiconductors containing iron, and development of nanocrystalline 

materials produced by controlled crystallization of amorphous alloys containing phosphorus 

and iron in combination with silicon or with d metals. At the same time, the amount of 

information on the constitution of the Fe-P-Si system is still insufficient. Most of the experimental 

data on phase equilibria were published long ago [1930Hum, 1933Sau, 1959Vog]. The 

reaction scheme, liquidus surface projection and isothermal section at room temperature of 

the Fe-FeP2-FeSi-Si partial system as well as a series of vertical sections were reported. Later 

certain information about the effect of silicon on the solubility of phosphorus in iron at 

different temperatures was presented in [1965Kan2]. The phase contents of the Fe-P-Si alloys 

annealed at different temperatures were reported in [1997Vav, 1998Vav, 1999Vav]. At the same 

time, new data on dissolution of the third component in the binary Fe-P and Fe-Si phases 

[1962Run, 1965Sab, 1984Jer] and about new crystal structures identified in the ternary 

system contradict the earlier version of the phase relations, and therefore, reinvestigation of 

the Fe-P-Si system using modern physico-chemical analysis techniques is required. 

The experimental works on the phase relations, crystal structures and thermodynamics 

are listed in Table 1. The crystal structure data of the binary and ternary phases existing in the 

Fe-P-Si system were published in [1933Sau, 1959Vog, 1962Run, 1965Sab, 1983And, 1984Jer, 

1991Men, 1993Bal, 1995Per, 1998Vav, 1999Vav, 2002Ito, 2002Tan, 2003Bal]. Information on 

thermodynamic properties, in particular activity of phosphorus in liquid iron with silicon 

additions, was experimentally obtained by [1979Yam, 1983Ban, 1983Yam, 1997Ued]. Reviews 

of literature data on phase equilibria in the Fe-P-Si system are presented in [1949Jae, 

1965Kan1, 1988Rag], crystal structures - in [1988Rag], thermodynamics - in [1979Yam, 

1983Ban]. A database of thermochemical parameters for liquid Fe based alloys containing Si 

and P was proposed by [1995Bou]. 


The Fe-P binary boundary system is accepted from [2002Per]. The Fe-Si and P-Si boundary 

systems are accepted from [Mas2]. 


Fe–P–Si 25 

1 

Crystallographic data for the known unary, binary and ternary Fe-P-Si phases are listed in 

Table 2. The investigations of the crystal structures of the phases deal mainly with the 

additions of the third component to the solid solutions based on the binary phases 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_25 

ß Springer 2009

2 25 

Fe–P–Si 

[1962Run, 1983And, 1984Jer, 2002Ito, 2002Tan] and with the ternary phases [1959Vog, 

1965Sab, 1968Sab, 1984Jer, 1995Per]. 

[1962Run] experimentally determined that solubility of silicon in δ (FeP) reaches about 

25 at.%. X-ray diffraction patterns of the ζ 2, FeSi 2–xP x phase (x = 0 to 0.10) obtained after hot 

pressing at 900˚C for 3.6 ks under the pressure of 25 MPa were published by [2002Ito]. The 

geometrical and electronic structures of this phase at x = 0.125 studied using the first 

principles pseudopotential calculations based on generalized gradient approximation (GGA) 

density function theory are presented in [2002Tan]. It was noted that the calculated structural 

parameters depend strongly on the kinds of dopants and sites. 

The ternary phase τ 1 was identified first by [1959Vog] at an approximate composition of 

FeSi 4P 4, with a negligible range of homogeneity. This phase was reported to melt congruently 

at a temperature of about 1210˚C. The existence of the τ 1 phase was confirmed by [1965Sab, 

1968Sab], but its crystal structure was identified much later by [1995Per] from single crystal 

studies. It was noted that this phase, similar to the NiSi3P4 structure type reveals a new family 

of ternary phases rich in silicon and phosphorus. The existence of a new ternary phase (τ2) was 

established in [1984Jer]. They observed a crystallographic hexagonal/orthorhombic transformation 

in the partially Si-substituted γ (Fe 2P) solid solution. The transformation temperature 

dependence is shown to increase linearly with increasing P/Si substitution. The τ 2,Fe 2Si xP 1–x 

phase with a body-centered orthorhombic structure was reported to be stable in the range of 

0.20 < x < 0.36 at the temperature of 997˚C (Table 2). [1997Vav, 1998Vav, 1999Vav] reported 

a new metastable ternary phase of an undetermined composition and type of structure 

labeled as FexSizPy. It was found in alloys rapidly quenched and then annealed at 500˚C during 

10 minutes. The compositions are Fe82Si2P16 and Fe78Si10P12 (in at.%). The presence of the 

same phase was determined also in the alloys Fe 80Si 6P 14, Fe 78Si 10P 12 and Fe 78Si 2P 20 rapidly 

quenched and then annealed at 600˚C during 10 minutes. In Table 2 this phase is labeled as 

ψ (Fe-P-Si). 


The Fe2P-FeSi quasibinary system was experimentally explored by [1930Hum, 1933Sau]. Its 

phase diagram is of the eutectic type, the eutectic temperature was reported to be 1185˚C 

(corrected later by [1959Vog] to 1183˚C). The eutectic point e 7 is located at the Fe 58.6Si 24.2P 17.2 

composition (Table 3). Solubilities of the third component in the γ (Fe 2P) and λ (FeSi) phases 

were declared by [1930Hum, 1933Sau] as negligible. However this statement contradicts the 

later reported data of [1984Jer] and [1965Sab] (Table 2), therefore the Fe 2P-FeSi phase 

diagram needs a revision. A similar situation turned out with the quasibinary systems FeP- 

FeSi, FeSi- FeSi4P4 and ζ1-FeSi4P4, proposed in [1959Vog], because a visible solubility of the 

third component was observed in the δ (FeP) [1962Run], λ (FeSi) and ζ1 (FeSi2(h)) phases 

[1965Sab]. The reported coordinates of the invariant points obtained in these three systems 

are listed in Table 3. The Si-FeSi 4P 4 system was also declared by [1959Vog] to be quasibinary. 


The temperatures, types of reactions and available compositions of the phases taking part 

in the invariant equilibria in the partial Fe-FeP2-FeSi-Si system are listed in Table 3. 



MSIT 1

The presented coordinates and a partial reaction scheme (Fig. 1) are adopted mainly from the 

data of [1959Vog] on the invariant reactions and liquidus surface constitution, with certain 

corrections according to the accepted boundary binary systems. In addition, the data of 

[1930Hum] about the invariant four-phase equilibria with the participation of liquid at 

1110˚C (U 2) and 1018˚C (E 6) are accepted. Like in the reaction scheme proposed by 

[1988Rag], the transition reaction U 1 has been introduced to eliminate the κ phase from the 

liquid equilibria. Also the invariant reactions at high phosphorous concentrations with 

the participation of a vapor phase at ambient pressure reported by [1959Vog] are omitted. 

But the solid-state transition reactions proposed by [1988Rag] were also omitted because of 

their hypothetical character, insufficiently confirmed by experimental results. 


A liquidus surface projection of the partial Fe-FeP2-FeSi-Si system shown in Fig. 2 is based 

on [1988Rag]. It is compiled mainly on the basis of the [1959Vog] experimental results 

involving data from [1930Hum] on the partial Fe 2P-related range. Two quasibinary eutectics 

e 10 and e 13 are inserted on the joins τ 1-μ and τ 1-δ respectively, although their positions can be 

very roughly given on these joins. The dashed monovariant lines indicate their tentative 

character. 

One can see in Fig. 2 that the constitution of the liquidus surface projection in the 

composition ranges rich in Fe and P require further investigations. 


The isothermal section of the partial Fe-FeP 2-SiP-Si system at room temperature was constructed 

by [1959Vog] from his own experimental results. It was shown that at this temperature 

the phases α, β, γ, δ, ε, λ, ζ 2, μ, (Si) and τ 1 take part in equilibria. No visible solubility of 

the third component in the binary phases was detected. Phase relations in the Fe rich corner 

(Fe-Fe3P-FeSi partial system) were plotted by dotted lines indicating the tentative character. 

Later in his review [1988Rag] attempted to correct this section in accordance with the newer 

boundary binary systems and using the data of [1962Run] on the solubility of up to 25 at.% Si 

in the δ phase. But this section needs further verification, because an essential solubility of the 

third component was determined also in the λ and ζ 2 phases. 

A schematic isothermal section of the Fe-Fe 3P-SiP-Si partial system at 800˚C is shown in 

[1965Kan1]. It’s peculiarity consists in the participation of the λ (FeSi) phase in equilibria with 

other binary phases (β and μ). According to the data of [1965Kan2], the solubility of 

phosphorus in (αFe) at 1000˚C decreases from 4.4 at.% (2.5 mass%) without silicon down 

to 2.2 at.% (1.3 mass%) at 7.6 at.% (4.0 mass%) Si. With temperature decreasing from 1000 to 

800˚C the solubility of P in (αFe) containing 1 at.% Si decreases from 4.0 to 1.9 at.%. 



3 

A series of temperature-composition sections was constructed by [1930Hum, 1959Vog] from 

their own experimental data. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_25 

ß Springer 2009

4 25 

Fe–P–Si 

The Fe 3P-FeSi and Fe 83P 17-FeSi sections [1930Hum] need corrections according to the 

established visible phosphorus solubility in the λ phase. The position of the liquidus curve of 

the joint crystallization of the β and λ phases also needs verification. The section at 5 mass% P 

(Fe 91.3P 8.7-Fe 53.4Si 39.6P 7.0 in at.%), according to [1930Hum] is shown in Fig. 3. The position of 

the border of the primary crystallization fields of the α and λ phases needs further amendment. 

The section at 8 mass% P (Fe86.4P13.6-Fe55.7Si33.0P11.3 in at.%) which was also presented by 

[1930Hum] is omitted here because mutual positions of the α, β, γ and λ liquidus surfaces are 

not established reliably. Phase contents of some alloys lying along the sections constructed in 

[1930Hum], in the as-cast and annealed states, were later reported by [1933Sau]. 

Three temperature-composition sections were proposed by [1959Vog]. The Fe 63.7P 36.3- 

Si 60.4P 39.6 (in at.%) section needs verification because of uncertainties in the primary crystallization 

fields of the τ 1 and μ phases. Vertical sections at 13 mass% P (Fe 78.8P 21.2-Si 88.1P 11.9 in 

at.%) and at 7 mass% Si, 16 to 26 mass% P (Fe 64.3Si 11.6P 24.1-Fe 52.4Si 10.9P 36.7 in at.%) are 

shown in Figs. 4 and 5, respectively. 


The effect of silicon on the activity coefficient of phosphorus in liquid iron alloys at different 

temperatures was investigated by [1979Yam, 1983Yam, 1997Ued]. The Knudsen cell - mass 

spectrometer combination measurements carried out at 1600˚C by [1979Yam, 1983Yam] 

show a linear increase of the activity coefficient of P with silicon content increasing up to 

12.1 mass%. As a result of the calculations, a value of εP Si = 11.9 ± 0.6 was obtained for the 

interaction parameter at 1600˚C. Thermodynamics of phosphorus in molten Fe-Si alloys were 

studied by [1997Ued] at 1450˚C by equilibrating the alloys in a controlled phosphorus partial 

pressure. The phosphorus content of molten Si in a certain phosphorus partial pressure 

decreases with the addition of iron, and it shows a minimum value at 23 at.% Fe. Interaction 

coefficients between phosphorus and iron in molten silicon were found to be ε P Fe = 7.43 and 

ρ P Fe = – 16.4 at iron content up to 65 at.%. Thermodynamic considerations using a ternary 

regular solution model demonstrated that the obtained results are explained by a strong 

interaction between Si and Fe. The possibility of dephosphorization of such alloys by calcium 

treatment was also evaluated using these results. 

The vapor pressure of phosphorus in liquid Fe-P-Si alloys with silicon content up to 12.1 

mass% was measured by [1983Ban] applying the transportation method at the temperature of 

1400˚C. The obtained results were treated by the model of interstitial solution proposed by J. 

Chipman. The effect of silicon on the activity coefficient of phosphorus in liquid iron was 

determined by assuming Si as substitutional element. The interaction parameter value was 

obtained as εP Si = 7.68 ± 0.44 for 1400˚C. From the set of experimental data obtained by 

[1983Ban], [1995Bou] assessed a thermodynamic dataset, but the experimental and calculated 

values show essential discrepancies. In opinion of [1995Bou], the experimental results are 

inconsistent at the Fe-P side, at negligible contents of silicon. 

[1993Din] thermodynamically calculated the activity interaction parameter between Si 

and P in liquid Fe at 1600˚C ε P Si = 13.53 that does not differ essentially from the experimental 

data obtained by [1979Yam, 1983Yam] and the data cited in [1988The]. 

The activation energy of crystallization of the Fe 82Si 2P 16 (in at.%) amorphous alloy 

was estimated by [1999Vav] using the Kissinger method, in terms of the variation in crystallization 

temperature (Tc) as a function of the heating rate in the range 3.75 to 40˚C·min –1 . 



MSIT 1

The obtained value was 471.5 ± 5.4 kJ·mol –1 . After measurements of viscosity of Fe-P-Si melts, 

from the slope of Arrhenius plots of kinematic viscosity, [2000Vav1] evaluated the activation 

energy for viscous flow: 11.0, 44.0 and 44.0 kJ·mol –1 for the alloys (in at.%) Fe 82Si 2P 16, 

Fe 78Si 2P 20 and Fe 80Si 6P 14, respectively. 



5 

The Fe-P-Si alloys find practical application in modern technology mainly in two aspects. 

Firstly, phosphorus usually serves as dopant in Si-semiconductor technology. In particular, the 

semiconducting iron disilicide ζ 2, FeSi 2 (r), is a potential candidate for practical use in the high 

temperature range (up to about 930˚C) because of its low cost of raw materials, its good 

resistance to oxidation, and its nontoxicity [2002Ito], with P substitution for Si as an n-type 

dopant possess lower thermal conductivity then the nondoped sample. Secondly, a considerable 

research effort has recently been concentrated on nanocrystalline materials produced by 

controlled crystallization of amorphous alloys, but its high diffusion mobility and tendency to 

nonuniform distribution leads to segregation brittleness [1999Vav]. In this aspect, a study of 

the influence of silicon additions on the segregation of phosphorus atoms in iron is desirable. 

The applied experimental techniques and investigated types of properties of Fe-P-Si alloys 

are presented in Table 4. 

[1981Yan] established that the addition of phosphorus to Fe-3 w/o Si alloys enhances the 

sinterability but decreases the maximum permeability (mu max) and increases the coercive 

force (Hc). These phenomena were discussed in terms of pore distribution, the formation of 

secondary phases in the grain and the formation of amorphous phase in the grain boundary. 

The resistivities of sintered compacts increase with the increase of the amount of phosphorus. 

The γ, Fe 2P (I) phase with additions of Si was reported by [1983And] to be ferromagnetic or 

possibly ferrimagnetic; the Curie temperature of Fe 2Si 0.25P 0.75 was reported as 570 K (297˚C). 

Later the Curie temperature of Fe 2Si xP 1–x alloys was found by [1984Jer] to increase with 

increasing substitution by silicon - from 216 K (–57˚C) at x = 0 to 660 K (387˚C) at x = 0.35. 

[1988Liu] reported that addition of 0.5 mass% Si reduces the ductile-brittle transition 

temperature determined by small scale Charpy impact test by about 100 K, and the fracture 

mode becomes transgranular. Addition of more Si increases the transition temperature, but 

the fracture mode remains to be transgranular. 

Mechanical, electrical, magnetic and other physical properties of Fe-P-Si amorphous alloys 

were studied by [1993Bal, 1997Vav, 1998Vav, 1999Vav, 2000Vav1, 2003Bal, 2004Vav]. In 

particular, it was concluded that the embrittlement of these alloys is governed by the amount 

of (αFe) precipitating during crystallization [1998Vav, 1999Vav]. The effects of P substitution 

for Si as n type dopant on the thermoelectric properties of hot-pressed ζ 2, FeSi 2 phase were 

reported by [2002Ito]. The Seebeck coefficient, electrical resistivity and thermal conductivity 

were measured from room temperature up to 1100 K (827˚C), and then the power factor and 

figure of merit were evaluated. The Seebeck coefficient of the hot-pressed specimens is 

negative, indicating that P atoms are definitely substituted for Si atoms as an n-type dopant 

in the ζ 2 phase. The electrical resistivity is significantly reduced by P doping, especially in the 

lower temperature range, and slightly decreases with increasing P content. The thermal 

conductivity of the P-doped sample is smaller than that of the nondoped sample in spite of 

the larger amount of metallic λ, FeSi phase, and this fact indicates that P solution into the ζ 2 

phase is effective for reducing the thermal conductivity. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_25 

ß Springer 2009

6 25 

Fe–P–Si 

Miscellaneous 

A high-resolution scanning Auger microprobe analysis was carried out by [1991Men] on 

matching fracture surfaces of symmetrical ∑ = 5 (013) bicrystals of Fe-3 mass% Si doped with 

270 ppm phosphorus which were grown from seeds by floating-zone melting. Phosphorus 

distribution on some regions of a fracture surface was found to alternate between high and low 

concentrations. These alternations were often associated with deformation bands, such as 

mechanical twins. The reverse pattern was found on the matching region on the opposite 

fracture surface. 

Investigations of thermo-diffusion processes in Fe-P-Si alloys were carried out by 

[1973Wan]. A measuring arrangement for studies of thermo-diffusion in molten iron alloys 

was described, the Soret coefficients of silicon and phosphorus in the Fe-P-Si heats were 

determined. The lattice and grain boundary tracer diffusion coefficients D* PL and P* P of 

phosphorus in the Fe98.91Si0.96P0.13 (at.%) alloy were measured by [1983Mat] in the temperature 

range from 710 to 882˚C. The effect of Si additions on D*PL and P*P was concluded to be 

small. The sintering and alloying behavior of ferrous metal powder ternary compact Fe-3 mass 

% Si-3 mass% Fe 3P (Fe 90.06Si 5.21P 4.73 in at.%) was studied by [1990Qu] using dilatometry and 

SEM. It was found that phosphorus and silicon behave synergetically; phosphorus enhances 

alloying between Fe and Si at temperatures in the range 900-1100˚C. The concentration of 

interstitially dissolved Fe atoms in a Si crystal doped with a rather high concentration of P was 

found by [1994Tak] to depend on the cooling rate of the crystal. It was measured to decrease 

with an increase in the concentration of P and a decrease in the cooling rate. It was reported by 

[1990Reb, 1998Vav] that Fe-P-Si alloys have a tendency to amorphization in the concentration 

range between 12 and 20 at.% P and 2 to 10 at.% Si, but later this range was precised by 

[1997Vav, 1999Vav, 2000Vav1] as between 14 and 20 at.% P and 10 at.% Si at cooling rates of 

10 5 to 10 6 K·sec –1 . Annealing was shown by [2000Vav2, 2003Bal] to give a rise to nanoscale 

crystallization of amorphous Fe-P-Si alloys. The process occurs in one, two or three steps, and 

the annealed alloys contain crystallites 30 to 140 nm in size. Later the crystallization behavior 

of amorphous Fe-P-Si alloys was studied by [2003Bal] applying Mössbauer spectroscopy and 

physico-chemical analysis. The resulting materials are found to contain nanocrystalline 

particles of a complex composition, characterized by a doublet and several sextets in the 

Mössbauer spectrum. The amorphous alloys containing 6 or 10 at.% Si were found to possess 

the highest thermal stability, while the alloys with 2 at.% Si have a tendency toward nanoscale 

crystallization, accompanied by hardening. 

. Table 1 

Investigations of the Fe-P-Si Phase Relations, Structures and Thermodynamics 


[1930Hum] Melting in vacuum furnace, optical microscopy, 

thermal analysis, chemical analysis, heating in 

vacuum 

[1933Sau] Melting in vacuum furnace, heating in vacuum, 

X-ray diffraction (Debye technique) 



The Fe-Fe 2P-FeSi region 

1000˚C, the Fe-Fe 2P-FeSi region 



MSIT 1



[1959Vog] Melting in Pythagoras crucible (calcium chloride 

cover), thermal analysis, optical microscopy, 


[1962Run] Induction melting, heating, X-ray diffraction 

(Guinier technique) 

[1965Kan1] Electrolytical isolation, X-ray diffraction, chemical 

analysis 



< 1500˚C, the Fe-FeP 2-SiP-Si 

region 

50 at.% Fe, 0 to 25 at.% Si 

1000˚C, 800˚C, 2.5 mass% P in the 

alloys 

[1965Kan2] X-ray diffraction, chemical analysis 1100-700˚C, ≤ 4 at.% P 

[1965Sab] Induction melting, optical microscopy, X-ray 

powder diffraction (Debye-Scherrer technique) 

1080˚C, the Fe-FeP2-SiP-Si region 

[1968Sab] Induction melting, optical microscopy, X-ray 

powder diffraction (Debye-Scherrer technique) 

1080˚C, the Fe-FeP 2-SiP-Si region 

[1979Yam] Melting, Knudsen cell-mass spectrometry 

Si 

εP in liquid phase, 1600˚C, 

≤ 12.1 mass% Si 

[1983And] Induction melting, X-ray powder diffraction 

(Haegg-Guinier camera) 

66.7 at.% Fe, ≤ 22.3 at.% Si 

[1983Ban] Transportation method 

Si 


≤ 12.1 mass% Si 

[1983Yam] Melting, Knudsen cell-mass spectrometry 

Si 


≤ 12.1 mass% Si 

[1984Jer] Induction melting, sintering, X-ray powder 

diffraction (Haegg-Guinier camera), Mössbauer 

spectroscopy 

66.7 at.% Fe, ≤ 22.3 at.% Si 

[1990Reb] 

57 

Fe Mössbauer spectroscopy 2 to 10 at.% Si, 12 to 20 at.% P 

[1991Men] Floating-zone technique, high-resolution 

scanning Auger spectroscopy of fracture surfaces 

Fe rich range 

[1993Bal] Arc melting, 57 Fe Mössbauer gamma- resonance 

spectroscopy, differential thermal analysis, X-ray 

diffraction 

[1995Per] Solution growth from molten Sn (single crystal 

preparation), powder synthesis, X-ray diffraction 

(Guinier technique) 

[1997Ued] Equilibration of alloys in controlled P partial 

pressure 

[1997Vav] Arc melting, X-ray diffraction, thermal analysis, 

TEM, electron diffraction, Mössbauer 

spectroscopy 

[1998Vav] Mössbauer spectroscopy, differential thermal 

analysis, X-ray diffraction 



MSIT 1 

2 to 10 at.% Si, 12 to 20 at.% P 

1127-777˚C, FeSi 4P 4 

1450˚C, ≤ 63 at.% Fe, ≤ 0.92 at.% P 

≤ 10 at.% Si 


2 to 10 at.% Si, 12 to 20 at.% P 

7 

DOI: 10.1007/978-3-540-70890-2_25 

ß Springer 2009

8 25 

Fe–P–Si 



[1999Vav] Mössbauer spectroscopy, differential thermal 

analysis 

[2002Ito] Arc melting, mechanical alloying, X-ray 

diffraction, SEM, EDX 

[2003Bal] Arc melting, liquid quenching, X-ray diffraction, 

DTA 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 



2 to 10 at.% Si, 12 to 20 at.% P 

Hot pressing at 900˚C (3.6 ks, 25 

MPa); ≤ 33.3 at.% Fe, ≤ 6.67 at.% P 

2 to 10 at.% Si, 12 to 20 at.% P 



α, (αδFe) cI2 dissolves 4.55 at.% P at 1048˚C, 4 at.% 

P at 1000˚C [2002Per] 

Im3m dissolves 19.5 at.% Si at ~1280˚C [Mas2] 

W dissolves 2.2 at.% P at 7.6 at.% Si, 

1000˚C [1965Kan2] 

(δFe) (h2) 1538 - 1394 

a = 293.15 pure Fe, T = 1360˚C [V-C2] 

(αFe) (r) (ferrite) 

< 912 

a = 286.65 pure Fe, T = 25˚C [V-C2] 

(γFe) (h1) (austenite) cF4 a = 364.68 pure Fe, T = 912˚C [V-C2] 

1394 - 912 Fm3m dissolves 0.56 at.% P and 3.19 at.% Si 

Cu 

at 1150˚C [Mas2] 

at 1 at.% Si dissolves 3.9 at.% P at 

1000˚C, 1.9 at.% P at 800˚C [1965Kan2] 

dissolves 0.8 at.% P at 1.2 mass% Si, 

1000˚C; 0.6 at.% P at 3.5 mass% Si 

1000˚C [1965Kan2] 

(P) (red) c*66 a = 1131 sublimation at 1 bar. Stable form of P. 

< 417 

Triple point at 576˚C, > 36.3 bar; triple 

point at 589.6˚C at 1 atm [Mas2, V-C2] 

(P) (white) c** a = 718 common form of P [Mas2, V-C2] 

< 44.14 - 

P (white) 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 




(P) (black) oC8 a = 331.36 T = 25˚C [Mas2, V-C2] 

Cmca b = 1047.8 

P (black) c = 437.63 

(αSi) cF8 a = 543.06 T = 25˚C [Mas2, V-C2] 

< 1414 Fm3m 

C (diamond) 

(βSi) (II) tI4 a = 468.6 T = 25˚C, p > 9.624 bar [Mas2, V-C2] 

I41/amd βSn 

c = 258.5 

(γSi) (III) cI16 

Im3m 

γSi 

a = 663.6 T = 25˚C, p > 16.208 bar [Mas2, V-C2] 

(δSi) (I) hP4 a = 380 T = 25˚C, p = 16.208-1.013 bar 

P63/mmc αLa 

c = 628 

[Mas2, V-C2] 

β, Fe3P tI32 a = 910.8 at 25 at.% P [V-C2] 

< 1166 I4 c = 445.5 

Ni3P a = 917.4 

c = 452.99 

T = 678˚C [1990Oka] 

γ, Fe2P (I) hP9 at 33.3 at.% P 

< 1370 at 1.013 kbar P62m [Mas2, V-C2] 

Fe2P a = 586.4 

c = 346.0 

at 33.3 at.% P [1984Jer] 

γ, Fe2SixP1–x a = 586.75 x = 0 to 0.17 at room temperature 

c = 345.81 

[1984Jer] 

a = 592.12 

c = 342.26 

x = 0.10, room temperature [1984Jer] 

Fe2P (II) oP12 a = 577.5 T = 800˚C, 80 kbar 

high pressure phase Pnma b = 357.1 [Mas2, V-C2] 

Co2Si c = 664.1 



MSIT 1 

9 

DOI: 10.1007/978-3-540-70890-2_25 

ß Springer 2009

10 25 

Fe–P–Si 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 



δ, FeP oP8 50 at.% P [Mas2] 

≲ 1370 Pnma a = 519.1 [1962Run] 

MnP b = 309.9 

c = 579.2 

a = 519.3 at 20˚C [1972Sel], symmetry 

b = 309.9 

diminished to space group Pn21a by 

c = 579.3 

slight shift of the P atoms 

δ, FeSixP1–x x = 0 to 0.5 [1962Run] 

a = 524.2 

b = 305.9 

c = 585.3 

x = 0.5 [1962Run] 

ε, FeP2 oP6 66 to 67 at.% P [Mas2] 

Pnnm a = 497.29 at 66.7 at.% P [1969Dah, 1990Oka] 


b = 565.68 

c = 272.30 

π, FeP4 (I) mP30 80 at.% P [Mas2] 

P21/c a = 461.9 [1978Jei] 

FeP4 b = 1367.0 

c = 700.2 

β = 101.48˚ 

FeP4 (II) oC20 a = 500.5 T = 1100˚C, 60 kbar 

high pressure phase C2221 b = 1021.3 [Mas2, V-C2] 

FeP4 c = 553.0 

α2,Fe4Si or Fe2Si (h) cP2 B2, ~ 10 to 22 at.% Si [Mas2] 

≲ 1280 Pm3m a = 281 consecutive annealing of a Fe66.3Si33.7 

CsCl 

(at.%) button at 1100˚C for 18 h and 

of powder at 1150˚C for 7 min 

[1974Koe, V-C2] 

α1,Fe3Si cF16 D03, 11 to 30 at.% Si [1982Kub, Mas2] 

≲ 1235 Fm3m 

BiF3 a = 565.0 [V-C2] 

κ, Fe2Si hP6 ~33.0 to ~34.3 at.% Si [1982Kub] 

1212 - ~1040 P3m1 a = 405.2 ± 0.2 [V-C2] 

Fe2Si c = 508.55 ± 0.03 


1060 - 825 P63/mcm a = 675.9 ± 0.5 [V-C2] 

Mn5Si3 c = 472.0 ± 0.5 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 



λ, FeSi cP8 ~ 49.6 to ~ 50.8 at.% Si [Mas2] 

< 1410 P213 dissolves 2.1 mass% P at 1080˚C 

FeSi 

[1965Sab] 

a = 451.7 ± 0.5 [V-C2] 

ζ1, FeSi2(h) tP3 

a = 448.61 to 447.64 0 to 4.56 mass% P (0 to 6 at.% P) at 

33.8 mass% Si, annealing at 1000˚C for 

100 h [1965Sab] 

69.5 to 73.5 at.% Si [Mas2] 

1220 - 937 P4/mmm a = 268.72 to 269.37 69.6 to 72.1 at.% Si, annealing at 

FeSi2 (h) c = 512.8 to 513.9 1080˚C for 100 h [V-C2] 

a = 269.09 at 5 mass% P, annealing at 1080˚C for 

c = 513.08 

100 h [1965Sab] 

ζ2, FeSi2(r) oC48 66.7 at.% Si [1982Kub] 

< 982 Cmca a = 986.3 ± 0.7 [V-C2] 

FeSi2 (r) b = 779.1 ± 0.6 

c = 783.3 ± 0.6 

μ, SiP oC48 50 at.% P [Mas2] 

≲ 1131 Cmc21 a = 351.18 single crystal studies [V-C2] 

SiP b = 2048.8 

c = 1360.7 

ω (Si-P) amorphous - metastable; amorphous phase forming 

≲ 1131 

from a gaseous mixture of SiH4 and PH3 at 450˚C. Decomposed at 600˚C into 

(Si) and the μ phase [Mas2] 

SiP 2 cP12 a = 570.5 studies of a single crystal Si 33.6P 66.4 

Pa3 

FeS 2 (pyrite) 


(at.%) heated in an evacuated silica 

tube at 900˚C [V-C2] 

τ1, FeSi4P4 aP9 [1959Vog, 1965Sab, 1968Sab] 

≲ 1210 P1 a = 487.61 single crystal annealed at T = 927˚C 

FeSi4P4 b = 554.52 

c = 606.43 

α = 85.33˚ 

β = 68.40˚ 

γ = 70.43˚ 

[1995Per] 

τ2,Fe2SixP1–x oI* 

? 

Fe2SixP1–x - 0.20 < x < 0.36, T = 997˚C [1984Jer] 



MSIT 1 

11 

DOI: 10.1007/978-3-540-70890-2_25 

ß Springer 2009

12 25 

Fe–P–Si 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 



ψ (Fe-Si-P) amorphous - metastable; in alloys (in at.%) Fe82Si2P16 

and Fe 78Si 10P 12, rapidly quenched and 

then annealed at 500˚C for 10 min; in 

alloys Fe80Si6P14, Fe78Si10P12 and 

Fe 78Si 2P 20, rapidly quenched and 

then annealed at 600˚C for 10 min 

[1997Vav, 1998Vav, 1999Vav] 

. Table 3 



Fe 


P Si 

L Ð δ + λ 1223 e2 L 50.0 22.7 27.3 

L+κ Ð α + λ - U1L ~ 68 ~ 2 ~ 30 

L Ð γ + λ 1183 e7 L 58.6 17.2 24.2 

L Ð γ + δ + λ 1166 E1 L 56.4 21.5 22.1 

L Ð (Si) + τ1 1123 e9 L 6.8 28.1 65.1 

L Ð μ + τ1 - e10 - - - - 

L Ð μ + (Si) + τ1 1116 E2 L 3.2 31.4 65.4 

L ÐÐζ1 + τ1 1115 e11 L 21.3 19.3 59.4 

L Ð ζ1 + (Si) + τ1 1113 E3 L 20.6 19.2 60.2 

L+γ Ð β + λ 1110 U2 L 68.1 9.1 22.8 

L Ð λ + τ1 1105 e12 L 31.1 21.7 47.2 

L Ð δ + τ1 - e13 - - - - 

L Ð λ + ζ1 + τ1 1096 E4 L 30.7 21.1 48.2 

L Ð λ + δ + τ1 1095 E5 L 31.7 22.9 45.4 

L Ð λ + β + α 1018 E6 L 76.8 12.0 11.2 



MSIT 1

. Table 4 

Investigations of the Fe-P-Si Materials Properties 


[1965Sab] PMT-3 mechanical testing, picnometry Microhardness, density 

[1981Yan] Hysteresigraph tracer technique Maximum permeability, coercive force 

[1983And] Mössbauer spectroscopy Curie temperature 

[1983Mat] Residual activity method Curie temperature 

[1984Jer] Mössbauer spectroscopy Curie temperature 

[1988Liu] Small scale Charpy impact test Ductile-brittle transition temperature 

[1993Bal] 

57 

Fe Mössbauer gamma-resonance Effective magnetic field acting upon the 

spectroscopy, mechanical tests 

nucleus, microhardness, plasticity of foils 

[1994Tak] ESR spectroscopy Magnetic susceptibility versus magnetic 

field 

[1997Vav] Electrical resistance and magnetic Electrical resistance, effective magnetic 

measurements 

field 

[1998Vav] Mechanical properties tests, electrical 

resistivity measurements 

Brittle temperature, electrical resistivity 

[1999Vav] Mechanical properties tests, magnetic 

measurements 

[2000Vav1] Rapid quenching, X-ray diffraction, thermal 

analysis, Mössbauer spectroscopy; 

viscosity measurements (rotational 

oscillations of a quartz beaker filled with 

the melt 

[2002Ito] Four probe dc method (computercontrolled 

equipment); laser flash method 

(thermal contact analyzer ULVAC TC-7000) 

[2003Bal] Mechanical properties tests, Mössbauer 

spectroscopy 

[2004Vav] Thermal annealing, pulsed photon 

processing 

[2006Jan] Mechanical properties tests, Auger 

electron spectroscopy 



MSIT 1 

Microhardness, plasticity, effective 

magnetic field, chemical shift 

Kinematic viscosity 


Seebeck coefficient, electrical resistivity, 

thermal diffusivity, specific heat, density, 

thermal conductivity 

Electrical resistance, microhardness 

Size of particles; microhardness 

Energy of intergranular fracture 

13 

DOI: 10.1007/978-3-540-70890-2_25 

ß Springer 2009

14 25 

. Fig. 1a 

Fe-P-Si. Reaction scheme, part 1 

Fe–P–Si 



MSIT 1

. Fig. 1b 

Fe-P-Si. Reaction scheme, part 2 



MSIT 1 


15 

DOI: 10.1007/978-3-540-70890-2_25 

ß Springer 2009

16 25 

Fe–P–Si 

. Fig. 2 

Fe-P-Si. Partial liquidus surface projection 



MSIT 1

. Fig. 3 

Fe-P-Si. Temperature - composition section at 5 mass% P, plotted in at.% 



MSIT 1 


17 

DOI: 10.1007/978-3-540-70890-2_25 

ß Springer 2009

18 25 

Fe–P–Si 

. Fig. 4 

Fe-P-Si. Temperature - composition section at 13 mass% P, plotted in at.% 



MSIT 1

. Fig. 5 

Fe-P-Si. Temperature - composition section at 7 mass% Si, plotted in at.% 



MSIT 1 


19 

DOI: 10.1007/978-3-540-70890-2_25 

ß Springer 2009

20 25 

Fe–P–Si 

References 

[1930Hum] Hummitzsch, W., Sauerwald, F., “The Iron-Phosphorus-Silicon System” (in German), Z. Anorg. Allg. 

Chem., 194, 113–138 (1930) (Morphology, Phase Diagram, Phase Relations, Experimental, *, 9) 

[1933Sau] Sauerwald, F., Teske, W., Lempert, G., “X-Ray Studies of the Cr-C and Fe-Si-P Systems” (in German), 

Z. Anorg. Chem., 210, 21–25 (1933) (Crys. Structure, Morphology, Experimental, *, 5) 

[1949Jae] Jaenecke, E., “Si-Fe-P” (in German), Kurzgefasstes Handbuch aller Legierungen, Winter Verlag, 

Heidelberg, 625–627 (1949) (Phase Diagram, Phase Relations, Review, *, 16) 

[1959Vog] Vogel, R., Giessen, B., “The Iron-Phosphorus-Silicon System” (in German), Arch. Eisenhuettenwes., 

30(10), 619–626 (1959) (Crys. Structure, Morphology, Phase Diagram, Experimental, #, 9) 

[1962Run] Rundqvist, S., “Phosphides of the B31 (MnP) Structure Type”, Acta Chem. Scand., 16(2), 287–292 


[1965Kan1] Kaneko, H., Nishizawa, T., Tamaki, K., “Phosphide-Phases in Ternary Alloys of Iron, Phosphorus and 

Other Elements” (in Japanese), Nippon Kinzoku Gakkai-shi, 29(2), 159–165 (1965) (Morphology, Phase 

Diagram, Phase Relations, Experimental, Review, *, 24) 

[1965Kan2] Kaneko, H., Nishizawa, T., Tamaki, K., Tanifuji, A., “Solubility of Phosphorus in α- and γ-Iron” (in 

Japanese), Nippon Kinzoku Gakkai-shi, 29(2), 166–170 (1965) (Phase Relations, Experimental, Review, 

*, 20) 

[1965Sab] Sabirzyanov, A.V., Shumilov, M.A., “The Solubility of Aluminium and Phosphorus in Constituents of 

High-Silicon Ferrosilicon” (in Russian), Tr. Ural’sk. Politekh. Ins., (144), 35–40 (1965) (Crys. Structure, 

Morphology, Phase Diagram, Phase Relations, Experimental, Phys. Prop., 14) 

[1968Sab] Sabirzyanov, A.V., Gel’d, P.V., “Some Features of the Peritectoid Transformation in β-Leboite (FeSi 2) 

Alloys Alloyed with Al, Ca and P” (in Russian), Tr. Ural’sk. Politekh. Inst., (167), 75–80 (1968) 

(Morphology, Phase Relations, Experimental, 6) as quoted by [1988Rag] 

[1969Dah] Dahl, E., “Refined Crystal Structures of PtP 2 and FeP 2”, Acta Chem. Scand., 23(8), 2677–2684 (1969) 

(Crys. Structure, Experimental) as quoted by [1990Oka] 

[1972Sel] Selte, K., Kjekshus, A., “Structural and Magnetic Properties of FeP”, Acta Chem. Scand., Ser. A, 26(3), 

1276–1277 (1972) (Crys. Structure, Experimental, Magn. Prop., 17) 

[1973Wan] Wanibe, Y., Sakao, H., Sugiyama, T., Maiwa, K., “Investigations into Thermo-Diffusion with Iron- 

Silicon, Iron-Phosphorus and Iron-Silicon-Phosphorus Alloys”, Arch. Eisenhuettenwes., 44(8), 579–583 

(1973) (Morphology, Experimental, Interface Phenomena) cited from abstract 

[1974Koe] Koester, W., “Micro- and Crystal-Structure of Iron-Silicon Alloys Containing up to 40 at.% Si”, Trans. 

Iron Steel Inst. Jpn., 14(6), 387–394 (1974) (Crys. Structure, Morphology, Phase Diagram, Phase 


[1978Jei] Jeitschko, W., Braun, D.J., “Synthesis and Crystal Structure of the Iron Polyphosphide FeP 4”, Acta Cryst. 

B, 34, 3196–3201 (1978) (Crys. Structure, Experimental, 30) 

[1979Yam] Yamada, K., Kato, E., “Mass Spectrometric Determination of Activities of Phosphorus in Liquid 

Fe-P-Si, Al, Ti, V, Cr, Co, Ni, Nb and Mo Alloys” (in Japanese), Tetsu to Hagane (J. Iron Steel Inst. Jpn.), 

65(2), 273–280 (1979) (Thermodyn., Calculation, Experimental, Review, 40) 

[1981Yan] Yang, H.K., Lee, H.G., Im, H.B., “The Magnetic Properties of Sintered Fe-P and Fe-3 w/o Si-P Alloys”, 

J. Korean Inst. Met., 19(6), 471–479 (1981) (Morphology, Experimental, Electr. Prop., Magn. Prop.) 




[1983And] Andersson, Y., “A New Ternary Phase in the Fe-P-Si System: Fe 2P 1–uSi u, 0.20 

Conference on Solid Compounds and Transition Elements, Proc. CNRS, Grenoble (France), IIIA13/ 

1-IIIA13/3 (1983) (Crys. Structure, Experimental, Magn. Prop.) cited from abstract 

[1983Ban] Ban-ya, S., Maruyama, N., Fujino, S., “The Effect of C, Si, Al and B on the Activity of Phosphorus in 

Liquid Iron”, Tetsu to Hagane, 69, 921–928 (1983) (Thermodyn., Calculation, Experimental, Review, 32) 

[1983Mat] Matsuyama, T., Hosokawa, H., Suto, H., “Tracer Diffusion of P in Iron and Iron Alloys”, Trans. Jpn. 

Inst. Met., 24(8), 589–594 (1983) (Morphology, Experimental, Interface Phenomena, Kinetics, Magn. 

Prop., 14) 


Activity Coefficient of P in Liquid Iron”, Trans. Iron Steel Inst. Jpn., 23(1), 51–55 (1983) (Thermodyn., 




MSIT 1


21 

[1984Jer] Jernberg, P., Yousif, A.A., Haeggstroem, L., Andersson, Y., “A Mössbauer Study of Fe 2P 1–xSi x (x ≤ 0.35)”, 

J. Solid State Chem., 53, 313–322 (1984) (Crys. Structure, Experimental, Theory, Electronic Structure, 


[1988Liu] Liu, C.M., Abiko, K., Kimura, H., “Effect of Silicon on the Grain Boundary Segregation of Phosphorus 

and the Phosphorus Induced Intergranular Fracture in High Purity Fe-Si-P Alloys” in “Strength of 

Metals and Alloys (ICSMA8)”, Proc. of the 8 th International Conference, Pergamon, 1101–1106 (1988) 

(Morphology, Experimental, Mechan. Prop.) cited from abstract 

[1988Rag] Raghavan, V., “The Fe-P-Si (Iron-Phosphorus-Silicon) System” in “Phase Diagrams of Ternary Iron 

Alloys”, Indian Inst. Met., Calcutta, 3, 162–171 (1988) (Crys. Structure, Phase Diagram, Phase Relations, 

Review, #, 11) 

[1988The] “The 19 th Committee on Steelmaking, The Japan Society for the Promotion of Science” in “Steelmaking 

Data Sourcebook”, Gordon and Bresch Science Publishers, 280 (1988) (Morphology, Thermodyn., 

Review) as quoted by [1993Din] 

[1990Oka] Okamoto, H., “The Fe-P (Iron-Phosphorus) System”, Bull. Alloy Phase Diagrams, 11(4), 404–412 

(1990) (Crys. Structure, Phase Diagram, Phase Relations, Thermodyn., Assessment, Review, Magn. 

Prop., *, 88) 

[1990Qu] Qu, X., Lund, J.A., Gowri, S., “Synergistic Alloying-Sintering Effects in Iron-Silicon-Phosphorus 

Compacts”, Diffusion and Defect Data - Solid State Data, Part B (Solid State Phenomena), B8-9, 319–329 

(1990) (Morphology, Experimental, Interface Phenomena) cited from abstract 

[1990Reb] Rebrikova, L.K., Kovneristyi, Yu.K., Vavilova, V.V., Levintov, B.L., “Phase Equilibria and Susceptibility 

to Amorphization of Fe-P-Si Alloys” (in Russian), Konferenciya po Fizicheskoi Chimii i Tekhnologii 

Fosfidov i Fosforsoderzhaschikh Splavov (Conf. on the Physical Chemistry and Technology of 

Phosphides and Phosphorus-Containing Alloys), Alma-Ata, (1990) (Morphology, Phase Diagram, 

Phase Relations, Experimental) as quoted by [1998Vav] 

[1991Men] Menyhard, M., Rothman, B., McMahon, C.J., Jr., Lejcek, P., Paidar, V., “On the Fracture Path and the 

Intergranular Phosphorus Distribution in Phosphorus-Doped Fe-Si Symmetrical Bicrystals”, Acta 

Metall. Mater., 39(6), 1289–1295 (1991) (Crys. Structure, Morphology, Experimental, Mechan. Prop., 4) 

[1993Bal] Baldokhin, Yu.V., Vavilova, V.V., Kovneristyi, Ya.K., Kolotyrkin, P.Ya., Rebrikova, L.K., “Mössbauer 

Investigation of the Segregation Processes in the Amorphous Alloys of the Systems Fe-P-M (M: Mn, Si, 

V)” (in Russian), Dokl. Akad. Nauk, 328(5), 575–579 (1993) (Crys. Structure, Phase Relations, Experimental, 

Magn. Prop., Mechan. Prop., 7) 


(China), 29(12), B527–B532 (1993) (Thermodyn., Calculation, Theory, 7) 

[1994Tak] Takahashi, H., Suezawa, M., Sumino, K., “Iron-Phosphorus Interaction in Si”, Mater. Sci. Forum, 

143–147, 1257–1262 (1994) (Morphology, Experimental, Kinetics, Magn. Prop., 12) 

[1995Bou] Bouchard, D., Bale, C.W., “Simultaneous Optimization of Thermochemical Data for Liquid Iron Alloys 

Containing C, N, Ti, Si, Mn, S, and P”, Metall. Mater. Trans. B, 26B, 467–484 (1995) (Phase Relations, 

Thermodyn., Calculation, Review, Theory, 85) 

[1995Per] Perrier, Ch., Vincent, H., Chaudouet, P., Chenevier, B., Madar, R., “Preparation and Crystal Structure 

of a New Family of Transition Metal Phospho-Silicides”, Mater. Res. Bull., 30(3), 357–364 (1995) (Crys. 


[1997Ued] Ueda, S., Morita, K., Sano, N., “Thermodynamics of Phosphorus in Molten Si-Fe and Si-Mn Alloys”, 

Metall. Mater. Trans. B, 28(6), 1151–1155 (1997) (Thermodyn., Experimental, 15) 


Si) Amorphous Alloys”, Inorg. Mater. (Engl. Trans.), 33(3), 275–281 (1997), translated from Neorg. 

Mater., 33(3), 333–339 (1997) (Phase Diagram, Phase Relations, Thermodyn., Experimental, Electr. 

Prop., Kinetics, Magn. Prop., 15) 

[1998Vav] Vavilova, V.V., Kovneristyi, Yu.K., Palii, N.A., “Correlation between the Annealing-induced 

Embrittlement of Fe-P-M (M = V, Mn, Si) Amorphous Alloys and the Content of α-Fe Precipitates”, 

Inorg. Mater. (Engl. Trans.), 34(6), 566–570 (1998), translated from Neorg. Mater., 34(6), 692–696 

(1998) (Crys. Structure, Morphology, Phase Relations, Experimental, Electr. Prop., Mechan. Prop., 17) 

[1999Vav] Vavilova, V.V., Baldokhin, Y.V., “Mössbauer Study of Rapidly Quenched Fe-P-E Alloys (E = V, Nb, Mo, 

Mn, Si)”, Russ. Metall. (Engl. Transl.), (1), 122–132 (1999) (Crys. Structure, Phase Diagram, Phase 

Relations, Thermodyn., Experimental, Review, Kinetics, Magn. Prop., Mechan. Prop., 20) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_25 

ß Springer 2009

22 25 

Fe–P–Si 

[2000Vav1] Vavilova, V.V., Baldokhin, Y.V., Kovneristyi, Yu.K., Matveev, V.M., “Fe-P-M (M = Si, Mn, V) Alloys: 

Viscosity in the Liquid State and Tendency to Amorphization”, Inorg. Mater. (Engl. Trans.), 36(7), 

703–708 (2000), translated from Neorg. Mater., 36(7), 845–851 (2000) (Morphology, Thermodyn., 

Calculation, Experimental, Kinetics, Phys. Prop., 13) 

[2000Vav2] Vavilova, V.V., Palii, N.A., Kovneristyi, Yu.K., Timofeev, V.N., “Nanocrystalline Fe-P-Si Alloys”, Inorg. 

Mater. (Engl. Trans.), 36(8), 783–787 (2000), translated from Neorg. Mater., 36(8), 945–949 (2000) 

(Morphology, Experimental, Kinetics) as quoted by [2003Bal] 

[2002Ito] Ito, M., Nagai, H., Oda, E., Katsuyama, S., Majima, K., “Effects of P Doping on the Thermoelectric 

Properties of β-FeSi 2”, J. Appl. Phys., 91(4), 2138–2142 (2002) (Crys. Structure, Morphology, Calculation, 

Experimental, Electr. Prop., 19) 

[2002Per] Perrot, P., Batista, S., Xing, X., “Fe-P (Iron-Phosphorus)”, MSIT Binary Evaluation Program, in MSIT 


ID: 20.16107.1.20, (2002) (Crys. Structure, Phase Diagram, Phase Relations, Thermodyn., Assessment, 

Phys. Prop., #, 23) 

[2002Tan] Tani, J.-i., Kido, H., “Geometrical and Electronic Structures of β-FeSi 1.875X 0.125 (X = B, Al, N or P)”, Jpn. 

J. Appl. Phys., 41(11A), 6426–6429 (2002) (Crys. Structure, Calculation, Electronic Structure, 21) 

[2003Bal] Baldokhin, Yu.V., Vavilova, V.V., Kovneristyi, Yu.K., Kolotyrkin, P.Ya., Palii, N.A., Solomatin, A.S., 

“Mössbauer Study of Nanoscale Crystallization in Amorphous Fe-P-Si Alloys During Annealing”, 

Inorg. Mater. (Engl. Trans.), 39(5), 479–484 (2003), translated from Neorg. Mater., 39(5), 576–582 

(2003) (Crys. Structure, Morphology, Experimental, Electr. Prop., Kinetics, Magn. Prop., Mechan. 

Prop., 8) 

[2004Vav] Vavilova, V.V., Ievlev, V.M., Isaenko, A.P., Kovneristyi, Y.K., Palii, N.A., Timofeev, V.N., “Effect of 

Thermal Annealing and Pulsed Photon Processing on the Relaxation and Crystallization of 

Amorphous Fe-P-Si Alloys”, Inorg. Mater., 40(2), 152–160 (2004) (Morphology, Experimental, Mechan. 


[2006Jan] Janovec, J., Pokluda, J., Jenko, M., Lejcek, P., Vlach, B., Hornikov, J., “Influence of Phosphorus on 

Energy of Intergranular Fracture in Fe-Si-P Alloys”, Surf. Interface Anal., 38(4), 401–405 (2006) 

(Morphology, Experimental, Mechan. Prop.) cited from abstract 


(1990) 





MSIT 1

Iron – Sulphur – Titanium 


Nataliya Bochvar, Lazar Rokhlin 

Introduction 

The presence of sulphur in iron and steel leads commonly to decrease of strength, ductility and 

corrosion resistance. The steels containing sulphur incline to cracking at high temperatures of 

hot working. Therefore, the sulphur content in commercial steels is strictly limited in 

steelmaking processes. Titanium additions to the steel melts result in precipitation of disperse 

spherical complex sulphides which are modificators of cast structure and decrease the sulphur 

danger. For successful control this process, the Fe-S-Ti phase diagram is of a great importance. 

There is a number of reports on the ternary sulphides in the Fe-S-Ti system. The ternary 

compound Ti2FeS4 was reported by [1968Plo1, 1968Plo2, 1973Mur1, 1973Mur3], who determined 

its crystal structure and lattice parameters. The ternary compound TiFe 2S 4 was studied 

by [1973Mur2]. [1970Dan, 1974Dan] reported two ternary compounds Ti 4FeS 8 and Ti 4Fe 3S 8, 

and their crystal structures. There are few reports about the phase equilibria in the Fe-S-Ti 

system. The liquidus surface and a number of the vertical sections in the region Fe-FeS-TiS- 

TiFe 2 were constructed by [1948Vog]. Phase equilibria at 600, 950 and 1300˚C were studied by 

[1957Hah], [1963Kan] and [1968Swi], respectively. 

The effect of Ti on the solubility and activity of S in liquid Fe at 1550 to 1640˚C was 

determined by [1966Sch, 1969Sch, 1973Buz, 1977Eji1, 1977Eji2, 1985Don, 1987Don]. 

In the review on the Fe-S-Ti phase diagram of [1988Rag], the liquidus surface and reaction 

scheme are presented based on data of [1948Vog]. 

[1995Bou] optimized the thermodynamic data for liquid alloys of iron containing Ti, S 

and other elements. 

The list of the experimental works on the Fe-S-Ti phase diagram is presented in Table 1. 

Binary systems 

The Fe-S binary system is accepted after [Mas2] supplemented by [1982Kub1]. The Fe-Ti 

binary system is accepted after [1982Kub2]. The S-Ti binary system is accepted after [Mas2] 

supplemented by [1986Mur]. 


Fe–S–Ti 26 

1 

Four ternary compounds found in the Fe-S-Ti system are given in Table 2. These are τ 1, 

Ti 2FeS 4; τ 2,TiFe 2S 4; τ 3,Ti 4FeS 8; τ 4,Ti 4Fe 3S 8 [1968Plo1, 1970Dan, 1973Mur1, 1973Mur2, 

1973Mur3, 1974Dan]. All the ternary compounds were established by preparation in the 

direct synthesis from the elements of stoichiometric ratio by heating up to temperatures 900 

or 1000˚C. The character of formation, the melting temperatures and the homogeneous ranges 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_26 

ß Springer 2009

2 26 

Fe–S–Ti 

of these compounds were not studied. The certain connection between crystal structures of the 

ternary phases τ 1, τ 3 and τ 4 was noted [1974Dan]. 

The binary FeS and TiS compounds dissolve some Ti and Fe, respectively. There is 

discrepancy in values of solubility. According to [1934Kle], the compounds FeS and TiS 

form continuous solid solution, whereas [1948Vog, 1963Kan, 1976Mal] established the 

limited solution between these compounds. According to [1948Vog], the maximum solubility 

of Ti in FeS is about 30 mass% whereas [1963Kan] determined these solubility to be about 7 

mass%. Absence of the continuous solid solution of FeS and TiS was confirmed by [1957Hah, 

1970Kur] with extension of the limited FeS-base solid solution similar to that reported by 

[1948Vog]. On the contrary, solubility Fe in TiS was estimated about 22 mass% according to 

[1963Kan] and about 10 mass% according to [1948Vog]. Along with them, further investigations 

are desirable in order to avoid these discrepancies. 

Continuous solid solution between FeS and TiS can be obtained under high pressure. 

Thus, [1991Mak] synthesized the alloys along FeS-TiS section at temperatures 2127 to 2227˚C 

under pressure about 70 kbar followed by quenching down to 577˚C. Using X-ray analysis, 

[1991Mak] established existence of the solid solution Ti 1–xFe xS at 0.2 ≤ x ≤ 1.0 with the NiAs 

type structure. The lattice parameter a decreased from 345.9 to 334.7 pm and the lattice 

parameter c increased from 589.1 to 628.9 pm if the alloy composition changed from FeS to 

Ti 0.8Fe 0.2S. 


[1948Vog] and [1963Kan] presented the section FeS-TiS as quasibinary system. However, this 

section can be recognized as the quasibinary one only in limits from the FeS side up to ~ 50 

mass% Ti because TiS forms from liquid by the peritectic reaction L + Ti 8S 9 Ð TiS at ~1780˚ 

C. FeS and TiS interact by invariant peritectic reaction at the temperature 1540˚C [1948Vog] 

or ~1370˚C [1963Kan]. The peritectic temperature 1540˚C by [1948Vog] should be assumed 

to be more reliable because of more experiments used. Figure 1 shows the FeS-TiS partial 

quasibinary section taking into account [1948Vog]. 

According to [1948Vog] the TiFe2-TiS section is the quasibinary one. This, however, can be 

accepted only below ~ 55 mass% Ti. This section is characterized by existence of the liquid 

miscibility gap, monotectic and eutectic invariant reactions. The reaction temperatures were 

not indicated. Moreover, [1948Vog] showed two maxima (monotectic and eutectic points) on 

the double saturation lines in the Fe-corner. These points are located very close to the Fe-TiS 

section [1948Vog]. In opinion of [1988Rag], close location of the monotectic and eutectic 

points on the double saturation lines to the Fe-TiS section seems to suggest the section to be 

quasibinary one. The temperatures of the monotectic and eutectic points are 1500˚C and 

~1440˚C, respectively. These values are taken from the vertical sections [1948Vog]. 


Five four-phase and four three-phase invariant equilibria were established for the Fe-FeS- 

TiS-TiFe 2 region of the Fe-S-Ti system by [1948Vog]. They are shown in the reaction 

scheme (Fig. 2) assumed, in general, after the review [1988Rag]. According to [1948Vog], 

temperatures of the points U1, U2, E1 are between 1390 and 1400˚C for U1, U2, and 1300˚C 



MSIT 1

for E 1.In[1988Rag] these temperatures were corrected to meet the accepted binary systems 

and taken as ~ 1360, ~1350, ~1280˚C, respectively. The temperature of U 3,p 2max,e 1max,e 2max 

points were taken as 1000, 1570, 1500, 1440˚C in this assessment from vertical section 

[1948Vog]. The temperatures of points e 3min,e 5max,U 4 were taken by [1988Rag] speculatively. 


There is only one article by [1948Vog] in which the liquidus surface in the Fe-FeS-TiS-TiFe 2 

region of the Fe-S-Ti system was described. [1948Vog] established existence of the miscibility 

gap in liquid state extending from Fe-corner to the TiFe 2-TiS section. Two liquids, L 1 

(metallic) and L 2 (sulphide) participate in invariant reactions e 1max, e 2max and U 2. There is 

one minimum point (c 2) on the line bounding the miscibility gap at the composition about 

77.2 mass% Fe, 21.2 mass% S, 1.6 mass% Ti. It is reasonable to suppose also the existence of 

the maximum point c1 on the line bounding the miscibility gap out of the studied area of the 

phase diagram (in the direction of the Ti corner from the section TiS-TiFe2 (Fig. 3). The 

liquidus surface is shown in Fig. 3 according to [1948Vog] evaluated in mass%. The liquidus 

surface includes the miscibility gap and six regions of primary crystallization: (δFe,αFe), (γFe), 

FeS, TiS, Ti 8S 9 and TiFe 2. 



3 

The isothermal section at 600˚C was studied by [1957Hah] in the FeS-TiS2-TiS region. The 

one-phase ranges of the NiAs and CdI 2 type structures are shown approximately. The 

isothermal section at 950˚C was constructed by [1963Kan] in the limits of the Fe-FeS-TiS- 

TiFe 2 region. [1963Kan] drew the tie lines in the two-phase areas joining (δFe,αFe) or (γFe) 

with two sulphides FeS and TiS. However, there is considerable disagreement in solubility 

limits of Ti and Fe in corresponding sulphides that was discussed earlier. This section and the 

section at 600˚C are not shown in this assessment. 

The isothermal section at 1300˚C was constructed by [1968Swi] in Fe corner of the Fe-S-Ti 

phase diagram. Figure 4 shows this isothermal section with the tie lines in two-phase area 

joining (γFe) with the sulphide TiS at various partial pressure of sulphur. Positions of the three 

upper tie lines were drawn based on data obtained for the high sulphur partial pressure. 

Positions of the two lower tie lines were drawn based on one or two data points only and, 

therefore, should be regarded as approximate. The phase boundary between (γFe) and 

sulphide TiS was established from the solubility measurements in the range from 0.1 to 

0.4 mass% Ti. The Fe contents in the sulphide TiS was not determined by [1968Swi] because 

the experimental data yielded only the sulphur to titanium ratio in the sulphide TiS and did 

not give the iron contents. 

The isotherm of solubility of S and Ti in the Fe rich liquid phase at 1600˚C is shown in 

Fig. 5 according to the calculation made by [1995Bou] using the experimental data [1973Buz, 

1987Don]. The existence of the minimum solubility on the curve may be explained by 

decrease of the sulphur activity resulting from the Ti presence. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_26 

ß Springer 2009

4 26 

Fe–S–Ti 


Seven vertical sections of the Fe-S-Ti phase diagram in limits of the Fe-FeS-TiS-TiFe 2 region 

were constructed by [1948Vog]. Two of them are reproduced in Figs. 6 and 7 with some 

corrections to meet the accepted binary phase diagrams. In accordance with this, temperatures 

of the four-phase invariant equilibria U1, U2, E1 are given in the reaction scheme (Fig. 2). 


The activity coefficient of sulphur was determined by [1966Sch, 1969Ban, 1969Sch, 1973Buz, 

1974Sig, 1977Eji1, 1977Eji2, 1985Don, 1987Don]. Titanium decreases the activity coefficient 

of sulphur in both liquid and solid iron. The first-order interaction coefficients in liquid iron 

at 1600˚C are eS Ti = –0.082 [1966Sch, 1969Sch, 1973Buz], –0.072 [1974Sig], –0.18 [1977Eji1, 

1977Eji2], –0.2 [1985Don, 1987Don]. According to [1969Ban] eS Ti = –0.072 at 1550˚C. The 

discrepancies in the reported activity coefficients could be caused by the different methods 

used in the experiments. 

[2001Sud] determined thermodynamic properties of the Fe-S melts containing different 

d- and f- metals (in particular, Ti) by the calorimetric method. The partial mole enthalpies of 

the melts were established and taken into account at the desulphurization of steels. 


[1973Mur2] reported the results of the magnetization and Mössbauer effect measurements on 

TiFe 2S compound. The temperature dependence of magnetization was constructed for various 

magnetic fields up to 18 kOe between 2 and 340 K. Mössbauer spectra were determined at 291, 

276 and 80 K. Magnetic transition temperature was determined at 285 K. 

[1973Mur3, 1968Plo2] constructed the temperature dependence of electric resistivity of 

Ti2FeS4. The Ti2FeS4 resistivity measured on single crystal sample [1973Mur3] was similar to 

the results obtained by [1968Plo2] on polycrystalline samples. However, the kink on the 

resistivity curve at Neel temperature of Ti 2FeS 4 was not observed in the [1968Plo2] results. 

Based on the X-ray investigation of quenched samples [1968Plo1] showed the absence of the 

temperature-dependent order-disorder transition in this compound. Unlike [1968Plo1], in 

[1973Mur1] the transition from vacancy-order state to vacancy-disorder state was observed at 

720 K during magnetic measurements of the Ti 2FeS 4 sample at the temperature between liquid 

nitrogen temperature and 1273 K. The sample showed antiferromagnetism with the Neel 

temperature at 138 K. This discrepancy of [1968Plo1, 1968Plo2] and [1973Mur1, 1973Mur3] 

results may be explained by the difference of heat treatments of the samples during preparations. 

[1974Dan] measured electric and magnetic properties of the TiFe xS 2 alloys at x = 0.25, 

0.33, 0.40, 0.50, 0.75 in the temperature range from 7 to 400 K. Measured alloys showed a 

competition between ferromagnetism and antiferromagnetism. 

The temperature dependence of magnetization and magnetic susceptibility of the alloys 

along the FeS-Ti 0.8Fe 0.2S section were established by [1991Mak]. The experiments were 

conducted under high pressure. [1991Mak] determined the temperatures of the magnetic 

phase transitions in these alloys and constructed the magnetic phase diagram of the FeS-TiS 

solid solution. 



MSIT 1

[2004Kim, 2005Nam] measured Mössbauer spectra of the Ti 0.025Fe 0.975S alloy at various 

temperatures between liquid nitrogen temperature and 600 K. The Neel temperature, crystallographic 

phase transition temperature and the Morin transition temperature were determined. 

Miscellaneous 


5 

[1965Sch] investigated a possibility of the sulphide formation in Fe-S-Ti system at 1600˚C. 

They discovered that the sulphide TiS was formed only at the lower than 1600˚C temperature 

during crystallization of the Fe-rich liquid phase. 

[1976Mal] investigated formation and nature of the sulphide phase in Fe-S-Ti and 

C-Fe-S-Ti systems. [1976Mal] showed that the titanium sulphide eutectic was formed between 

the branches of the austenite dendrites during the solidification of Fe-S-Ti alloys with low 

S and Ti contents. With increasing concentrations of Ti and S the amount of sulphide eutectic 

increased and at approximately 0.5 mass% S and 2.5 mass% Ti the alloy possessed a purely 

eutectic structure. The titanium sulphide eutectic was formed in C-Fe-S-Ti alloys even at low 

Ti content together with a titanium carbide eutectic. 

Also, the mechanism of the titanium sulphides formation around the branches of the 

austenite dendrites in the Fe-S-Ti alloys during crystallization was studied by [1981Sam], who 

gave the mathematical description of this process. 

Using an electron microprobe analyzer, [1968Ska] studied the effect of Ti additions on the 

morphology, size and mode of precipitation of sulphides in pure iron with high sulphur 

content. 

In the review [1968Hul] the transition-element compounds with the structure of various 

types (pyrite, marcasite, CdI 2, NiAs and others) were discussed. 

[1995Bou] presented a database of thermochemical parameters for liquid iron-base alloys 

containing Ti, S and other elements. Expressions for the interaction parameters of the solutes 

and the Gibbs energies of formation of the carbides, nitrides and sulphides of titanium were 

simultaneously optimized. It was shown that the resulting thermochemical database reproduced 

the experimental data satisfactorily. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_26 

ß Springer 2009

6 26 

Fe–S–Ti 

. Table 1 

Investigations of the Fe-S-Ti Phase Relations, Structures and Thermodynamics 


[1934Kle] Alloys were prepared by melting of FeS 

with 1, 5, 10, 20, 44% TiS 2 at different 

temperature from 1360 to 1630˚C. 

Chemical, thermal and microstructure 

analyses 

[1948Vog] Krupp WW Fe, Ti (95%), pure S were 

melted in alumina crucible in Ar. The 

thermal analysis, optical microscopy, 

chemical analysis of the separated layers, 

X-ray analysis 

[1957Hah] The direct synthesis of elements. 900 to 

1000˚C for 48 hour, then 600˚C for more 

week. X-ray analysis 

[1963Kan] Electrolytic isolation of sulphides from 

ternary alloys. Chemical and X-ray 

analyses 

[1965Sch] Alloys were prepared in induction furnace 

in argon atmosphere. Chemical and 

metallographic analyses 


in argon atmosphere at 1600˚C. Chemical 

analysis, thermodynamic 

[1968Plo1] Synthesis of stoichiometric ratio Ti 

(99.99%), Fe (99.99%), powder S 

(99.999%) in evacuated silica tube at 600, 

800 and 1000˚C during one week. 

Quenching from 1300˚C into ice water, 

then annealing at 800, 1000˚C and slowcooled 

at the rate of 10 K·h –1 . X-ray 

measurement. 

[1968Swi] Flat plates (0.03 by 2 by 4) from 

specimens of Fe-Ti alloys made in 

induction furnace were equilibrated at 

1300˚C in resistance furnace in H 2S-H 2 

mixture. Chemical analysis, electron 

microprobe. 

[1969Ban] Electrolytic Fe, pure Ti and pure iron 

sulphide. Alumina crucibles, resistance 

furnace, exposed to a fixed sulphur 

potential gas for 4 to 12 hours at 1550˚C, 

quenching. Gravimetrical and chemical 

analyses, calculation, thermodynamic. 


Range Studied 

1000 to 1600˚C The partial FeS-TiS 

section from 0 to 40 mass% TiS 

At the temperatures from 1500 to 800˚C 

in Fe-FeS-TiS-TiFe 2 composition range. 

Liquidus surface and vertical sections. 

Invariant equilibria. 

Phase relations at 600˚C in the FeS-TiS 2- 

TiS composition range. 

950˚C, Fe-rich alloys with S from 0 to 

40 mass% and Ti from 0 to 60 mass%. The 

isothermal section at 950˚C. 

1600˚C, Fe alloys with 0.6 to 4.3 mass% Ti 

and 0.1 mass% S 

Solubility of Ti and S in Fe liquid at 

1600˚C, activity coefficient of S in Fe 

liquid 

Ternary compound Ti 2FeS 4. Crystal 

structure and order-disorder transition. 

Fe-Ti alloys with 0.12, 0.24, 0.38, 

0.54 mass% Ti and 0 to 0.08 mass% S. The 

temperature range from 1150 to 1300˚C. 

Solubility of S in Fe-Ti alloys at 1300˚C 

1550˚C, the effect Ti on the activity 

coefficient of S in liquid iron 



MSIT 1




in argon atmosphere at 1600˚C. Chemical 

analysis, thermodynamic 

[1970Dan] Synthesis of elements with TiS2 in silica 

tubes at 900˚C for 5 h. X-ray analysis 

[1973Buz] Electron-probe analysis and X-ray 

diffraction, thermodynamic. 

[1973Mur1] Direct reaction of Fe (99.99%), Ti (99.99%), 

powder S (99.999%) in an evacuated silica 

tube at 500˚C for 1 week, then at 900˚C 

for 1 week. Chemical and X-ray analyses, 

magnetic measurements. 

[1973Mur2] Direct reaction of highly pure elements in 

an evacuated silica tube at 750˚C for 

2 weeks. Chemical and X-ray analyses, 

magnetic measurements on torsion 

balance magnetometer. 

[1973Mur3] Single crystal of Ti 2FeS 4 was prepared in 

sealed evacuated tube from powder 

sample with 10 –6 MmHg, Cl 2 gas as a 

growth agency. X-ray diffraction, 

measurement of electric resistivity. 

[1974Dan] Synthesis of elements with TiS2 in silica 

tubes at 900˚C for 5 h and 1000˚C for 10 

h X-ray analysis, electric and magnetic 

measurements 

[1976Mal] Alloys were prepared in vacuum electric 

furnace in alundum crucibles from 

carbonyl Fe, metallic Ti and elemental S. 

X-ray microanalyser, microprobe and 

microstructure analyses. 

[1977Eji1, 

1977Eji2] 

Alloys were prepared by melting Fe-S in 

induction furnace with addition of Ti 

under argon. Thermodynamic properties 

[1987Don] High purity Fe (99.99%) and Ti (99.7%) 

and iron sulphide (powder). High 

frequency induction furnace, argon gas. 

Stabilization at 1640˚C for 10 min and 

quenching. Stabilization at 1560˚C for 10 

min and quenching. Optical pyrometer, 

chemical analysis, energy dispersive 

spectroscopy, thermodynamic. 



MSIT 1 



Range Studied 

Solubility of Ti and S in Fe liquid at 

1600˚C, activity coefficient of S in 

Fe liquid 

Ternary compounds Ti 4FeS 8 and Ti 4Fe 3S 8. 

Crystal structure and lattice parameters 

Solubility of Ti and S in Fe liquid and 

activity coefficient of S in liquid Fe at 

1600˚C. 

Ternary compound Ti 2FeS 4. Crystal 

structure and lattice parameters. 

Ternary compound TiFe 2S 4. Crystal 

structure and lattice parameters. 

Single crystal of Ti 2FeS 4. Lattice 

parameters. 

Alloys along Fe xTiS 2 at x = 0.25, 0.5, 0.75 

(ternary compounds Ti4FeS8, Ti2FeS4 and 

Ti 4Fe 3S 8). Crystal structure and lattice 

parameters. 

Cast alloys in Fe-corner, S varied from 

0.009 to 0.1 mass% and Ti from 0.012 to 

0.53 mass%. The effect of Ti and S 

contents on the sulphide formations. 

1600˚C, solubility S and Ti in Fe liquid, 

interaction parameters, activity 

coefficient 

7 

Series of liquid Fe-Ti-S alloys in 

temperature range of 1560 to 1640˚C. 

The TiS solubility product and sulphurtitanium 

interaction parameter at 1600˚C. 

DOI: 10.1007/978-3-540-70890-2_26 

ß Springer 2009

8 26 

Fe–S–Ti 



[2004Kim] Alloys were prepared by direct reaction of 

the elements (of high purity, better than 

99.9%) in evacuated and sealed quartz 

tubes at 1000˚C for 7 days followed by 

quenching. X-ray diffraction, Mössbauer 

measurements. 

[2005Nam] Alloys were prepared by direct reaction of 

the elements (of high purity, better than 

99.995%) in evacuated quartz ampoules 

at 600˚C for 1 day, then at 1000˚C for 3 

days followed by quenching. X-ray 

diffraction, Mössbauer measurements. 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Range Studied 

Alloy FeS with 1.25 at.% Ti (Ti 0.025Fe 0.975S). 

Crystal structure and lattice parameters at 

room temperature 

Alloy FeS with 1.25 at.% Ti (Ti0.025Fe0.975S). 

Crystal structure and lattice parameters at 

room temperature 

Lattice 

Parameters 


δα, (δFe,αFe) cI2 (δFe) and (αFe) merges and dissolves 9.8 at.% Ti at 

Im3m 

W 

1290˚C in Fe-Ti system [1982Kub2] 

(δFe) dissolves ~0.24 at.% S at 1365˚C 

1538 - 1394 [Mas2] 

a = 293.15 [Mas2] 

a = 293.78 at 1480˚C [V-C2] 

(αFe) dissolves 0.033 at.% S at 1365˚C [Mas2] and 3.08 at. 

< 912 

% Ti at 900˚C 

[1982Kub2] 

a = 286.65 at 25˚C [Mas2] 

(γFe) cF4 dissolves 0.09 at.% S at 1365˚C [Mas2] and 0.8 at.% 

1394 - 912 Fm3m 

Ti at 1120˚C [1982Kub2] 

Cu a = 364.67 at 915˚C [Mas2] 

a = 366.00 at 1167˚C [V-C2] 

(βS) mP48 a = 1102 100 at.% S [Mas2] 

115.22 - 95.9 P21/a b = 1096 

βS c =1090 

β = 96.7˚ 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


(αS) oF128 100 at.% S 

< 95.5 Fddd a = 1046.4 at 25˚C [Mas2] 

αS b = 1286.60 

c = 2448.60 

(βTi) cI2 dissolves 0.01 at.% S at 1212˚C [Mas2] and 22 at.% 

1670 - 882 Im3m 

Fe at 1085˚C [1982Kub2] 

W a = 330.65 [Mas2] 

(αTi) hP2 dissolves 0.02 at.% S at ~885˚C [Mas2] and 

< 882 P63/mmc 0.055 at.% Fe at 590˚C [1982Kub2] 

Mg a = 295.06 

c = 468.35 

at 25˚C [Mas2] 

γFeS hP4 50 to 55 at.% S 

1188 - 315 P63/mmc [Mas2] 

NiAs dissolves about 27 at.% Ti along FeS- TiS section 

[1948Vog] 

a = 344.36 ± 5 

c = 587.59 ± 0.05 

[V-C2] 

βFeS hP24 50 to ~52 at.% S [Mas2], troilite 

315 -< 138 P62c a = 599.8 ± 1.1 [V-C2] 

βFeS c = 1171 ± 1 

a = 596.9 ± 0.2 quenching from 1000˚C, for Ti0.025Fe0.975S c = 1169 ± 5 [2004Kim, 2005Nam] 

αFeS hP6 50 to ~52 at.% S [Mas2] 

< 138 P63/mmc a = 345.59 ± 0.05 [V-C2] 

αFeS c = 577.89 ± 0.05 

βFeS2 cP12 ~66.7 at.% S [Mas2], pyrite 

743 - 444.6 Pa3 

βFeS2 a = 541.8 ± 0.2 [V-C2] 

αFeS2 oP6 ~66.7 at.% S [Mas2], marcasite 

< 444.6 Pnnm a = 444.31 ± 0.09 [V-C2] 

αFeS2 b = 542.15 ± 0.09 

c = 338.71 ± 0.06 

TiFe2 hP12 25.8 to 34.4 at.% Ti at 1200˚C 

< 1427 P63/mmc [1982Kub2] 

MgZn2 a = 478.5 ± 0.2 

c = 779.9 ± 0.3 

[V-C2] 



MSIT 1 


9 

DOI: 10.1007/978-3-540-70890-2_26 

ß Springer 2009

10 26 

Fe–S–Ti 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


TiFe cP2 49.8 to 51.8 at.% Ti at 1080˚C 

< 1317 Pm3m [1982Kub2] 

ClCs a = 297.89 ± 0.03 [V-C2] 

Ti6S h** ~14 at.% S [Mas2] 

< 885 - a = 296.7 [1986Mur] 

- c = 1450 

Ti3S t** 25 at.% S [Mas2] 

< 1305 - a = 997.8 [1986Mur] 

- c = 490 

Ti2S oP 31 to 35 at.% S [Mas2] 

< 1410 36 a = 1406 [V-C2] 

Pnnm b = 1135 

Ta2P c = 332 

TiS, (Ti1+xS) hP2 46 to 49.7 at.% S [Mas2] 

≲ 1780 - 935 P6m2 dissolves about 8.8 at.% Fe along TiS- FeS section 

CW 

[1948Vog] 

a = 327.2 

c = 643.8 

[1986Mur] 

TiS hP4 ~49.7 at.% S [Mas2] 

< 935 P63/mmc a = 329.6 [V-C2] 

NiAs c = 639.8 

Ti8S9 hR18 ~52.6 at.% S [Mas2] 

≲ 1975 R3m a = 342.3 [1986Mur] 

- c = 2646 

Ti8S10 hP18 ~55.6 at.% S [Mas2] 

≲ 1850 P63/mmc a = 343.9 [1986Mur] 

- c = 2893 

Ti16S21 hR37.1 ~56.6 at.% S [Mas2] 

R3m a = 344.1 [1986Mur] 

- c = 6048 

Ti2.67S4 hP6.8 57.9 to 61.4 at.% S [Mas2] 

P63mc a = 343.85 [1986Mur] 

- c = 1143.22 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Lattice 

Parameters 


(4H) 2 mC40.14 Superlattice structure based on Ti2.67S4 Cc 59.8 to 60.3 at.% S [Mas2] 

- a = 594.395 

b = 1029.51 

c = 2285.83 

[1986Mur] 

(4H) 3 mC59.8 Superlattice structure based on Ti2.67S4 Cc [Mas2] 

- a = 1030 

b = 592 

c = 3490 

[1986Mur] 

Ti7S12 hR19.1 ~62.8 at.% S [Mas2] 

R3m a = 342.0 [1986Mur] 

Ti7S12 c = 3432.6 

TiS2 hP3 64.4 to 66.7 at.% S [Mas2] 

P3m1 a = 340.73 [1986Mur] 

CdI2 c = 569.53 

TiS3 mP8 ~75 at.% S [Mas2] 

< 632 P21/m a = 499 [1986Mur] 

- b = 338 

c = 877.84 

β = 97.324˚ 



MSIT 1 

11 

DOI: 10.1007/978-3-540-70890-2_26 

ß Springer 2009

12 26 

Fe–S–Ti 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


* τ1,Ti2FeS4 mC14 a = 592.7 slowly cooling [1973Mur1] 

C2/m b = 342.8 

Cr3S4 c = 1145.8 

β = 90.1˚ 

a = 592.8 

b = 342.2 

c = 1149.1 

β = 90.0˚ 

quenching from 400˚C [1973Mur1] 

a = 592.7 

b = 342.0 

c = 1147.9 

β = 90.0˚ 


a = 592.2 

b = 342.6 

c = 1148.2 

β = 90.0˚ 


a = 592.6 

b = 342.8 

c = 1145.7 

β = 90.1˚ 

single crystal [1973Mur3] 

a = 592.9 

b = 342.6 

c = 1146 

β = 90.1˚ 

quenching from 1000˚C [1968Plo1] 

a = 595 

b = 341.7 

c = 1153 

β = 90.2˚ 

[1974Dan] 

* τ2, TiFe2S4 mC14 a = 598 annealing at 750˚C [1973Mur2] 

C2/m b = 343 

Cr3S4 c = 1116 

β = 91.7˚ 

* τ3,Ti4FeS8 mC52 [V-C2] 

C2/m a = 1181 [1970Dan, 1974Dan] 

Ti4FeS8 b = 683 

c = 1140 

β = 90.4˚ 

* τ4, Ti4Fe3S8 mC120 [V-C2] 

C2/m a = 1184 [1970Dan, 1974Dan] 

- b = 685 

c = 2320 

β = 90.3˚ 



MSIT 1

. Fig. 1 

Fe-S-Ti. Partial quasibinary FeS-TiS section 



MSIT 1 


13 

DOI: 10.1007/978-3-540-70890-2_26 

ß Springer 2009

14 26 

. Fig. 2 

Fe-S-Ti. Partial reaction scheme 

Fe–S–Ti 



MSIT 1

. Fig. 3 

Fe-S-Ti. Liquidus surface projection in the Fe-FeS-TiS-TiFe 2 region 



MSIT 1 


15 

DOI: 10.1007/978-3-540-70890-2_26 

ß Springer 2009

16 26 

Fe–S–Ti 

. Fig. 4 

Fe-S-Ti. Partial isothermal section at 1300˚C 



MSIT 1

. Fig. 5 

Fe-S-Ti. Solubility S and Ti in liquid Fe at 1600˚C 



MSIT 1 


17 

DOI: 10.1007/978-3-540-70890-2_26 

ß Springer 2009

18 26 

Fe–S–Ti 

. Fig. 6 

Fe-S-Ti. Partial vertical section from the binary 94Fe-6S towards the binary 90Ti-10Fe (mass%) 

alloys 



MSIT 1


. Fig. 7 

Fe-S-Ti. Partial vertical section from Ti-corner towards the binary 70Fe-30S (mass%) 



MSIT 1 

19 

DOI: 10.1007/978-3-540-70890-2_26 

ß Springer 2009

20 26 

Fe–S–Ti 

References 

[1934Kle] Kleffer, J., “The Metallurgy of Titanium Sulphide in the Haglund Process” (in German), Metall Erz, 

3(14), 307-320 (1934) (Morphology, Phase Diagram, Phase Relations, Experimental, 59) 

[1948Vog] Vogel, R., Kasten, G.-W., “The Iron-Sulphur-Titanium Phase Diagram” (in German), Arch. Eisenhuettenwes., 

19, 65-71 (1948) (Experimental, Morphology, Phase Diagram, Phase Relations, 4) 

[1957Hah] Hahn, H., Harder, B., Brockmueller, W., “Ternary Chalcogenides. X. The Reaction of Ti Sulphides with 

Sulphides of Divalent Transition Metals” (in German), Z. Anorg. Allg. Chem., 288(5-6), 260-268 (1957) 

(Crys. Structure, Experimental, Phase Relations, 8) 

[1963Kan] Kaneko, H., Nishizawa, T., Tamaki, K., “Study on Phase Diagram of Sulfides in Steel” (in Japanese), 

Nippon Kinzoku Gakkai Shi, 27(7), 312-318 (1963) (Phase Diagram, Experimental, Phase Relations, 

*, 23) 

[1965Sch] Schindlerova, V., Buzek, Z., “The Experimental Investigation of the Possible Formation of Sulphides in 

Systems of Fe-S-Al, Fe-S-Ti and Fe-S-Zr at 1600˚C” (in Czech), Sb. Ved. Pr. Vys. Sk. Banske Ostrave, 

Rada Hutn., 11(3), 443-447 (1965) (Experimental, Morphology, Phase Relations, 11) 

[1966Sch] Schindlerova, V., Buzec, Z., “Effect of Aluminum Titanium, Manganese, Zirconium, and Cerium on 

the Solubility and Activity of Sulphur in Molten Iron at 1600˚C” (in Czech), Hutn. Listy, 21(3), 

169-175 (1966) (Experimental, Phase Relations, Thermodyn., 14) 

[1968Hul] Hulliger, F., “Crystal Chemistry of Chalcogenides and Pnictides of the Transition Elements”, Struc. 

Bonding, 4, 83-229 (1968) (Crys. Structure, Review, 532) 

[1968Plo1] Plovnick, R.H., Vlasse, M., Wold, A., “Preparation and Structural Properties of Some Ternary 

Chalcogenides of Titanium”, Inorg. Chem., 7(1), 127-129 (1968) (Crys. Structure, Experimental, 9) 

[1968Plo2] Plovnick, R.H., Perloff, D.S., Vlasse, M., Wold, A., “Electrical and Structural Properties of Some 

Ternary Chalcogenides of Titanium”, J. Phys. Chem. Solids, 29, 1935-1940 (1968) (Crys. Structure, 

Electr. Prop., Experimental, 8) 

[1968Ska] Skala, J., Riman, R., “The Influence of Certain Elements (Al, Mn, Cr and Ti) on the Chemical 

Composition of Iron Sulphides” (in Czech), Sb. Ved. Pr. Vys. Sk. Banske Ostrave, Rada Hutn., 14(3), 

115-122 (1968) (Crys. Structure, Morphology, Experimental, 2) 

[1968Swi] Swisher, J.H., “Sulfur Solubility and Internal Sulfidation of Iron-Titanium Alloys”, Trans. Met. Soc. 

AIME, 242, 2433-2439 (1968) (Experimental, Phase Diagram, Phase Relations, Thermodyn., #, 13) 

[1969Ban] Ban-ya, S., Chipman, J., “Sulphur in Liquid Iron Alloys: II – Effect of Alloys Elements”, Trans. AIME, 

245(1), 133-143 (1969) (Experimental, Thermodyn., 18) 

[1969Sch] Schindlerova, V., Buzek, Z., “The Effect of Al, Ti, Mn, Zr and Ce on the Solubility and Activity of S in 

Molten Fe at 1600˚C” (in German), Freiberger Forschungshefte, 117B, 43-58 (1969) (Experimental, 

Phase Relations, Thermodyn., *, 14) 

[1970Dan] Danot, M., Rouxel, J., “M xTiS 2 Systems (M = Alkali Metal or Transition Metal of the First Period x = 

0 to 1); MTi 4S 8 and M 3Ti 4S 6 (M = Fe, Co, Ni) Superstructures” (in French), Compt. Rend. Acad. Sci. 

Paris, Ser. C, 271, 998-1001 (1970) (Crys. Structure, Experimental, 7) 

[1970Kur] Kurihara, J., “Synthetic Products in the Ti-S and Fe-Ti-S Systems” (in Japanese), Denki Kagaku, 38 

(11), 842-848 (1970) (Crys. Structure, Experimental) as quoted by [1988Rag] 


Iron at 1600˚C”, “Metall. Chem. - Appl. Ferrous Metall.”, Int. Symp., Sheffield, July 1971, Iron Steel Inst, 

London, 173-177 (1973) (Crys. Structure, Experimental, *, 8) 

[1973Mur1] Muranaka, S., “Order-Disorder Transition of Vacancies in FeTi 2S 4”, Mater. Res. Bull., 8, 679-686 (1973) 

(Crys. Structure, Experimental, Magn. Prop., 3) 

[1973Mur2] Muranaka, S., “Magnetic Properties of Fe 2TiS 4”, J. Phys. Soc. Jpn., 35, 1553 (1973) (Experimental, 


[1973Mur3] Muranaka, S., Takada, T., “Growth and Electrical Properties of FeMX 4 (M = Ti, V; X = S, Se) Single 

Crystals.”, Bull. Inst. Chem. Res., Kyoto Univ., 51(5), 287-294 (1973) (Crys. Structure, Electr. Prop., 


[1974Dan] Danot, M., Rouxel, J., Gorochov, O., “Electrical, Magnetic and Structural Properties of the Phase 

M xTiS 2 (M = Fe, Co, Ni)” (in French), Mater. Res. Bull., 9, 1383-1392 (1974) (Experimental, Electr. 

Prop., Magn. Prop., *, 24) 

[1974Sig] Sigworth, G.K., Elliott, J.F., “The Thermodynamics of Liquid Dilute Iron Alloys”, Met. Sci., 8, 298-310 




MSIT 1


21 

[1976Mal] Malinochka, Ya.N., Balakina, N.A., Shmelev, Yu.S., “The Sulphide Phases in Fe-Ti-S and Fe-C-Ti-S 

Alloys”, Russ. Metall., (6), 169-174 (1976), translated from Izv. Akad. Nauk SSSR, Met., 6, 212-216 

(1976) (Experimental, Kinetics, 15) 

[1977Eji1] Ejima, A., Suzuki, K., Harada, N., Sanbongi, K., “Sulphur Equilibria in Molten Fe-La-S, Fe-Ti-S, and 

Fe-Zr-S Systems” (in Japanese), Tetsu to Hagane, 63(6), 943-952 (1977) (Experimental, Phase Relations, 


[1977Eji2] Ejima, A., Suzuki, K., Harada, N., Sanbongi, K., “Sulphur Equilibria in Molten Fe-La-S, Fe-Ti-S, and 

Fe-Zr-S Systems”, Trans. Iron Steel Inst. Jpn., 17(6), 349-358 (1977) (Experimental, Morphology, 


[1981Sam] Samoylovich, Yu.A., Bryksin, V.M., “Rhytmic Growth of Dendritic Branches in Fe-Ti-S Melts”, Russ. 

Metall., (5), 170-173 (1981), translated from Izv. Akad. Nauk SSSR, Met., (5), 218-220 (1981) (Experimental, 


[1982Kub1] Kubaschewski, O., “Iron-Sulphur” in “Iron Binary Phase Diagrams”, Springer-Verlag Berlin/Heidelberg, 

and Verlag Stahluesen GmbH, Düsseldorf, Germany, 125-128 (1982) (Phase Diagram, Phase Relations, 

Crys. Structure, Thermodyn., Review, 20) 

[1982Kub2] Kubaschewski, O., “Iron-Titanium” in “Iron Binary Phase Diagrams”, Springer-Verlag Berlin/Heidelberg, 

and Verlag Stahluesen GmbH, Düsseldorf, Germany, 152-156 (1982) (Phase Diagram, Phase 

Relations, Crys. Structure, Thermodyn., Review, 26) 

[1986Mur] Murray, J.L., “The S-Ti (Sulphur-Titanium) System”, Bull. Alloy Phase Diagrams, 7(2), 156-163 (1986) 

(Crys. Structure, Phase Diagram, Phase Relations, Review, 57) 

[1985Don] Donahue, F.M.III, Pehlke, R.D., “Equilibrium between Sulfur and Titanium in Liquid Iron”, J. Met., 37 

(11), A96-A96 (1985) (Experimental, Thermodyn., Abstract, 0) 

[1987Don] Donahue, F.M.III, Pehlke, R.D., “Equilibrium between Sulfur and Titanium in Liquid Iron”, Metall. 

Trans. B, 18(B), 681-685 (1987) (Experimental, Thermodyn., *, 14) 

[1988Rag] Raghavan, V., “The Fe-S-Ti (Iron-Sulphur-Titanium) System” in “Phase Diagrams of Ternary Iron 

Alloys”, Indian Inst. Metal., Calcutta, 2, 299-306 (1988) (Crys. Structure, Phase Diagram, Phase 

Relations, Review, *, #, 22) 

[1991Mak] Makovetskii, G.I., Yanushkevich, K.I., “Structure and Magnetic Properties of Solid Solutions of Iron 

Sulphide-Titanium Sulphide System” (in Russian), Fiz. Tverd. Tela, 33(11), 3280-3283 (1991) (Experimental, 

Phase Relations, Magn. Prop., 8) 

[1995Bou] Bouchard, D., Bale, C.W., “Simultaneous Optimization of Thermochemical Data for Liquid Iron 

Alloys Containing C, N, Ti, Si, Mn, S, and P”, Metall. Mater. Trans. B, 26B, 467-484 (1995) (Phase 

Relations, Theory, Thermodyn., #, 85) 

[2001Sud] Sudavtsova, V.S., Sharkina, N.O., Kudin, V.G., “Thermodynamic Properties of the Liquid Melts in the 

Fe-S and Fe-S-Metals Systems”, Russ. J. Phys. Chem., 75(7), 1061-1064 (2001), translated from Zh. Fiz. 

Khim., 75(7), 1178-1181 (2001) (Thermodyn., Experimental, 13) 

[2004Kim] Kim, E.C., “Crystallographic and Magnetic Properties of Iron Sulfides Doped with 3d Transition 

Metals”, J. Mater. Sci. Letter., 19, 693-694 (2000) (Crys. Structure, Magn. Prop., Experimental, 8) 

[2005Nam] Nam, H.D., Kim, E.C., Han, J.S., “Mössbauer Study of Iron Sulfides Doped with 3d-Transition Metals”, 

Solid State Commun., 135(5), 327-329 (2005) (Crys. Structure, Magn. Prop., Experimental, 8) 


(1990) 





MSIT 1 

DOI: 10.1007/978-3-540-70890-2_26 

ß Springer 2009

Iron – Silicon – Titanium 


Wei Xiong, Yong Du, Chao Zhang 

Introduction 

The major contributions to the determination of the phase equilibria in the Fe-Si-Ti system 

are due to [1938Vog, 1956Ben, 1966Mar, 2003Loe]. The phase equilibria of the Fe-Si-Ti 

system were first investigated by [1938Vog], whose work was briefly reviewed by [1949Jae]. 

A liquidus projection was constructed in the Fe-TiFe 2-τ 2-FeSi region [1938Vog]. [1956Ben] 

(and apparently [1954Ben]) determined the austenitic phase transformation temperature to 

establish the limit of the austenitic iron region in the Fe-Si-Ti system. The isothermal section 

at 800˚C previously constructed by [1966Mar] was recently modified by [2003Loe], who also 

presented isothermal sections at 1150 and 1000˚C. 

So far, seven stable ternary compounds were reported: τ 1 (TiFeSi 2)[1966Mar, 1967Mar, 

1968Mar, 1982Ste, 1982Yar, 1990Ang, 2005Sai], τ 2 (TiFeSi) [1938Vog, 1965Mar, 1966Fre, 

1966Mar, 1967Far, 1967Mar, 1968Mar, 1970Jei, 2003Loe, 2005Sai], τ 3 (TiFe 4Si 3)[1966Mar, 

1974Ste, 2003Loe], τ 4 (TiFe 7Si 2)[2003Loe], τ 5 (Ti 46Fe 10Si 44) [1966Mar], τ 6 (Ti 45Fe 15Si 40) 

[1966Mar], and τ 7 [1993Jud, 1997Boe]. Further work is needed to determine the crystallographic 

data of τ 5 and τ 6. In addition, four metastable ternary phases, TiFe 2Si [1970Jac, 

1972Jac, 1977Nic1, 1977Nic2], Ti 2Fe 1–xSi x (0.03

2 27 

Fe–Si–Ti 

parameters for the λ Ti(Fe 1–xSi x) 2 phase with x value of 0, 0.074, 0.255, and 0.375, respectively. 

Recently, using X-ray diffraction, optical microscopy and first principles calculations, 

[2007Yan] performed a systematic crystallographic investigation on the λ phase with x value 

of 0.25 and revealed that Si substitution for λ stabilizes the ternary Laves C14 phase with 

respect to the corresponding binary Laves phases. The first principles calculations by 

[2007Yan] showed that the λ Ti(Fe0.75Si0.25)2 phase is a very weak ferromagnet. 

The solubility of Fe in Ti5Si3 is about 4 at.% [1966Mar], and that of Ti in α1 is about 6.25 

at.% [1977Nic2]. These measured solubilities [1966Mar, 1977Nic2] were confirmed in the 

work of [2003Loe]. 

[1966Mar] first reported the τ 1 phase with an orthorhombic unit cell, and measured a 

density of 4.69 g·cm –3 . Employing single crystal X-ray diffraction, a comprehensive crystallographic 

study on τ 1 was carried out by [1982Ste], who predicted the density of τ 1 with a value 

of 5.078 g·cm –3 . 

The τ2 ternary compound found by [1938Vog], was firstly considered to have a hexagonal 

structure by [1966Mar, 1968Mar], but later corrected to be orthorhombic by [1970Jei], 

but often showing pseudohexagonal twinning. [1970Jei] determined the complete crystal 

structure of τ 2.[1966Mar] measured a density of 5.57 g·cm –3 for τ 2, while [1967Far] reported 

a lower experimental value of 5.46 g·cm –3 together with the measured melting point at 

1760 ± 20˚C for a single-phase τ 2 sample. Additionally, in the work of [1966Fre], τ 2 was 

observed to be resistant against oxidation in air up to 400˚C but oxidizing rapidly at much 

higher temperatures. 

In the work of [2005Sai], the Curie temperatures and saturation magnetizations of τ1 and 

τ2 were studied using a vibrating sample magnetometer. The τ1 phase showed a low saturation 

magnetization of 1.72·10 3 T and a Curie temperature of 644˚C. The τ 2 phase exhibits a 

saturation magnetization of 3.77·10 2 T and a Curie temperature of 455˚C. 

[1966Mar] found that the τ 3 phase has a similar crystal structure as TiCo 4Si 3. This was 

later confirmed by [1974Ste], who reported for the τ 3 phase a hexagonal unit cell, which 

was confirmed by [2003Loe]. It is worthy to mention that the phase τ 3 found at 800˚C by 

[1966Mar] was observed by [2003Loe] at the higher temperatures 1000 and 1150˚C only, but 

not at 800˚C. This may be because of insufficient annealing after leaving the temperature range 

of stability, either by [1966Mar] orby[2003Loe]. Thus, some experiment to clarify the 

temperature range of stability of τ 3 is desirable. 

By X-ray diffraction, [2003Loe] found a new phase, τ 4, at 1150˚C, and determined it to be 

isotypic to αMn with a mean lattice parameter of 883.7 pm. 

Phases τ 5 and τ 6 were reported by [1966Mar] in the experimental isothermal section at 

800˚C, but their crystal structures are still unknown. 

[1997Boe] prepared a "ternary intermetallic phase" Ti 25Fe 60Si 15 by sintering powdermixtures 

of the pure elements. The reported mass ratios of the elemental powders correspond 

to a formula Ti25Fe56Si19. [2003Loe] at 1150˚C found this composition to be inside the 

homogeneity range of the Laves phase λ Ti(Fe 1–xSi x) 2. Also [1997Boe] assumed the C14 

Laves phase structure for this phase, thus it must not be treated as an extra ternary phase. 

For the composition investigated [1997Boe] determined a melting temperature of 1470˚C and 

a Curie temperature of 212 ± 5˚C. 

A metastable TiFe 2Si phase in a Fe-7Si-1.75Ti (at.%) alloy was reported by [1970Jac, 

1972Jac, 1977Nic1, 1977Nic2], appearing as finely dispersed particles inside the λ phase. The 

TiFe2Si phase with the L21 structure is a metastable extension of the D03 (Fe3Si) phase with 

one of the two different Fe positions occupied by Ti. 



MSIT 1

[1992Man] found a commensurate phase in a melt-spun Ti 2Fe 1–xSi x (0.03 < x < 0.06) 

alloy, which is a metastable CsCl type phase with the lattice parameter close to 298 pm. A bcc 

metastable phase was found in the rapidly solidified Fe-4Si-68Ti (at.%) alloy by [1997Tiw], 

while [1997Tiw, 2003Man] reported an icosahedral phase in the rapidly solidified Fe-6Si-68Ti 

(at.%) alloy. The orientational relationship of the bcc phase with the icosahedral phase has 

been discussed by [1997Tiw]. 


Table 3 lists the experimentally observed invariant equilibria by [1938Vog, 1978Hao]. 

The liquid compositions are estimated from the liquidus drawing in [1987Rag] and should 

be considered as tentative only. 

Based on the results of [1938Vog], a reaction scheme (Fig. 1) for the Fe rich alloys was 

given by [1987Rag]. [1978Hao] identified a eutectic reaction with the temperature of 1210˚C 

and the composition of Fe-4.3Si-9.5Ti (mass%). Regarding the impure Ti used by [1938Vog] 

this eutectic may be identical to E 1 in Figs. 1, 2 and Table 3. 


The only study of the liquidus surface of the Fe-Si-Ti system is that of [1938Vog]. Although the 

Ti for alloy preparation was only 95% purity, and the melting losses were nearly 20 mass%, 

the experimental data of [1938Vog] still can provide a basis for understanding the solidification 

behavior of the Fe rich alloys of this system. In consequence, the liquidus surface in the 

Fe-TiFe 2-τ 2-FeSi region, which was constructed by [1938Vog] and modified by [1987Rag], is 

shown in Fig. 2. 


Fe–Si–Ti 27 

3 

[1956Ben] presented boundaries of the (αFe) range against the (αFe) + (γFe) two-phase field 

at seven different temperatures (1100, 1060, 1055, 1032, 1012, 980 and 960˚C). However, this 

figure is apparently problematic. Both phases, (αFe) and (γFe) are dilute and Henry’s law is 

still approximately valid at the compositions inside this figure. That means, that the kink-like 

changes of curvatures of the lines drawn by [1956Ben] are not realistic. They seem to be 

artifacts due to limits of the accuracy of the measurements and due to incompatibilities 

between the ends of the lines in the accepted binary Fe-Ti system and the ternary measurements. 

Figure 3 shows the boundaries presented by [1956Ben] modified in the present work in 

order to be consistent with Henry’s law. 

[2003Loe] measured the partial isothermal sections with less than 35 at.% Si at 1150, 1000, 

and 800˚C, which are shown in Figs. 4 to 6, respectively. The isothermal section at 800˚C 

(Fig. 6) is merged with the Si rich part reported by [1966Mar] and modified to reduce 

artificially large homogeneity ranges of the phases. 

All three isothermal sections are corrected slightly in order to agree with the accepted 

binary phase diagrams and to remove some violations of the Schreinmaker rule. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_27 

ß Springer 2009

4 27 

Fe–Si–Ti 


Seven of the eight measured vertical sections at Fe rich corner by [1938Vog] are in question, 

not only due to the high weight losses during the melting but also because phase relationships 

at 1150 and 1000˚C are inconsistent with those measured by [2003Loe]. Since the phase 

relationships for the vertical section from Fe94.8Si5.2 to Ti31Fe67.31Si3.69 (mass%) agree with 

those reported by [2003Loe], this section is presented in Fig. 7. 


In the work of [2007Yan], the enthalpy of formation of Ti(Fe 0.75Si 0.25) 2 measured by an 

isoperibolic calorimeter is –55.9 ± 1.6 kJ·mol –1 of atoms, which agrees well with the value of 

–52.6 kJ·mol –1 of atoms derived by a first principles calculation. 


The investigations of Fe-Si-Ti materials properties are summarized in Table 4. Magnetic 

properties of the ternary phases are described in the section Solid Phases. 

[1978Hao] reported that the eutectic in the Fe rich corner of the Fe-Si-Ti system could be 

suitable for development of materials for directionally solidified turbine blades operating up 

to 1150˚C, since its good oxidation resistance and attractive low specific gravity could meet 

several important criteria associated with the manufacture of the turbine blades. 

[1997Boe] reported that the powder-metallurgically produced Laves phase with the 

composition TiFeSi is a promising high temperature material. It has high strength and 

brittleness at room temperature and a good corrosion resistance against neutral and acidic 

aqueous solutions. 

[2001Ito] investigated the effect of Ti doping on the thermoelectric performance of hotpressed 

FeSi2(h), and did not find a significant influence on the thermoelectric properties. 

[2004Kim] investigated the as quenched amorphous Ti78Fe15Si7 alloy with a large supercooled 

liquid region (61 K). The tensile fracture strength for this amorphous alloy was 1318 

MPa and increased up to 1876 MPa for a volume fraction of 15% primary (βTi) phase. 

The work of [2003Loe, 2004Loe] found that the Fe-Si-Ti alloys could be strengthened by 

precipitation of the stable Laves phase λ, which is a hard and brittle intermetallic phase. The 

yield stress as well as the brittle-to-ductile transition temperature increases with the Ti content 

[2003Loe, 2004Loe]. Furthermore, [2004Loe] pointed out that a beneficial oxidation behavior 

is expected for ternary Fe-Si-Ti alloys with moderate Si and Ti contents. 

Miscellaneous 

Figure 8 shows the lattice parameter and unit cell volume of the λ phase versus Si content 

measured by [1966Mar, 1968Mar], who annealed the alloys at 800˚C for 3 months. The 

average magnetization and lattice parameter of the Ti xFe 2–xSi alloys (0 ≤⊊ x ≤⊊ 0.7) by 

[1977Nic1] are shown in Figs. 9 and 10, respectively. In the work of [1990Ang], Ti prefers to 

concentrate in τ1 during the precipitation when the overall Fe composition (in mass%) of the 



MSIT 1

synthetic alloys is much higher than that of Ti. Figure 11 shows the thermomagnetic curves of 

the τ 1 and τ 2 phases measured by [2005Sai]. In the work of [2005Ste], some general rules for 

the occurrence of the different Laves phase polytypes are derived from a study of experimental 

phase diagram of Fe-Si-Ti system. The study showed that the solubility of Si added to the Laves 

phase λ cannot simply be explained by size effects. 

. Table 1 

Investigations of the Fe-Si-Ti Phase Relations, Structures and Thermodynamics 



Range Studied 

[1938Vog] Thermal analysis, metallography Liquidus projection in the Fe-TiFe2 τ2-FeSi region 

[1956Ben] Dilatation measurement The austenitic iron region 

[1963Bar] X-ray diffraction λ, Ti(Fe1–xSix) 2 (x = 0, 0.074, 0.255, 

0.375) 

[1965Mar, 

1966Fre] 

X-ray diffraction τ2 [1966Mar] X-ray single crystal diffraction analysis, 

microstructural analysis 

[1967Far] X-ray diffraction, metallography, thermal 

analysis, density measurement. 

[1967Mar, 

1968Mar] 

X-ray diffraction, microstructural analysis τ1 and τ2 

[1970Jac] Electron microscopy, X-ray diffraction, 

electron probe microscopy 

[1970Jei] Metallography, single crystal X-ray diffraction τ 2 

Isothermal section at 800˚C, τ 1, τ 2, τ 3, 

τ 5, τ 6, the solubility of Fe in Ti 5Si 3 

Reaction temperature, melting 

temperature and density of τ 2 

TiFe 2Si 

[1972Jac] Transmission electron microscopy TiFe2Si [1974Ste] Single crystal X-ray diffraction τ3 [1977Nic1, 

1977Nic2] 

Vibrating sample magnetometry, X-ray 

diffraction 

The magnetization and lattice 

parameter of TiFe 2Si 

[1978Hao] Differential thermal analysis, energy dispersive The eutectic temperature of the Fe- 

X-ray analysis 

4.3Si-9.5Ti (mass%) alloy 

[1982Ste, 

1982Yar] 

Single crystal X-ray diffraction τ1 [1992Man] X-ray diffraction, transmission electron 

microscopy, energy dispersive X-ray analysis 

[1997Boe] Specific magnetization measurement, 

calorimeter and high temperature dilatometer 

[1997Tiw, 

2003Man] 



X-ray diffraction, transmission electron 

microscopy 

MSIT 1 


Ti 2Fe 1–xSi x (0.03

6 27 

Fe–Si–Ti 



[2003Loe] X-ray diffraction, differential thermal analysis, 

metallography, electron microscopy 

[2005Sai] X-ray diffraction, scanning electron 

microscopy, vibrating sample magnetometer 

[2007Yan] X-ray diffraction, optical microscopy, first 

principles calculation, isoperibolic calorimetry 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Range Studied 

τ 2, τ 3, τ 4, isothermal sections at 800, 

1000, 1150˚C 

Curie temperatures and saturation 

magnetization of τ 1 and τ 2 

Crystal structure and enthalpy of 

formation of λ, Ti(Fe 1–xSi x) 2 (x = 0.25) 

Lattice 

Parameters 


(βTi) cI2 a = 330.65 at 900˚C [Mas2] 

1670 - 882 Im3m 

W 

(αTi) hP2 a = 295.06 at 25˚C [Mas2] 

< 882 P63/mmc Mg 

c = 468.35 


1394 - 912 Fm3m 

Cu 

(αδFe) cI2 

(δFe) Im3m a = 293.15 pure Fe at 1390˚C [V-C2, Mas2] 

1538 - 1394 W 

(αFe) 

< 912 


(αSi) cF8 a = 543.06 at 25˚C [Mas2] 

< 1414 Fd3m 

C (diamond) 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


λ, Ti(Fe1–xSix) 2 hP12 Laves C14 phase 

P63/mmc 0 ≤ x ≤ 0.375 [1963Bar] 

MgZn2 a = 479.0 

c = 781.1 

at x =0[V-C2] 

TiFe2 a = 478.9 at x = 0.074 

< 1427 c = 779.6 

a = 479.7 

c = 775.7 

at x = 0.255 

a = 480.3 

c = 772.5 

at x = 0.375 

a = 478.0 

c = 765.2 

[1977Nic2] 

a = 480.45 ± 0.034 at x = 0.25 [2007Yan] 

c = 776.86 ± 0.08 

a = 479.7 ± 0.2 at 800˚C, 41.0 - 67.0 at.% Fe, 0 - 27.5 at.% Si, 

c = 773.8 ± 0.9 24.3 - 35.6 at.% Ti 

at 1000˚C, 24.5 - 72.3 at.% Fe, 0 - 26.3 at.% Si, 

23.1 - 39.6 at.% Ti 

at 1150˚C, 40.8 - 72.3 at.% Fe, 0 - 27.1 at.% Si, 

22.4 - 44.9 at.% Ti [2003Loe] 

TiFe cP2 [Mas2] 

< 1317 Pm3m a = 297.6 [V-C2] 

CsCl a = 298.1 ± 0.1 at 800˚C, 46.6 - 50.3 at.% Fe, 0 - 18.4 at.% Si, 

49.7 - 52.2 at.% Ti 

at 1000˚C, 46.6 - 50.3 at.% Fe, 0 - 1.3 at.% Si, 

49.7 - 52.8 at.% Ti 

at 1150˚C, 0 - 1.7 at.% Si [2003Loe] 

TiSi2 oF24 [Mas2] 

< 1500 Fddd a = 826.71 [V-C2] 

TiSi2 b = 480.00 

c = 855.05 

TiSi oP8 [Mas2] 

< 1570 Pmm2 or 

Pnma 

a = 654.4 [V-C2] 

b = 363.8 

FeB c = 499.7 

Ti5Si4 tP36 [Mas2] 

< 1920 P41212 a = 670.2 [V-C2] 

Zr5Si4 c = 1217.4 



MSIT 1 


7 

DOI: 10.1007/978-3-540-70890-2_27 

ß Springer 2009

8 27 

Fe–Si–Ti 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


Ti5Si3 hP16 [Mas2] 

< 2130 P63/mcm a = 746.10 ± 0.3 [V-C2] 

Mn5Si3 c = 515.08 ± 0.1 

at 800˚C, 0 - 3.1 at.% Fe, 35.8 - 38.7 at.% Si, 

61.2 -64.2 at.% Ti 

at 1000˚C, 0 - 3.9 at.% Fe, 33.3 - 38.8 at.% Si, 

61.2 - 64.2 at.% Ti 

at 1150˚C, 0 - 1.7 at.% Fe [2003Loe] 

Ti3Si tP32 [Mas2] 

< 1170 P42/n a = 1019.6 [V-C2] 

Ti3P c = 509.7 

α1, Fe3Si cF16 D03, 11.0 to 30.0 at.% Si [1982Kub] 

≤ 1235 Fm3m a = 565.0 [V-C2] 

BiF3 The solubility of Ti in α1 is not less than 6.25 

at.% [1977Nic2] 

at 800˚C, 64.2-84.8 at.% Fe, 15.2-27.3 at.% Si, 

0-10.8 at.% Ti 

at 1000˚C, 68.0-81.2 at.% Fe, 0-7.3 at.% Ti at 

1150˚C, 0 - 6.2 at.% Ti [2003Loe] 

α2, Fe-Si cP2 B2, 10.0 to 22.0 at.% Si [1982Kub] 

≤ 1280 Pm3m a = 281 [V-C2] 

CsCl at 800˚C 0 - 0.9 at.% Ti 

at 1150˚C 0 - 2.1 at.% Ti [2003Loe] 

β, Fe2Si hP6 at 1150˚C, 0 - 2.9 at.% Ti [2003Loe] 

1212 - 1040 P3m1 ~33.0 to ~34.3 at.% Si [1982Kub] 

Fe2Si a = 405.2 ± 0.2 

c = 508.55 ± 0.03 

[V-C2] 

Fe5Si3 hP16 [1982Kub] 

1060 - 825 P63/mcm a = 675.9 ± 0.5 [V-C2] 

Mn5Si3 c = 472.0 ± 0.5 at 1000˚C 57.0 - 62.5 at.% Fe, 37.1 - 37.5 at.% 

Si, 0 - 5.9 at.% Ti 

at 1150˚C 56.5 -57.9 at.% Fe, 37.2 - 37.5 at.% 

Si, 2.9 - 4.6 at.% Ti [2003Loe] 


< 1410 P213 FeSi 

a = 451.7 ± 0.5 [V-C2] 

ζα, FeSi2(h) tP3 69.5 to 73.5 at.% Si [1982Kub] 

1220 - 937 P4/mmm a = 269.01 [V-C2] 

FeSi2 c = 513.4 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Lattice 

Parameters 


9 

ζβ, FeSi2(r) oC48 66.7 at.% Si [1982Kub] 

< 982 Cmca a = 986.3 ± 0.7 [V-C2] 

FeSi2 b = 779.1 ± 0.6 

c = 783.3 ± 0.6 

* τ1, TiFeSi2 oP48 at 800˚C 50 at.% Si, 20-29 at.% Ti 

Pbam [1966Mar] 

TiMnSi2 a = 861.37 ± 0.08 

b = 953.4 ± 0.1 

c = 763.96 ± 0.04 

[1982Ste] 

a = 856.0 

b = 953.0 

c = 764.0 

[1966Mar, 1967Mar, 1968Mar] 

a = 858.7 ± 0.3 [1982Yar] 

b = 947.9 ± 0.5 

c = 762.6 ± 0.2 

Curie temperature is 644˚C [2005Sai] 

* τ2, TiFeSi oI36 at 1150˚C 30.2 to 37.3 at.% Fe, 32.7 to 

< 1760 ± 20 Ima2 

33.0 at.% Si, 30.0 to 37.0 at.% Ti 

TiFeSi 

[2003Loe] 

at 1000˚C 30.3 to 35.3 at.% Fe, 32.3 to 37.2 

at.% Si, 29.9 to 37.2 at.% Ti [2003Loe] 

a = 699.7 ± 0.2 at 800˚C 30.3 to 35.7 at.% Fe, 32.6 to 32.8 at.% 

b = 1083.0 ± 0.5 Si, 31.6 to 37.0 at.% Ti [2003Loe] 

c = 628.7 ± 0.2 

a = 699.9 ± 0.4 

b = 1073.0 ± 0.6 

[1970Jei] 

c = 628.8 ± 0.6 [2003Loe] 

Curie temperature is 455˚C [2005Sai] 

* τ3, TiFe4Si3 hP168 [1966Mar] 

> 800 P6/mmm a = 1720.6 

c = 798.1 

[1974Ste] 

a = 1708.9 

c = 797.1 

[2003Loe] 

* τ4, TiFe7Si2 cI58 at 1150˚C 67.4 to 68.4 at.% Fe, 20.9 to 21.7 

1233 - ~1000 I43m 

at.% Si, 10.7 to 10.9 at.% Ti; 

αMn at 1000˚C 68.9-69.0 at.% Fe, 19.8 to 20.0 at.% 

Si, 11.1 to 11.2 at.% Ti [2003Loe] 

a = 883.7 [2003Loe] 

* τ5,Ti46Fe10Si44 - - [1966Mar] 

* τ6,Ti45Fe15Si40 - - [1966Mar] 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_27 

ß Springer 2009

10 27 

Fe–Si–Ti 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


TiFe2Si (m) cF16 Metastable extension of the D03 α1 phase, 

Fm3m 

Fe3Si a = 570.9 [1977Nic2] 

Ti68Fe28Si4 (m) c* a = 1130.0 [1997Tiw], metastable bcc phase 

Ti68Fe26Si6 (m) - - [1997Tiw, 2003Man], metastable icosahedral 

phase 

Ti2Fe1–xSix (m) cP2 a = 298.0 0.03

. Table 4 

Investigations of the Fe-Si-Ti Materials Properties 


[1978Hao] Oxidation measurement water 

displacement method 

[1997Boe] Archimedes technique, hardness and 

fracture toughness measurement, 

indentation crack length method, 

ultrasonic measurement, 

potentiodynamic measurement 

[2001Ito] Ordinary DC method and laser flash 

thermal constant analyzer 

[2003Loe, 

2004Loe] 

Vickers hardness and microhardness 

testing, uniaxial compression, weighting, 

four-point bending test 


oxidation resistance, density 

Density, mechanical properties of τ 7 (up to 

600˚C). The elastic constants, Young’s 

modulus, Shear modulus, and Poisson’s 

ratio, corrosion resistance of τ 7 against 

neutral and acidic aqueous solutions 

The electrical resistivity, thermoelectric 

power, and thermal conductivity from 

room temperature to 900˚C 

Hardness, yield stress, oxidation 

resistance, ductility and brittle-to-ductile 

transition temperature 

[2004Kim] Tensile testing Tensile fracture strength of the 

amorphous alloy Ti 78Fe 15Si 7 



MSIT 1 

11 

DOI: 10.1007/978-3-540-70890-2_27 

ß Springer 2009

12 27 

Fe–Si–Ti 

. Fig. 1 

Fe-Si-Ti. Partial reaction scheme of the Fe corner 



MSIT 1

. Fig. 2 

Fe-Si-Ti. Partial liquidus surface projection in the Fe corner 



MSIT 1 


13 

DOI: 10.1007/978-3-540-70890-2_27 

ß Springer 2009

14 27 

Fe–Si–Ti 

. Fig. 3 

Fe-Si-Ti. Joint solubility of both Ti and Si in (αFe) at different temperatures 



MSIT 1

. Fig. 4 

Fe-Si-Ti. Partial isothermal section at 1150˚C 



MSIT 1 


15 

DOI: 10.1007/978-3-540-70890-2_27 

ß Springer 2009

16 27 

Fe–Si–Ti 

. Fig. 5 




MSIT 1

. Fig. 6 




MSIT 1 


17 

DOI: 10.1007/978-3-540-70890-2_27 

ß Springer 2009

18 27 

Fe–Si–Ti 

. Fig. 7 

Fe-Si-Ti. Vertical section from Fe 94.8Si 5.2 to Ti 31Fe 67.31Si 3.69 (mass%), plotted in at.% 



MSIT 1


. Fig. 8 

Fe-Si-Ti. Lattice parameters and unit cell volume of the λ Ti(Fe 1–xSi x) 2 phase vs Si content 



MSIT 1 

19 

DOI: 10.1007/978-3-540-70890-2_27 

ß Springer 2009

20 27 

Fe–Si–Ti 

. Fig. 9 

Fe-Si-Ti. The average magnetization of the Ti xFe 3–xSi alloys (0≤x≤0.7) vs outer electron 

concentration 



MSIT 1


21 

. Fig. 10 

Fe-Si-Ti. The lattice parameter of the Ti xFe 3–xSi alloys (0≤x≤0.7) vs outer electron concentration 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_27 

ß Springer 2009

22 27 

Fe–Si–Ti 

. Fig. 11 

Fe-Si-Ti. Thermomagnetic curves of τ 2 and τ 1 



MSIT 1

References 


23 

[1938Vog] Vogel, R., Schlueter, W., “The Iron Corner of the Iron-Silicon-Titanium System” (in German), Arch. 

Eisenhuettenwes., 12(4), 207–212 (1938) (Phase Diagram, Experimental, #, *, 10) 

[1949Jae] Jaenecke, E., “Fe-Si-Ti” (in German), Kurzgefasstes Handbuch aller Legierungen, Winter Verlag, Heidelberg, 

622–623 (1949) (Phase Diagram, Review, 1) 

[1954Ben] Bentle, G.G., “γ-loop Studies in the Fe-Si and Fe-Si-Ti Systems”, Ph.D. Thesis, Vanderbilt Univ., U.S.A., 

(1954) (Phase Diagram, Experimental) 

[1956Ben] Bentle, G.G., Fishel, W.P., “γ-Loop Studies in the Fe-Si and Fe-Si-Ti Systems”, Trans. AIME, 206, 

1345–1348 (1956) (Phase Diagram, Experimental, #, 5) 

[1963Bar] Bardos, A.M., Bardos, D.I., Beck, P.A., “The Effective Atomic Radius of Silicon in Ternary Laves Phase 

Alloys”, Trans. Metall. Soc. AIME, 227, 991–993 (1963) (Crys. Structure, Experimental, 12) 

[1965Mar] Markiv, V.Y., Voroshilov, Y.V., Gladyshevskii, E.I., “Ternary Laves Phases in the Systems Ti-Co-Si(Ge) 

and Zr-Fe-Si(Ge)”, Inorg. Mater., 1(6), 818–821 (1965), translated from Izv. Akad. Nauk SSSR, Neorg. 

Mater., 1(6), 890–893 (1965) (Crys. Structure, Experimental, 5) 

[1966Fre] Freundlich, W., Farrokhi-Mochai, N., “Two Intermetallic Ternary Phases-ZrFeSi and TiFeSi” (in 

French), Compt. Rend. Acad. Sci. Paris, 262, 1000–1001 (1966) (Crys. Structure, Experimental, 0) 

[1966Mar] Markiv, V.Ya., Lysenko, L.A., Gladyshevskii, E.I., “Titanium-Iron-Silicon System”, Russ. J. Inorg. Chem., 

2(11), 1713–1716 (1966), translated from Izv. Akad. Nauk SSSR, Neorg. Mater., 2(11) 1980–1984 (1966) 

(Crys. Structure, Phase Diagram, Phase Relations, Experimental, #, *, 15) 

[1967Far] Farrokhi-Mochai, N., “A Study of the Solid Phases in the Fe-Si-Ti, Fe-Si-Zr, and Fe-Si-V Systems” 

(in French), Rev. Chim. Miner., 4, 1–25 (1967) (Crys. Structure, Phase Diagram, Experimental, Phys. 

Prop., 0) 

[1967Mar] Markiv, V.Y., Gladyshevskii, E.I., Skolozdra, R.V., Kripyakevich, P.I., “Ternary Compounds of the RXX 2 

Type in the Ti-V(Fe, Co, Ni)-Si and Similar Systems”, Dop. Akad. Nauk Ukrain. SSR, (A)3, 266–269 


[1968Mar] Markiv, V.Y., Gladyshevskii, E.I., Kripyakevich, P.I., Fedoruk, T.I., Lysenko, L.A., “A Study of the Phase 

Equilibria and Crystal Structures of Compounds in the Ti-Fe(Co,Ni)-Si Systems” (in Russian), Diagrammy 

Sostoyaniya Metallich. Sistem, Nauka, Moscow, 137–145 (1968) (Crys. Structure, Phase Diagram, 

Phase Relations, Experimental, 29) 

[1970Jac] Jack, D.H., “Intermetallic Precipitate in an Fe-Ti-Si Alloy”, Met. Sci. J., 4, 22–24 (1970) (Crys. Structure, 


[1970Jei] Jeitschko, W., “The Crystal Structure of TiFeSi and Related Compounds”, Acta Crystallogr., Sect. B: 

Struct. Crystallogr. Crys. Chem., B26, 815–822 (1970) (Crys. Structure, Experimental, 24) 

[1972Jac] Jack, D.H., Honeycombe, R.W.K., “Age Hardening of an Fe-Ti-Si Alloy”, Acta Metall., 20, 787–796 

(1972) (Phase Relations, Experimental, Mechan. Prop., 30) 

[1974Ste] Steinmetz, J., Albrecht, J.M., Malaman, B., “A New Family of Ternary Silicides of the General Formula 

TT 4Si 3 (T = Ti, Nb, Ta; T = Fe, Co, Ni)” (in French), Compt. Rend. Acad. Sci. Paris, 279C, 1119–1120 


[1977Nic1] Niculescu, V., Budnick, J.I., “Limits of Solubility, Magnetic Properties and Electron Concentration in 

Fe 3–xT xSi System”, Solid State Commun., 24(9), 631–634 (1977) (Crys. Structure, Experimental, Theory, 


[1977Nic2] Niculescu, V., Burch, T.J., Raj K., Budnick, J.I., “Properties of Heusler-Type Materials Fe 2TiSi and 

FeCo 2Si”, J. Mag. Mag. Mater., 5(1), 60–66 (1977) (Crys. Structure, Experimental, 12) 

[1978Hao] Haour, G., Mollard, F., Lux, B., Wright, G., “New Eutectics Based on Fe, Co or Ni”, Z. Metallkd., 69(1), 

26–32 (1978) (Phase Relations, Experimental, Interface Phenomena, Mechan. Prop., Morphology, Phys. 

Prop., 24) 


(1982) (Phase Diagram, Review, #, *, 23) 

[1982Ste] Steinmetz, J., Venturini, G., Roques, B., Engel, N., Chabot, B., Parthe, E., “TiMnSi 2 and TiFeSi 2 with 

New Orthorhombic-Type Structure”, Acta Crystallogr., Sect. B: Struct. Crystallogr. Crys. Chem., B38, 


[1982Yar] Yarmolyuk, Y.P., Sikiritsa, M., Akselrud, L.G., Lysenko, L.A., Gladyshevskii, E.I., “The Crystal Structure 

of ZrCrSi 2”, Sov. Phys. Crystallogr., 27(6), 652–653 (1982), translated from Kristallografiya, 27, 




MSIT 1 

DOI: 10.1007/978-3-540-70890-2_27 

ß Springer 2009

24 27 

Fe–Si–Ti 

[1987Rag] Raghavan, V., “The Fe-Si-Ti (Iron-Silicon-Titanium) System” in “Phase Diagrams of Ternary Iron Alloys”, 

Ind. Inst. Techn., Delhi, Vol. 1, 65–72 (1987) (Crys. Structure, Phase Diagram, Phase Relations, Review, 

#, *, 14) 

[1990Ang] Anglezio, J.C., Servant, C., “Characterization of Metallurgical Grade Silicon”, J. Mater. Res., 5, 


[1992Man] Mandal, P., Mandal, R.K., Tiwari, R.S., Srivastava, O.N., “Commensurate Ordering in Rapidly 

Solidified Ti-Fe-Si Alloys”, Phys. Rev. B, Condens. Matter, 45(13), 7521–7524 (1992) (Crys. Structure, 


[1993Jud] Juda, T. (in German), Thesis, Technical Univ. Dresden (1990) as quoted by [1997Boe] 

[1997Boe] Boehm, A., Pischang, K., Kieback, B., “Processing and Properties of the New Intermetallic Phase 

Fe 12Ti 5Si 3”, Metall, 51(10), 554–556 (1997) (Crys. Structure, Experimental, Magn. Prop., Phys. Prop., 5) 

[1997Tiw] Tiwari, R.S., Mandal, P., Srivastava, O.N., “Quasicrystalline and Related Phases in Titanium Based Alloy 

Systems”, Prog. Cryst. Growth Charact., 34, 271–285 (1997) (Crys. Structure, Experimental, 28) 


Performance of β-FeSi 2”, J. Alloys Compd., 315, 251–258 (2001) (Crys. Structure, Experimental, Electr. 

Prop., 18) 

[2003Loe] Loeffler, F., “Investigation of the Ternary Systems Fe-Si-Mg and Fe-Si-Ti: Phase Equilibria and Mechanical 

Properties of the Alloys” (in German), Ph.D. Thesis, RWTH Achen, Germany (2003) (Crys. Structure, 

Morphology, Phase Diagram, Experimental, Mechan. Prop., #, *, 95) 

[2003Man] Mandal, P., “Structural Disorder in Ti-Fe-Si Icosahedral Quasicrystal”, J. Alloys Compd., 361, 96–101 

(2003) (Crys. Structure, Morphology, Experimental, 23) 

[2004Kim] Kim, K.B., Ko, B.C., Pak, S.J., “Formation of Nanocrystals in Ti 78Fe 15Si 7 Amorphous Alloy with a Wide 

Supercooled Liquid Region”, Mater. Sci. Eng. A, 366(2), 421–425 (2004) (Crys. Structure, Morphology, 

Experimental, Mechan. Prop., 14) 

[2004Loe] Loeffler, F., Palm, M., Sauthoff, G., “Iron-Rich Iron-Titanium-Silicon Alloys with Strengthening 

Intermetallic Laves Phase Precipitates”, Steel Res. Int., 75(11), 766–772 (2004) (Phase Relations, Morphology, 

Experimental, Mechan. Prop., Phys. Prop., 38) 

[2005Sai] Saito, T., Wakabayashi, K., Yamashita, S., Sasabe, M., “Production of Fe-Ti-Si Alloys From the 

Ilmenite Ore and Their Magnetic Properties”, J. Alloys Compd., 388, 258–261 (2005) (Experimental, 


[2005Ste] Stein, F., Palm, M., Sauthoff, G., “Structure and Stability of Laves Phases Part II – Structure Type 

Variations in Binary and Ternary Systems”, Intermetallics, 13(10), 1056–1074 (2005) (Crys. Structure, 

Phase Relations, Theory, 249) 

[2007Yan] Yan, X.L., Chen, X.Q., Grytsiv, A., Witusiewicz, V.T., Rogl, P., Podloucky, R., Giester, G., “On the 

Ternary Laves Phases {Sc,Ti} 2M 3Si (M = Cr, Mn, Fe, Co, Ni) with MgZn 2-Type”, J. Alloys Compd., 429, 

10–18 (2007) (Cry. Structure, Thermodyn., Calculation, Experimental, Review, Electronic Structure, 



(1990) 





MSIT 1

Iron – Silicon – Vanadium 


Honghui Xu, Yong Du, Weihua Sun, Lijun Zhang 

Introduction 

Fe–Si–V 28 

1 

A critical evaluation of the Fe-Si-V system was first performed by [1982Ray], and subsequently 

abridged in [1988Ray]. The experimental data reviewed by both [1982Ray] and [1988Ray] 

on this system include: (1) a liquidus projection in the Fe-FeSi-VSi 2-V region by [1940Vog]; 

(2) the isothermal section at 1000˚C for the entire composition range by [1965Gla] and that at 

1100˚C for Si poor alloys (up to 40 at.% Si) by [1966Bar]; and (3) the homogeneity range of 

the Fe-V σ phase into the Fe-V-Si ternary system at 1175˚C by [1960Gup]. Later, the Fe-Si-V 

system was partially updated by [1994Rag, 2002Rag]. [1994Rag] presented two partial isothermal 

sections in the order-disorder region of Fe rich alloys at 800 and 700˚C that had been 

originally presented by [1989Koz]. [2002Rag] reproduced a vertical section at 5 at.% V and 

0-25 at.% Si for temperatures between 1200-600˚C that was based on the results of [1994Koz]. 

The first investigation of the phase equilibria in the Fe-Si-V system was carried out by 

[1940Vog], who examined the liquidus surface in the region of Fe-FeSi-VSi 2-V by thermal 

analysis, and a limited metallographic observation of the solid alloys. 20 g samples were 

prepared from Krupp WW iron, silicon (described as “technical”) from Kallbaum and 

ferrovanadium alloys containing 60 and 53 mass% V, respectively. No specific details with 

regard to purity were given. Some 80 ternary alloys were examined, the compositions of which 

lay on composition lines from the silicon corner to the compositions 10, 20, 30, 40, 50 and 60 

mass% V on the Fe-V axis. The vertical section through FeSi to VSi 2 was also investigated by 

[1940Vog]. A ternary compound T (Fe 4V 5Si 4) was reported for the first time, and its 

incongruent formation was established. [1940Vog] presented the liquidus surface in the region 

of Fe-FeSi-VSi 2-V and seven vertical sections. 

It should be noted that the liquidus projection proposed by [1982Ray] based on [1940Vog] 

that had been corrected in accordance with later versions of the binary phase diagrams must be 

further modified in order to bring the phase relationships into agreement with the currently 

accepted binary phase diagrams, especially with regard to the Si-V system. The V 3Si phase, 

which melts congruently according to the currently accepted V-Si phase diagram, was assumed 

by [1982Ray] to form through a peritectic reaction of V 5Si 3 +LÐ V 3Si. The V 6Si 5 phase, 

which is a stable compound and forms through the peritectic reaction V 5Si 3 +LÐ V 6Si 5, was 

not indicated on the liquidus surface proposed by [1982Ray]. 

The first investigation of the solid-state equilibria was carried out by [1960Gup], who 

determined the homogeneity range of the σ phase at 1175˚C. The σ phase was found to be 

strongly stabilized by Si, and the σ homogeneity range increased markedly with increasing 

silicon content up to about 4 mass%, after which it decreased with further silicon addition. 

[1965Gla] determined the isothermal section of the Fe-Si-V system at 1000˚C over the 

entire composition range. The Fe-Si-Valloys were prepared from silicon (99.96% Si), carbonyl 

iron (≥99.99% Fe) and vanadium (99.62% V). Alloy samples in the as cast and annealed 

condition (annealed at 1000˚C for 100 h, at 1200˚C for 30 h and at 800˚C for 500 h) were 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_28 

ß Springer 2009

2 28 

Fe–Si–V 

examined by metallography and X-ray analysis. Three ternary compounds were shown to exist 

at 1000˚C. Nevertheless, it should be noted that the V 6Si 5 phase, which is stable at 1000˚C 

according to the recently accepted Si-V phase diagram [Mas2], was not present on the 

isothermal section at 1000˚C given by [1965Gla]. The VSi 2 phase, which is regarded as 

approximately stoichiometric, was shown to have some homogeneity. 

[1966Bar] established a partial isothermal section at 1100˚C up to a silicon content of 

40 at.% Si. The same three ternary phases were reported to exist at 1100˚C. 

The three ternary compounds mentioned above were reported by [1960Gup, 1961Bar, 

1961Gla, 1962Gla, 1965Gla, 1966Bar, 1971Sho, 1976Sho]. These phases were given as the 

R-, χ-, and D- or δ phases. By comparing the composition of D- or δ phase with that of the T 

phase proposed by [1940Vog], it would seem that they are one and the same. For convenience, 

the first reported ternary compound, originally called T by [1940Vog] is designated τ 1 here. 

Similarly, the remaining two ternary compounds R and χ are referred to as τ 2 and τ 3, 

respectively. 

The influence of V on the order-disorder transitions in the Fe-Si bcc phase and the phase 

transformation of the Fe rich Fe-Si-V alloys were studied by [1976Nic, 1985Wan, 1988Fuk, 

1989Koz, 1990Zha, 1994Koz, 2004Doi, 2004Nis, 2006Doi]. The phase equilibria involving Fe 

rich alloys were investigated at 800˚C by [1989Koz, 1994Koz], 700˚C by [1989Koz], and 600˚C 

by [1994Koz]. [1994Koz] also determined a vertical section at 5 at.% in the temperature range 

1200-600˚C, where the (α + α 1) field dominates at lower temperatures and the α 2 phase field is 

stable only above 1050˚C. 

[1974Bur, 1975Pic] measured the site occupancy of V in substituted Fe3Si, using neutron 

diffraction studies. [1976Ber, 1977Nic, 1983Bus, 1991Kud, 2003Kaw, 2004Nas, 2004Nis, 

2006Cui] studied the crystal structures and various physical properties of ternary Fe 3–xV xSi 

(0 ≤ x ≤ 1) alloys having the Heusler structure because of their interesting electronic and 

magnetic properties. 

[1983Roz] measured the mixing enthalpies and component activities of ternary melts at 

1627˚C. 

Information on the investigation of phase equilibria and thermodynamics of the Fe-Si-V 

system are summarized in Table 1. 


The Fe-V binary system is accepted from [Mas2]. The Fe-Si phase diagram is taken from 

[1982Kub]. The V-Si phase diagram is taken from [Mas2] but with a slight modification owing 

to the work of [2007Zha]. [2007Zha] reinvestigated the stability of V 6Si 5 via a hybrid approach 

of Calphad, XRD and first principle methods. According to [2007Zha], the decomposition 

temperature for the reaction V6Si5 Ð V5Si3 + VSi2 is 460˚C, which is significantly lower than 

the temperature of 1160 ± 100˚C recommended in [Mas2]. Figure 1 presents the Si-V phase 

diagram from [2007Zha]. 


The crystallographic data of the phases in the Fe-Si-V system and their temperature ranges of 

stability are listed in Table 2. 



MSIT 1


3 

Three ternary phases have been found in the system. A fourth compound was mentioned 

by [1965Gla], however no information on its composition or crystal structure was given. 

The τ 1 ternary phase was established for the first time by [1940Vog], and later its existence 

was confirmed by [1965Gla, 1966Bar] at 1000 and 1100˚C. The τ 1 phase is isostructural 

with tetragonal Mn 5Si 2. It exists in a rather wide composition range, from 32 to 45 at.% Fe 

at 1100˚C and from 30 to 40 at.% Fe at 1000˚C, according to [1966Bar] and [1965Gla]. Its 

lattice parameters at a composition of Fe44V26Si30 were determined by [1971Sho]. Subsequently, 

the structure model for the τ1 phase was refined by [1976Sho] using a full-matrix least 

squares analysis and diffractometer data from the isotypic Mn 5Si 2 phase. 

There is good agreement in the studies of the composition and crystal structure of the τ 2 

phase, which has the rhombohedral structure, and it may be described in terms of a hexagonal 

unit cell. The crystal structure of the τ 2 phase was determined by [1961Bar] at the composition 

of Fe 41V 37Si 22, and by [1965Gla] at the composition of Fe 2V 2Si. The extent of the homogeneity 

range of the τ 2 phase changes and shifts as the temperature decreases. At 1000˚C the phase 

contains more Si and less Fe than at 1100˚C [1965Gla, 1966Bar]. No information is available 

concerning the formation of the τ2 phase. 

[1961Gla, 1965Gla, 1966Kim, 1967Far] made contributions to the determination of the 

crystal structure of the τ 3 phase, Fe 5V 3Si 2, which was established for the first time by 

[1961Gla]. There is good agreement over its composition and crystal structure. The τ 3 phase 

has the αMn type structure and exists in a rather wide composition range, from 33 to 47 at.% 

Fe at 1100˚C and from 32 to 44 at.% Fe at 1000˚C, according to [1966Bar] and [1965Gla]. The 

τ 3 phase and the above-mentioned τ 2 phase were observed by [1965Gla] in as-cast alloys 

quenched after melting in a resistance furnace, and also in arc-melted specimens. Therefore, 

crystallization of both of these phases from the liquid is not improbable. 

[1967Far] reported the existence of the ternary phases Fe 0.175VSi and Fe 3VSi as well as 

Fe 2V 2Si (τ 2) and Fe 5V 3Si 2 (τ 3). The Fe 3VSi which has a structure similar to αMn and a 

composition coinciding with that of the τ 2 phase, is ferromagnetic with a Curie point at 

318˚C. The Fe 0.175VSi phase is very likely to be the solid solution of Fe in V 6Si 5, as its atomic 

silicon content is approximately equal to that of the stable V 6Si 5 phase in the Si-V binary 

system. 

[1984Sin] reported a ternary phase at 400˚C around the composition of Fe50V25Si25 with 

an orthorhombic structure and lattice parameters a = 751.7, b = 721.4, c = 691.7. At higher 

temperatures (1000 and 1100˚C), this phase is not stable because of the existence of the solid 

solution of V in Fe 3Si in this composition range. For the same composition (Fe 2VSi), 

[1995Kaw] reported the αMn structure type at 300 K (designated here as τ 4), which exhibits 

a tetragonal deformation at low temperatures. Subsequently, [1998Kaw] suggested that Fe 2VSi 

phase has a tetragonally distorted Heusler structure below 120 K, with an antiferromagnetic 

ordering. [2006Nas] reported that Fe 2VSi, which has the Heusler structure (L2 1) at room 

temperature, takes on the αMn structure (A2) above 1100˚C. A single-phase Fe2VSi alloy with 

a αMn structure type was produced by [2006Nas] using the single-roller melt-spinning 

technique under a purified argon atmosphere. When the sample was annealed at 800˚C, its 

structure transformed into the Heusler structure (L2 1). When annealed again at 1100˚C and 

quenched into ice, the structure of the sample almost returned to the αMn structure. This 

structural transformation is unusual because the high temperature phase takes more 

complex structure than the low temperature phase [2006Nas]. By means of neutron diffraction 

study and Rietveld analysis with the RIETAN 2000 program, [2006Nas] refined the 

structural parameters of the αMn structured Fe2VSi phase including the site occupancy. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_28 

ß Springer 2009

4 28 

Fe–Si–V 

Further investigations are required in the area of the existence of the τ 4 phase in relation to the 

phase equilibria with other phases in the region. According to [1965Gla], the solubility of V in 

Fe 5Si 3, FeSi and FeSi 2 at 1000 ˚C was measured to be about 37, 14 and 2 at.% V, respectively; 

and that of Fe in V 3Si and V 5Si 3 about 22 and 13 at.% Fe, respectively. At 1100 ˚C, according to 

[1966Bar], the solubility of Fe in V 5Si 3 was determined to be about 22 at.% Fe. Though Fe 5Si 3 

is not stable at 1100 ˚C in the Fe-Si binary system, the phase that was denoted as N2 by 

[1966Bar] and off the Fe-Si binary side is very likely to be the V-stabilized Fe5Si3 phase because 

it had a composition range corresponding to part of the composition range of the (Fe,V) 5Si 3 

solid solution at 1000˚C given by [1965Gla]. 


The quasibinary system FeSi-VSi2 reported by [1940Vog] is shown in Fig. 2. 

The FeSi2-VSi2 section is also likely to be quasibinary by taking into account the congruent 

melting of the binary compounds and the existence of the FeSi-VSi 2 quasibinary section 

making it impossible for the appearance of alternative equilibria. 


Five four-phase and two three-phase invariant equilibria involving the liquid phase have been 

detected experimentally [1940Vog] for the Fe-FeSi-VSi2-V region. Later, these experimental 

results were reinterpreted by [1982Ray] owing to the publication of revised versions of the 

binary Fe-Si and Si-V phase diagrams. In the present evaluation, it is necessary for more 

invariant reactions to be added in order to account for six binary silicides, instead of the three 

(FeSi, VSi 2 and V 2Si) known at the time of [1940Vog]. Also, the extensions of their composition 

ranges have been taken into account. It is reasonable to replace the reaction V from 

[1940Vog] (FeSi + α 1 Ð L+τ 1) by two reactions U 6 (L + FeSi Ð Fe 2Si + τ 1) and U 7 (L + τ 1 Ð 

Fe2Si + α1) (Table 3). This interpretation correlates better with the experimental data of 

[1940Vog]; namely the monovariant curve L Ð FeSi + α falls monotonously to the binary 

eutectic (1195˚C in [1940Vog]) on the Fe-Si side. 

A monovariant e 10(max) should result from the probable quasibinary section FeSi 2-VSi 2, 

as mentioned above. Taking into account the two three-phase invariant reactions (e 5(max) 

and e 10(max)), two four-phase ternary eutectic reactions should be assumed, E 1 and E 2. 

The reaction scheme proposed in the present evaluation is shown in Fig. 3. The invariant 

equilibria are listed in Table 3 showing the origin of the reactions. 


Only one experimental study of the liquidus surface [1940Vog] is available. It was reported for 

the Fe-FeSi-VSi 2-V region. It was amended later by [1982Ray]. Further amendments have been 

made in this evaluation as the currently accepted Si-V phase diagram shows essential differences 

with the older versions used by [1940Vog] and [1982Ray]. Figure 4 presents the 

amended liquidus projection based on the experimental data of [1940Vog], reinterpreted by 

[1982Ray] and modified in the present evaluation to ensure agreement with the accepted 



MSIT 1

inary diagrams. New fields of primary crystallization are added tentatively for the regions not 

considered in [1940Vog]. The location and the temperatures of the invariant points established 

by [1940Vog] are retained in the present evaluation (P 1,U 5,p 2(max), e 5(max)). The 

locations of the monovariant curves are also taken from [1940Vog]. The monovariant lines 

after [1940Vog] are shown in Fig. 4 by thick solid lines. The monovariant lines added here are 

shown by thick dashed lines. 



5 

The isothermal sections at 1100 and 1000˚C have been constructed from the results of 

experimental investigations undertaken by [1966Bar] and [1965Gla], respectively. 

According to [1966Bar], τ 1 and τ 2 both enter into equilibrium with the ordered Fe 3Si 

phase, whereas this does not appear in the diagram presented by [1965Gla]. Consequently, no 

equilibrium between τ1 and τ2 was possible in the diagram of [1966Bar]. 

There are also some other differences between the two isothermal sections given by 

[1965Gla] and [1966Bar]. [1965Gla] indicated that the V 3Si phase extended into the ternary 

system with approximately constant silicon content, whereas [1966Bar] suggested that the 

phase extends with approximately constant vanadium content. [1986Kan] confirmed the 

conclusions of the review of [1982Ray] relating to the solubility limit of Fe in V 3Si and 

the variation in lattice parameter. The results of [1965Gla] on the shape of the V 3Si phase 

field seem to be more reliable. Although the temperature difference is not large, the solubility 

of Fe in V3Si at 1100˚C was considerably lower than at 1000˚C. It should be noted that the 

solubility of Fe in V5Si3 and the homogeneity ranges of the three ternary phases τ1, τ2 and τ3 

reported by [1966Bar] for 1100˚C are visibly larger than those at 1000˚C given by [1965Gla]. 

The phase denoted as N 2 by [1966Bar] has a composition range corresponding to part of 

the composition range of the (Fe,V) 5Si 3 solid solution at 1000˚C given by [1965Gla]. This may 

be an indication that Fe 5Si 3 is stabilized by the addition of V, so that a ternary phase with the 

same structure as Fe 5Si 3 may exist at higher temperatures than in the Fe-Si binary system. 

Besides, it should be mentioned that the Fe 2Si phase, which is stable at 1100˚C, was missing in 

the presented isothermal section. 

Figures 5 and 6 show the isothermal sections at 1100 and 1000˚C, respectively, which are 

due mainly to [1966Bar] and [1965Gla]. Slight corrections have been made in order to bring 

the phase relationships into agreement with the currently accepted binary phase diagrams. The 

Fe 2Si phase missing in [1966Bar] is added to Fig. 5. For Si contents above 40 at.%, tentative 

equilibria are shown similar to those given for 1000˚C. The V 6Si 5 phase missing in [1965Gla]is 

added to Fig. 6. The VSi 2 phase is treated as a line compound. The stability ranges of the α, α 1, 

α 2 phases are modified in Figs. 5 and 6 to be in agreement with the data of [1994Koz]. 

Figures 7 to 9 show partial isothermal sections at 800, 700 and 600˚C as determined by 

[1989Koz, 1994Koz]. The isothermal section at 600˚C [1994Koz] is very similar to that at 700˚ 

C[1989Koz], showing a wide α + α 1 two-phase field. It was reported by [1989Koz] that the 

extent of the α 2 +α 1 two-phase field decreases markedly on increasing the temperature from 

700 to 800˚C. Using the Bragg-Williams-Gorsky model, [1994Koz] calculated isothermal 

sections at 800 and 600˚C, taking into account the atomic and magnetic interaction energies 

up to the second nearest neighbor. The calculated sections are in good agreement with 

experiment [1994Koz]. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_28 

ß Springer 2009

6 28 

Fe–Si–V 


Seven vertical sections through the Si corner were constructed by [1940Vog] based on their 

own experimental data. They clearly demonstrate the peritectic formation of the ternary 

compound τ 1 and a maximum on the liquidus surface of the V 5Si 3 phase. Nevertheless, they 

cannot be accepted in the present evaluation because the interpretation of phase equilibria was 

based on older versions of the binary phase diagrams that have since been superseded, and 

moreover, they are not in accordance with two isothermal sections reported later by [1966Bar] 

and [1965Gla]. 

Figure 10 shows the vertical section determined by [1994Koz] for silicon contents between 

0-25at.% at 5 at.% V. The results of [1988Fuk, 1989Koz, 1990Zha, 1994Koz] show that the 

addition of vanadium reduces the stability of the α 2 phase, narrowing its homogeneity range 

until it disappears at 1040˚C (α /(α + α 1)) and at 1050˚C ((α 1 + α 2)/α 1) at a V content of 

5 at.%. 


[1983Roz] measured the mixing enthalpies and component activities in ternary melts at 

1627˚C. The Fe-Si-V alloy melts show a negative deviation from Raoult’s law. 


Ternary Fe 3–xV xSi (0 ⊊ x ⊊ 1) alloys with the Heusler structure (L2 1) show very interesting 

electronic and magnetic properties. These properties were studied by [1976Nic, 1976Ber, 

1977Nic, 2003Kaw, 2004Nas, 2006Cui]. Using X-ray, magnetization and spin-echo NMR 

techniques, [1976Nic] measured the changes in atomic ordering, their effect on local moment 

and internal field distributions in the Fe 3–xV xSi (0 ⊊ x ⊊ 1) alloys. [1976Ber] measured the 

magnetic properties and superconductivity of Fe3–xVxSi. The role of the outer electrons on 

solubility limits and bulk magnetic properties of Fe3–xVxSi alloys was investigated by 

[1977Nic]. [2003Kaw] measured thermoelectric properties, such as the thermal diffusivity, 

electrical resistivity, and Seebeck coefficient in the temperature range from 300 to 1073 K, of 

Fe 3–xV xSi (0 ⊊ x ⊊ 1) alloys. [2004Nas] measured the Seebeck coefficient, electrical resistivity, 

and magnetization of Fe 3–xV xSi alloys with 0.6 ≤ x ≤ 1 and compared the results with those of 

Fe 3xV xAl. The electronic structures of Fe 3–xV xSi in the concentration range between x = 0 and 

x = 1 were studied by [2006Cui] using photoemission spectroscopy (PES). 

[1978Hao] determined the eutectic temperature and composition as well as the oxidation 

resistance of the alloys Fe63V30Si7 and Fe65V29Si6 (in mass%). 

[1983Bus] studied the magneto-optical properties of the Fe 2VSi compound annealed at 

800˚C for 10 d. Using X-ray diffraction, [1995Kaw] and [1998Kaw] measured the tetragonal 

deformation of Fe 2VSi at low temperatures [1995Kaw], and the thermal expansion of Fe 2VSi 

compounds below room temperature [1998Kaw]. [2004Nis] investigated the magnetic properties 

of Fe 2VSi by means of NMR experiments using 51 V for two samples that had been 

quenched after annealing at 800 and 900˚C, respectively. 

Information on the investigation of the materials properties are listed in Table 4. 



MSIT 1

Miscellaneous 

Figure 11 shows the variation of the lattice parameter a and superconducting transition 

temperatures in V 3–xFe xSi alloys as a function of iron content [1978Soz]. 

. Table 1 

Investigations of the Fe-Si-V Phase Relations, Structures and Thermodynamics 

Reference Method/ Experimental Technique 

[1940Vog] Thermal analysis, X-ray analysis and 

metallography 

Temperature/ Composition/ Phase Range 

Studied 

Fe-FeSi-VSi 2-V region, from liquidus to 

1100˚C 

[1960Gup] X-ray analysis Around the σ phase at 1175˚C 

[1961Gla] X-ray analysis Fe5V3Si2 [1961Bar] X-ray analysis Fe 41V 37Si 22 

[1962Gla] X-ray analysis Fe2V2Si (τ2), Fe5V3Si2 (τ3) [1965Gla] X-ray analysis, metallography 800, 1000, 1200˚C and as-cast state, entire 

composition range 

[1966Bar] Metallography, X-ray analysis, chemical 

analysis 

< 40 at.% Si, 1100˚C 

[1966Kim] X-ray analysis, electrical properties, 

magnetic properties, Mössbauer 

Fe 50V 30Si 20 at 4, 77 and 300 K 

[1967Far] X-ray analysis Fe2.5V1.5Si, Fe3VSi [1971Sho] X-ray analysis Fe44V26Si30 Fe–Si–V 28 

7 

[1974Bur] Neutron diffraction Fe3Si; Site occupation of V in dilutely 

substitued Fe3Si [1975Pic] Neutron diffraction Fe2.948V0.052Si alloy; Site occupation of V in 

Fe3Si [1976Nic] Neutron diffraction Fe3–xVxSi alloys (0≤ x ≤1.0); changes in the 

atomic ordering, their effect on local 

moment and internal field distributions 

[1976Sho] X-ray analysis V26.5Fe44Si29.5 [1978Hao] Thermal analysis, SEM Fe63V30Si7 and Fe65V29Si6 alloys (in mass%); 

oxidation resistance 

[1978Soz] X-ray analysis Solid solution (V,Fe) 3Si, ≤ 10 at.% V 

[1983Roz] Measurements of mixing enthalpies and 

activities 

The Fe-Si-V alloy melts, at 1267˚C 

[1984Sin] X-ray analysis, metallography Fe3Si - V3Si section, 400 and 1000˚C; 

V50Fe25Si25 ternary phase 

[1985Wan] Magnetic properties, X-ray analysis, SEM Fe-6.5Si (mass%) alloy; effect of vanadium 

on ordering phase separation in Fe-Si alloy 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_28 

ß Springer 2009

8 28 

Fe–Si–V 


Reference Method/ Experimental Technique 

Temperature/ Composition/ Phase Range 

Studied 

[1986Kan] X-ray analysis (Fe,V) 3Si alloys; phase separation of α and 

α1 in (Fe1–xVx) 3 Si alloys 

[1988Kum] Thermodynamic calculation Fe rich ternary alloys, at 950, 1050, 1150, 

and 1250˚C; bcc-fcc equilibrium 

[1988Fuk] TEM observation of phase separation with α and 

α1 in Fe-Si-V alloys 

[1989Koz] TEM Fe rich Fe-Si-V alloys, 700, 800˚C; phase 

separation of α and α1 [1990Zha] Thermodynamic calculation α2 (B2) +α1 (D03) two phase field; influence 

of V on the order-disorder reactions in the 

Fe-Si bcc (α) phase, 

[1991Kud] Ab initio calculation of electronic 

structures and magnetic moments 

Fe3–xVxSi [1994Koz] Phase separation of α and α 1, ordering, 

TEM, thermodynamic calculation 

Fe rich ternary alloys, 600˚C, 800˚C, 600- 

1200˚C 

[1995Kaw] X-ray analysis Fe2VSi, at 300 K 

[1998Kaw] Thermal expansion, X-ray analysis Fe2VSi, below room temperature, 120 K 

[2003Kaw] X-ray analysis, EDX Fe3–xVxSi 

[2004Doi] TEM Fe72V13Si15, 1200, 650˚C; aging 

precipitation of α1 in α 

[2004Nas] X-ray analysis, measurements of Seebeck 

coefficient, electrical resistivity, and 

magnetization 

Fe3–xVxSi (0.6 ≤ x ≤ 1.0) 

[2004Nis] Neutron diffraction, magnetic 

susceptibility measurement 

[2006Cui] electronic structures, photoemission 

spectroscopy (PES) 

Fe 2VSi, 800˚C, 900˚C 

Fe 3–xV xSi (0 ≤ x ≤ 1.0) annealed at 850˚C for 

5 days 

[2006Nas] X-ray analysis and neutron diffraction Fe2VSi, 800˚C,1100˚C 

[2006Doi] TEM Fe70.5V16.2Si13.3, 1200˚C, 650˚C; phase 

separation of α and α1 DOI: 10.1007/978-3-540-70890-2_28 Landolt‐Börnstein 


MSIT 1

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Lattice 

Parameters 


α, (αδFe,V) cI2 

< 1910 Im3m 

W 

(δFe) 

1538 - 1394 

a = 293.15 pure Fe at 1390˚C [V-C2, Mas2] 

(V) 

< 1910 

a = 302.4 pure V at 25˚C [Mas2] 

(αFe) 

< 912 



1394 - 912 Fm3m 

Cu 


P63/mmc Mg 

c = 396.0 

(αSi) cF8 a = 543.06 T = 25˚C [Mas2, V-C2] 

< 1414 Fm3m 

C (diamond) 

(βSi) (II) tI4 a = 468.6 T = 25˚C, p > 9.624 bar [Mas2, V-C2] 

I41/amd βSn 

c = 258.5 

(γSi) (III) cI16 

Im3m 

γSi 

a = 663.6 T = 25˚C, p > 16.208 bar [Mas2, V-C2] 

(δSi) (I) hP4 a = 380 T = 25˚C, p = 16.208-1.013 bar [Mas2, V-C2] 

P63/mmc αLa 

c = 628 

α1,Fe3Si cF16 D03 < 1235 Fm3m a = 565.0 [V-C2] 

BiF3 11.0 to 30.0 at.% Si [1982Kub] 

α2, Fe-Si cP2 B2 

< 1280 Pm3m a = 281 [V-C2] 

CsCl 10.0 to 22.0 at.% Si [1982Kub] 

β, Fe2Si hP6 a = 405.2 ± 0.2 [V-C2] 

1212 - 1040 P3m1 

Fe2Si c = 508.55 ± 0.03 19.93 to 21.31 at.% Si [1982Kub] 



MSIT 1 

9 

DOI: 10.1007/978-3-540-70890-2_28 

ß Springer 2009

10 28 

Fe–Si–V 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


η, Fe5Si3 hP16 [1982Kub] 

1060 - 825 P63/mmc a = 675.9 ± 0.5 [V-C2] 

Mn5Si3 c = 472.0 ± 0.5 

ε, FeSi cP8 a = 451.7 ± 0.5 [V-C2] 

< 1410 P213 FeSi 

49.6 to 50.8 at.% Si [1982Kub] 

ζα, FeSi2(h) tP3 a = 269.01 [V-C2] 

1220 - 937 P4/mmm 

FeSi2 c = 513.4 69.5 to 73.5 at.% Si [1982Kub] 

ζβ, FeSi2(r) oC48 [1982Kub] 

< 982 Cmca a = 986.3 [V-C2] 

FeSi2 b = 779.1 

c = 783.3 

σ, FeV tP30 a = 896.5 [V-C2] 

< 1252 P42/mnm σCrFe 

c = 463.3 39.9 to 70.4 at.% Fe [Mas2] 

V3Si cP8 a = 472.72 [V-C2] 

< 1925 Pm3n 

Cr3Si 19 to 25.5 at.% Si [Mas2] 

V5Si3 tI32 a = 943 [V-C2] 

< 2010 I4/mcm 

Si3W5 c = 471 

V6Si5 oI44 a = 1596.6 [V-C2, Mas2] 

1670 - 1160 Ibam b = 750.1 

Ti6Ge5 c = 485.8 

VSi2 hP9 a = 457.5 [V-C2] 

< 1677 P6222 

CrSi2 c = 638.5 

* τ1,Fe4V5Si4 tP56 30 to 40 at.% Fe 

P41212 a = 888 [1965Gla] 

Mn5Si2 c = 867 

a = 883.3 

[1965Gla] 

c = 864.6 [1971Sho] atFe44V26Si30 * τ 2,Fe 2V 2Si hR53 45.5 to 52 at.% Fe 

R3 a = 1079.9 [1965Gla] 

Co5Cr2Mo3 c = 1924.3 [V-C2] 

a = 1079 

c = 1924.0 [1961Bar] atFe 41V 37Si 22 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


* τ3,Fe5V3Si2 cI58 

I33m 

αMn 

a = 884.3 [1962Gla, 1965Gla] 32 to 44 at.% Fe 

* τ4,Fe2VSi cF16 L21 Heusler structure phase 

Fm3m 

AlCu2Mn a = 567.4 at 300 K [1995Kaw] 

t* a = 568.8 at 10 K [1995Kaw]. 

- c = 562.3 Transition to the tetragonal structure occurs at 

120 K [1998Kaw] 

. Table 3 





Fe Si V 

11 

Comment 

L+V5Si3 Ð τ1 1510 p2 (max) L 38 32 30 [1940Vog] 

L+V6Si5 Ð V5Si3 + VSi2 1500 U1 - - - - this work 

L+V5Si3 Ð τ1 +V3Si 1450 U2 - - - - this work 

L+V3Si Ð α + τ1 1400 U3 L 46.5 12.5 41 [1940Vog] 

L+τ1 + α2 Ð α1 1370 P1 L 48 13 39 [1940Vog] 

L+α2 + τ1 Ð α1 1350 P2 - - - - this work 

L Ð VSi2 + FeSi 1310 e5 (max) - - - - this work 

L+V5Si3 Ð VSi2 + τ1 1260 U4 L 27.5 49 23.5 [1940Vog] 

L + VSi2 Ð FeSi + τ1 1235 U5 L 60 36 4 [1940Vog] 

L + FeSi Ð Fe2Si + τ1 1202 U6 - - - - this work 

L+τ1 Ð Fe2Si + α1 1201 U7 L 66 31 3 [1940Vog] 

L Ð VSi2 + FeSi2 1200 e10 (max) - - - - this work 

L Ð VSi2 + FeSi2 + (Si) 1180 E1 - - - - this work 

L Ð VSi2 + FeSi2 + FeSi 1150 E2 - - - - this work 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_28 

ß Springer 2009

12 28 

Fe–Si–V 

. Table 4 

Investigations of the Fe-Si-V Materials Properties 

Reference Method/ Experimental Technique Type of Property 

[1976Nic] Magnetometer Magnetic properties 

[1983Bus] Saturation moment, Polar Kerr rotation Magnetic properties, 

optical properties 

[1991Kud] Ab initio calculation Magnetic properties 

[2003Kaw] Laser flash, measurements of electrical resistivity, 

thermoelectric power and density 

Thermoelectric property 

[2004Nis] Measurements of thermoelectric power, magnetization 

and electrical resistivity 

Magnetic and electric 

properties 



MSIT 1

. Fig. 1 

Fe-Si-V. Si-V binary phase diagram 



MSIT 1 


13 

DOI: 10.1007/978-3-540-70890-2_28 

ß Springer 2009

14 28 

Fe–Si–V 

. Fig. 2 

Fe-Si-V. Quasibinary system VSi 2-FeSi 



MSIT 1

. Fig. 3 

Fe-Si-V: Partial reaction scheme 



MSIT 1 


15 

DOI: 10.1007/978-3-540-70890-2_28 

ß Springer 2009

16 28 

Fe–Si–V 

. Fig. 4 

Fe-Si-V. Partial liquidus surface in the Fe-FeSi-VSi 2-V region 



MSIT 1

. Fig. 5 

Fe-Si-V. Isothermal section at 1100˚C 



MSIT 1 


17 

DOI: 10.1007/978-3-540-70890-2_28 

ß Springer 2009

18 28 

Fe–Si–V 

. Fig. 6 

Fe-Si-V. Isothermal section at 1000˚C 



MSIT 1

. Fig. 7 

Fe-Si-V. Partial isothermal section at 800˚C 



MSIT 1 


19 

DOI: 10.1007/978-3-540-70890-2_28 

ß Springer 2009

20 28 

Fe–Si–V 

. Fig. 8 




MSIT 1

. Fig. 9 




MSIT 1 


21 

DOI: 10.1007/978-3-540-70890-2_28 

ß Springer 2009

22 28 

Fe–Si–V 

. Fig. 10 

Fe-Si-V. Vertical section at 5 at.% V with the silicon content of 0-25 at.% 



MSIT 1


23 

. Fig. 11 

Fe-Si-V. Variation of the lattice parameter (1) and superconducting transition temperature (2) in 

the V 3–xFe xSi alloys with x 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_28 

ß Springer 2009

24 28 

Fe–Si–V 

References 

[1940Vog] Vogel, R., Jentzsch-Uschinski, C., “The Iron-Silicon-Vanadium Alloys” (in German), Arch. Eisenhuettenwes., 

13, 403–408 (1940) (Phase Diagram, Phase Relations, Morphology, Experimental, *, 9) 

[1960Gup] Gupta, K.P., Rajan, N.S., Beck, P.A., “Effect of Si and Al on the Stability of Certain σ Phases”, Trans. 

Met. Soc. AIME, 218, 617–624 (1960) (Experimental, Phase Diagram, Phase Relations, 18) 

[1961Bar] Bardos, D.I., Gupta, K.P., Beck, P.A., “New Ternary R Phases with Silicon”, Nature, 192, 744 (1961) 


[1961Gla] Gladyshevskii, E.I., Kripyakevich, P.I., Teslyuk, M.Yu., Zarechnyuk, O.S., Kuz’ma, Yu.B., “Crystal 

Structures of Some Intermetallic Compounds”, Sov. Phys.-Crystallogr., 6, 207–208 (1961), translated 

from Kristallografiya, 6(2), 267 (1960) (Crys. Structure, Experimental, 11) 

[1962Gla] Gladyshevskii, E.I., “Crystal Structure of Compounds and Phase Equilibria in Ternary Systems of Two 

Transition Metals and Silicon”, Sov. Powder Metall. Met. Ceram. (Engl. Transl.), 1(4), 262–265 (1962) 

(Crys. Structure, Experimental, Phase Diagram, Phase Relations, 17) 

[1965Gla] Gladyshevsky, E.I., Shvets, G.N., “Phase Equilibrium Diagram of Ternary V-Fe-Si Alloys and Crystal 

Structure of the Compounds”, Russ. Metall., 2, 63–65 (1965), translated from Izv. Akad. Nauk SSSR, 

Met., (2), 120–127 (1965) (Experimental, Phase Diagram, Phase Relations, *, 2) 

[1966Bar] Bardos, D.I., Beck, P.A., “Electron Phases in Certain Ternary Alloys of Transition Metals with Silicon”, 

Trans. Met. Soc. AIME, 236, 64–69 (1966) (Experimental, Phase Diagram, Phase Relations, *, 16) 

[1966Kim] Kimball, C.W., Phillips, W.C., Nevitt, M.V., Preston, R.S., “Magnetic Hyperfine Interactions and 

Electric Quadrupolar Coupling in Alloys of Iron with the α-Manganese Structure”, Phys. Rev., 146(2), 

375–378 (1966) (Crys. Structure, Electr. Prop., Magn. Prop., Experimental, 18) 

[1967Far] Farrokhi-Mochai, N., “A Study of the Solid Phases in the Fe-Si-Ti, Fe-Si-Zr, and Fe-Si-V Systems” (in 

French), Rev. Chim. Miner., 4, 1–15 (1967) (Crys. Structure, Phase Relations, Phase Diagram, Experimental, 

23) 

[1971Sho] Shoemaker, C.B., Shoemaker, D.P., “On Structures of Transition-Metal Phases with Approximately 

30 at.% Si”, Metall. Trans., 2, 2296–2299 (1971) (Crys. Structure, Experimental, 11) 

[1974Bur] Burch, T.J., Litrenta, T., Budnick, J.I., “Hyperfine Studies of Site Occupation in Ternary Systems”, Phys. 

Rev. Letters, 33(7), 421–424 (1974) (Crys. Structure, Experimental, 12) 

[1975Pic] Pickart, S., Litrenta, T., Burch, T., Budnick, J.I., “Site Preference of Dilute Transition Metal Solutes in 

Fe3Si”, Phys. Lett. A, 53A(4), 321–323 (1975) (Crys. Structure, Experimental, 4) 

[1976Ber] Bergner, R.L., Rao, V.U.S., Sanker, S.G., “Superconducting and Magnetic Properties of V 3–xFe xSi and 

V 3–xMn xSi”, AIP Conf. Proc., 29, 325–326 (1976) (Experimental, Magn. Prop., Supercond., 4) 

[1976Nic] Niculescu, V., Raj, K., Budnick, J.I., Burch, T.J., Hines, W.A., Menotti, A.H., “Relating Structural, 

Magnetisation and Hyperfine Field Studies to a Local Environment Model in Fe 3–xV xSi and 

Fe 3–xMn xSi”, Phys. Rev. B, 14(9), 4160 (1976) (Crys. Structure, Magn. Prop., Experimental, 26) 

[1976Sho] Shoemaker, C.B., Shoemaker, D.P., “The Crystal Structure of Mn 5Si 2 and the D phase (V-Fe-Si)”, Acta 

Crystallogr., Sect. B: Struct. Crystallogr. Crys. Chem., B32(7), 2306–2313 (1976) (Crys. Structure, 


[1977Nic] Niculescu, V., Budnick, J.I., “Limits of Solubility, Magnetic Properties and Electron Concentration in 

Fe 3–xTi xSi System”, Solid State Commun., 24(9), 631–634 (1977) (Crys. Structure, Experimental, Phase 

Relations, Magn. Prop., 17) 


26–32 (1978) (Experimental, Phase Diagram, Phase Relations, 24) 

[1978Soz] Sozontova, G.N., Shtolts, A.K., Geld, P.V., Medvedev, A.I., “Superconducting Solid Solutions of 

(V,Fe) 3Si, (V,Fe) 3Ge and (V,Fe) 3Ga”, Russ. Metall., (2), 172–174 (1978), translated from Izv. Akad. Nauk 

SSSR, Met., (2), 217–219 (1978) (Experimental, Phase Diagram, Phase Relations, 5) 


(1982) (Phase Diagram, Phase Relations, Review, #, *, 23) 

[1982Ray] Raynor, G.V., Rivlin, V.G., “8: Critical Evaluation of Constitution of Iron-Silicon-Vanadium System”, 

Int. Met. Rev., 27(5), 289–306 (1982) (Phase Diagram, Phase Relations, Review, 32) 

[1983Bus] Buschow, K.H.J., van Engen, P.G., Jongebreur, R., “Magneto-Optical Properties of Metallic 

Ferromagnetic Materials”, J. Magn. Magn. Mater., 38, 1–22 (1983) (Experimental, Magn. Prop., Optical 

Prop., 23) 



MSIT 1


25 

[1983Roz] Rozhikhina, I.D., Tolstoguzov, N.V., “Practical Use of Data on the Heat of the Dissolution of Fe-V-Si 

Molten Alloys”, Izv. V.U.Z. Chern. Metall., (4), 12–15(1983) (Experimental, Thermodyn., 4) 

[1984Sin] Singh, M., Bhan, S., “Structural Studies on V 3Si-Fe 3Si System”, Cryst. Res. Technol., 19(9), K81–K83 

(1984) (Experimental, Morphology, Phase Diagram, Phase Relations, Crys. Structure) 

[1985Wan] Wang, S., “Effect of Vanadium on Ordering Phase Separation in Fe-Si Alloy”, Acta Metall. Sin., 21(6), 

427–37 (1985) (Phase Relations, Experimental, Crys. Structure, Magn. Prop., 21) 

[1986Kan] Kanematsu, K., “Stability of Crystal Structure of (Fe,V) 3M and (Fe,Ni) 3M (M = Si, Ge, Sn) and Its 

Analysis Based on Rigaid Band Model”, Trans. Jpn. Inst. Met., 27(4), 225–234 (1986) (Crys. Structure, 


[1988Fuk] Fukaya, M., Kozakai, T., Miyazaki, T., “Phase Separation in Fe-Si-V and Fe-Si-Co Ordered Alloys” (in 

Japanese), Nippon Kinzoku Gakkai-Si, 52(4), 369–374, (1988) (Experimental, Phase Diagram, Phase 


[1988Kum] Kumar, K.C.H., Raghavan, V., “BCC-FCC Equilibrium in Ternary Iron Alloys”, J. Alloy Phase Diagrams, 

4(1), 53–71 (1988) (Experimental, Phase Relations, Thermodyn., 27) 

[1988Ray] Raynor, G.V., Rivlin, V.G., “Fe-Si-V” in “Phase Equilibria in Iron Ternary Alloys”, Inst. Metals, London, 

452–466 (1988) (Phase Diagram, Phase Relations, Crys. Structure, Review, 11) 

[1989Koz] Kozakai, T., Zhao, P.Z., Miyazaki, T., “Phase Separations in Fe rich Fe-base Ternary Ordering Alloy 

Systems”, Met. Abstr. Light Metals and Alloys, 23, 32–33 (1989/1990) (Crys. Structure, Experimental, 


[1990Zha] Zhao, P.Z., Kozaki, T., Miyazaki, T., “Analysis of Ordering and Phase Separation in Alloys of the Ternary 

System Fe-Si-V with bcc Structure based on the Model of Bragg-Williams-Gorsky”, J. Jpn. Inst. Met., 

54(2), 139–145 (1990) (Crys. Structure, Phase Relations, Calculation, 27) 

[1991Kud] Kudrnovsky, J., Christensen, N.E., Andersen, O.K., “Electronic-Structures and Magnetic-Moments of 

Fe 3+ySi 1–y and Fe 3–xV xSi Alloys with D0 3-Derived Structure”, Phys. Rev. B, 43(7), 5924–5933 (1991) 

(Crys. Structure, Electronic Structures, Magn. Prop., Calculation, 33) 

[1994Koz] Kozakai, T., Miyazaki, T., “Experimental and Theoretical Investigations on Phase Diagrams of Fe Base 

Ternary Ordering Alloys”, ISIJ Int., 34(5), 373–383 (1994) (Phase Diagram, Experimental, Calculation, 


[1994Rag] Raghavan, V., “Fe-Si-V (Iron-Silicon-Vanadium)”, J. Phase Equilib., 15(6), 633–634 (1994) (Phase 


[1995Kaw] Kawakami, M., Nishizaki, S., Fujita, T., “Tetragonal Deformation in Fe 2VSi at Low Temperatures”, 

J. Phys. Soc. Jpn., 64(11), 4081–4083 (1995) (Crys. Structure, Experimental, 6) 

[1998Kaw] Kawakami, M., Uchimura, T., “Crystal Structure Transformation in Fe 2VSi and Its Substituted Compounds”, 

J. Phys. Soc. Jpn., 67(8), 2758–2760 (1998) (Crys. Structure, Phase Relations, Experimental, 7) 

[2002Rag] Raghavan, V., “Fe-Si-V (Iron-Silicon-Vanadium)”, J. Phase Equilib., 23(5), 447 (2002) (Phase Relations, 

Review, 6) 

[2003Kaw] Kawaharada, Y., Uneda, H., Kurosaki, K., Yamanaka, S., “Thermoelectric Properties of Fe-V-Si 

Heusler Type Compounds”, J. Alloys Compd., 359, 216–220 (2003) (Crys. Structure, Phys. Prop., 


[2004Doi] Doi, M., Sakai, D., Koyama, T., Kozakai, T., Moritani, T., “TEM Observations of the Precipitation of A2 

Particles in DO 3 Precipitates in Fe-Si-V Alloy System”, Trans Tech Publications. Materials Science Forum, 

449–452(1), 529–532 (2004) (Crys. Structure, Phase Relations, Experimental, 9) 

[2004Nas] Nashima, O., Kanomata, T., Yamaguchi, Y., Abe, S., Harada, T., Suzuki, T., Nishihara, H., Koyama, K., 

Shishido, T., Watanabe, K., Kaneko, T., “Magnetic and Electrical Properties of Fe 3–xV xSi”, J. Alloys 

Compd., 383(1-2), 298–301 (2004) (Crys. Structure, Electr. Prop., Magn. Prop., Experimental, 12) 

[2004Nis] Nishihara, H., Ono, K., Neumann, K.U., Ziebeck, K.R.A., Kanomata, K., “NMR of 51 V in a 

Heusler Alloy Fe 2VSi”, J. Alloys Compd., 383(1-2), 302–307 (2004) (Magn. Prop., Crys. Structure, 


[2006Cui] Cui, Y.T., Kimura, A., Miyamoto, K., Sakamoto, K., Xie, T., Qiao, S., Nakatake, M., Shimada, K., 

Taniguchi, M., Fujimori, S.-I., Saitoh, Y., Kobayashi, K., Kanomata, T., Nashima, O., “Electronic 

Structures of Fe 3–xV xSi Probed by Photoemission Spectroscopy”, Phys. Status Solidi A, 203(11), 

2765–2768 (2006) (Crys. Structure, Electronic Structure, Experimental, 5) 

[2006Doi] Doi, M., Moritani, T., Kozakai, T., Wakano, M., “Transmission Electron Microscopy Observations of 

the Phase Separation of D0 3 Precipitates in an Elastically Constrained Fe-Si-V Alloy”, ISIJ Int., 46(1), 

155–160 (2006) (Morphology, Phase Relations, Experimental, 22) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_28 

ß Springer 2009

26 28 

Fe–Si–V 

[2006Nas] Nashima, O., Yamaguchi, Y., Higashi, H., Goto, T., Kaneko, T., Sasamori, S., Kimura, H., Kobayashi, K., 

Kainuma, R., Ishida, K., Kanomata, T., “Unusual Complex High Temperature Structure of Fe 2VSi”, 

J. Alloys Compd., 417(1-2), 150–154 (2006) (Crys. Structure, Phase Relations, Experimental, 8) 

[2007Zha] Zhang, C., Wang, J., Du, Y., Zhang W.J., “An Investigation on the Thermodynamic Stability of V 6Si 5”, 

J. Mater. Sci., 42(16), 7046–7048 (2008) (Phase Diagram, Experimental, Thermodyn., Calculation, 20) 


(1990) 





MSIT 1

Iron – Silicon – Zirconium 


Yong Du, Wei Xiong, Weiwei Zhang, Hailin Chen, Weihua Sun 

Introduction 

The only contribution to the measurement of the Fe-Si-Zr phase diagram is the work by 

[1971Lis], who determined the isothermal section at 800˚C using 110 alloys. The existence of 

six ternary compounds is reported: τ 1, ZrFeSi [1963Spi, 1965Mar, 1966Fre, 1967Far, 1969Jei, 

1969Yar, 1971Lis], τ 2,Zr 2Fe 3Si [1965Mar, 1969Tes, 1971Lis, 1978Mit], τ 3,Zr 4Fe 4Si 7 [1967Far, 

1969Jei, 1971Lis, 1996Eve], τ 4, ZrFe 2Si 2 [1967Vor, 1971Lis], τ 5,Zr 6Fe 16Si 7 [1971Lis, 1984Cha], 

and τ 6,Zr 3Fe 5Si 12 [1974Lys]. The previously reported stoichiometry of ZrFeSi 2 [1967Far] for 

τ 3 was corrected to be Zr 4Fe 4Si 7 by [1996Eve]. So far, there is no information on the melting 

behavior of these phases. [1978Hao] identified one eutectic in Fe rich side of the Fe-Si-Zr 

system. But the phases participating in the eutectic reaction are not specified [1978Hao]. 

In the literature, there are two pieces of experimental information on the thermodynamic 

properties of Fe-Si-Zr melts. One is the enthalpy of dissolution for Zr in FeSi melt at 1597˚C 

[1989Sud1], the other is enthalpies of mixing for the Fe-Si-Zr melt at 1627˚C below 40 at.% Zr 

[1989Sud2]. Information on phase relations, crystal structures and thermodynamics is summarized 

in Table 1. 

Further work is necessary to measure the phase relationships over wide composition and 

temperature ranges, especially the phase equilibria involving liquid. 


The binary Fe-Si and Si-Zr systems are accepted from [Mas2]. [2002Ste] redetermined the 

whole Fe-Zr phase diagram by means of differential thermal analysis (DTA), X-ray diffraction 

(XRD), electron probe microanalysis (EPMA), and metallography. This newly established 

phase diagram is adopted in the present work. 


Fe–Si–Zr 29 

1 

The crystallographic data of the phases in the Fe-Si-Zr system and their temperature ranges of 

stability are listed in Table 2. Five ternary compounds (τ 1, τ 3, τ 4, τ 5 and τ 6) are treated as the 

stoichiometric ones due to the lack of experiments. The homogeneity range of the τ 2 phase at 

800˚C given in Table 2 is estimated from the isothermal section drawing in [1971Lis] and 

should be considered as tentative only. The τ 1 phase was first reported by [1963Spi], who 

annealed alloys at 1100˚C for 3 d in argon-filled fused silica capsules. This phase is characterized 

by a rather restricted range of homogeneity around the composition ZrFeSi [1963Spi]. 

The existence of τ 1 is confirmed by subsequent investigators [1965Mar, 1966Fre, 1967Far, 

1969Jei, 1969Yar, 1971Lis] using XRD technique. The decomposition temperature of this 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_29 

ß Springer 2009

2 29 

Fe–Si–Zr 

ternary phase is determined to be about 1800˚C [1967Far]. [1969Jei] is responsible for the 

determination of its space group using XRD. 

Using XRD method, four groups of authors [1965Mar, 1969Tes, 1971Lis, 1978Mit] contributed 

to the crystal structure determination of the τ 2 phase. The lattice parameters calculated 

by them are consistent with each other within the estimated experimental errors. 

The τ3 phase was first reported by [1967Far] and its existence was confirmed by [1969Jei, 

1971Lis, 1996Eve]. This phase shows a large homogeneity range with an excess of Fe or a 

deficiency of Si, and melts at a temperature of above 2000˚C [1967Far]. Subsequently, the 

space group of this phase was determined by [1969Jei] and its stoichiometry was reported to 

be Zr 4Fe 4Si 7 [1996Eve]. 

[1967Vor] published the crystal structure data for τ 4 without giving experimental details. 

The occurrence of this compound was confirrmed by [1971Lis] using both XRD and optical 

microscopy. 

Using XRD method, [1971Lis, 1984Cha] reported the existence of τ5. Another ternary 

compound τ6 was found by [1974Lys] employing XRD technique. The crystallographic data 

for τ 5 was established [1971Lis]. For τ 6, however, no crystal structure data are available. 

Zr 2Fe and Zr 2Si were found to form a continuous series of solid solution at 800˚C by 

[1971Lis], who also reported that the solid solubility of Si in ZrFe 2 is about 5 at.%, and that of 

Fe in ZrSi 2 about 5 at.%. For the other binary compounds, negligible solid solubilities of the 

third element were observed [1971Lis]. [1985Tro, 1987Bla] reported the lattice parameters for 

the (Zr 1–xSi x)Fe 2 with x = 0.2 and 0.5, respectively. 

According to [1985Tro] and [1987Bla], the measured solid solubilities of Si in α, ZrFe2 are 

16.7 (in the temperature range of 800-1500˚C) and 6.7 at.% (in the temperature range of 900- 

1200˚C), respectively. These authors did not give the specified temperature which corresponds 

to the measured solubility. 

Based on the literature data, [1981Kot] analyzed the crystal structures and compositions of 

the ternary compounds formed in the systems R-M-Si (R = Ce, Hf, Ti, Sc, Y, Zr and M = Fe, 

Co, Cu, Ni, Mn) in view of electronegativities and the atomic radii of the components. They 

reported that Sc indicates the similar behavior with Zr and Hf when the ternary compound 

formation with Si and M is taken into account. This feature found by [1981Kot] can be used 

for the investigation of the other systems. 


Based on differential thermal analysis and optical microstructure observations of two alloys, 

[1978Hao] identified one eutectic with the eutectic temperature of 1310˚C and the eutectic 

composition of about 77.9Fe-7.9Si-14.2Zr (mass%). Mentioning (δFe) phase participating in 

the eutectic reaction, [1978Hao] did not identify the remaining two solid phases associated 

with the eutectic reaction. Based on the information on the invariant equilibria in Fe-rich side 

of the Fe-Zr and Fe-Si systems, the remaining two solid phases could be (γFe) and β, ZrFe 2. 

This invariant equilibrium is given in Table 3. 


Figure 1 presents the experimental isothermal section at 800˚C based on [1971Lis]. The 

solubility of Si in the Fe2Zr phase was shown by [1971Lis] in the direction of the Si-Zr binary 



MSIT 1

axis that is in contradiction with [1985Tro] and [1987Bla]. Therefore in Fig. 1 the shape of the 

Fe 2Zr phase is modified to present the Si solubility in the direction of the Fe-Si binary axis. The 

phase borders at the binary sides reported by [1971Lis] are amended slightly in Fig. 1 in order 

to bring them into agreement with the accepted binary phase diagrams [Mas2, 2002Ste]. 


[1989Sud1] measured the enthalpy of dissolution of Zr in FeSi melt at 1597˚C by means of 

drop calorimetry. These data are reproduced in Table 4 and used to derive the partial and 

integral enthalpies of the corresponding compositions by [1989Sud1]. Using a drop calorimetry, 

[1989Sud2] determined the enthalpies of mixing for the Fe-Si-Zr melt at 1627˚C below 40 

at.% Zr. These experimental results [1989Sud2] are reproduced in Fig. 2. Preliminary thermodynamic 

calculation of the Fe-Si-Zr system was performed by [1995Gue], who also measured 

the solubility of Fe in ZrSi2 at 800˚C. In the modeling of [1995Gue], ternary compounds were 

not considered. 


[1978Hao] reported that although the eutectic in the Fe rich corner of the Fe-Si-Zr system 

could be suitable for development as materials for directionally solidified turbine blades 

operating up to 1150˚C, its oxidation resistance should be enhanced in order to meet several 

important criteria associated with the manufacture of the turbine blades. Oxidation tests 

indicated a rapid attack of the primary silicide phase, starting only after about 20 min of 

exposure [1978Hao]. The effects of Zr substitution on thermoelectric power, electrical resistivity, 

thermal conductivity, Seebeck coefficient, and phase transformation of thermoelectric 

materials β-FeSi 2 are investigated by [2001Ito, 2002Ito]. It was found that Zr substitution is 

quite effective for enhancing the thermoelectric performance of β-FeSi 2. 

The influence of Si addition on the structure (including short-range order) and stability 

of amorphous Fe-Si-Zr alloys was investigated by [1988Bie] using X-ray diffraction and 

Mössbauer spectroscopy and by [1991Mic] employing Mössbauer spectroscopy and magnetization 

measurement. Mössbauer spectroscopy was also utilized to investigate the effect of Si 

addition on the mean values of the hyperfine magnetic field for the compounds Zr(Fe 1–xSi x) 2 

with x ≤ 0.17 [1990Das, 1992Sar]. 

Using a metallographic microscope, [1985Tro] measured the microhardness of 

Zr 0.8Si 2Fe 0.2. Following the same technique, [1987Bla] determined the microhardness for 

several alloys (Zr xSi 1–x)Fe 2 (x = 0.9, 0.8, 0.7, 0.6, 0.5). It was found [1987Bla] that the 

microhardness decreases with increasing Si content. The measured microhardness along the 

vertical section ZrFe2 - SiFe2 is presented in Fig. 3 [1987Bla]. 

Table 5 lists some investigations of the materials properties of the Fe-Si-Zr system. 

Miscellaneous 


3 

Figure 4 shows lattice parameter variation of the Zr 2(Fe,Si) 1 phase versus Si content measured 

by [1971Lis], who annealed the alloys at 800˚C for 500 h. The measured lattice parameters 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_29 

ß Springer 2009

4 29 

Fe–Si–Zr 

along the vertical section ZrFe 2 - SiFe 2 are presented in Fig. 5 [1987Bla]. A linear dependence 

of the lattice parameters measured for the ZrFe 2-Zr 0.5Si 0.5Fe 2 system means that 50% Zr in 

ZrFe 2 can be substituted by Si (16.7 at.% Si) according to [1987Bla]. This experimental 

observation seems to be in contradiction with the work of [1971Lis], who reported that the 

solubility of Si in ZrFe 2 is 5 at.% at 800˚C. In the work due to [1987Bla], temperature of 

annealing was given in the range of 800-1500˚C. Therefore, if the annealing temperature was 

higher than 800˚C, the results from [1987Bla] could be interpreted in a way that the solubility 

of Si increases with temperature. The same solid solution was investigated by [1985Tro] with 

annealing temperature 900-1200˚C, and 20% of Zr was found to be substituted by Si (6.7 at.% 

Si). This value (6.7 at.% Si) is between the solubility value obtained by [1971Lis] (5 at.% Si) 

and by [1987Bla] (16.7 at.% Si). This implies that the temperature of annealing in the work of 

[1987Bla] is higher than that in [1985Tro] and thus confirms the idea that the solubility of Si 

increases with temperature. 

. Table 1 

Investigations of the Fe-Si-Zr Phase Relations, Structures and Thermodynamics 

Reference 



[1963Spi] X-ray diffracrion (XRD) formation, crystal structure of τ1, (ZrFeSi) 

[1965Mar] XRD formations, crystal structures of τ1, and τ2 (Zr2Fe3Si) [1966Fre] XRD formation, crystal structure of τ1 [1967Far] XRD formations, crystal structures of τ1, and τ3 (Zr4Fe4Si7) [1967Vor] XRD formation, crystal structure of τ4 (ZrFe2Si2) [1969Jei] XRD formations, crystal structures of τ1 and τ3 

[1969Yar] XRD formation, crystal structure of τ 1 

[1971Lis] XRD, optical misroscopy 

(OM) 

[1978Hao] Differential thermal 

analysis (DTA), OM 

formation, crystal structures of τ 1, τ 2 (Zr 2Fe 3Si), τ 3, τ 4, τ 5 

(Zr 6Fe 16Si 7) and τ 6 (Zr 3Fe 5Si 72); isothermal section at 

800˚C 

data on reaction L Ð(δFe) + (γFe) +Zr 6Fe 23 

[1978Mit] XRD, OM formation, crystal structure τ 2 

[1984Cha] XRD formation, crystal structure of τ 5 

[1985Tro] XRD lattice parameter of Zr0.8Si2Fe0.2 in the temperature 

range of 900 to 1200˚C 

[1987Bla] XRD lattice parameter of Zr0.8Si2Fe0.2 in the temperature 

range of 800 to 1500˚C 

[1989Sud1] Drop calorimetry enthalpy of dissolution of Zr in FeSi melt at 1597˚C 

[1989Sud2] Drop calorimetry enthalpies of mixing for the Fe-Si-Zr melt at 1627˚C 

below 40 at.% Zr 



MSIT 1


Reference 



[1995Gue] CALPHAD, electron probe 

microanalysis (EPMA) 

Approximate calculation of phase equilibria without 

including any ternary compounds; experimental 

solubility of Fe in ZrSi 2 at 800˚C 

[1996Eve] XRD formation, crystal structure of τ 3 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Lattice 

Parameters 


α, (αδFe) cI2 

< 1910 Im3m 

(δFe) 

1538 - 1394 

W a = 293.15 pure Fe at 1390˚C [V-C2, Mas2] 

(αFe) 

< 912 


(γFe) cF4 a = 366.60 [V-C2] 

1394 - 912 Fm3m 

Cu 

a = 364.67 [Mas2] 

(Si) cF8 a = 543.06 at 25˚C [Mas2] 

< 1414 Fd3m 

C (diamond) 

a = 542.86 [V-C2] 

(βZr) cI2 a = 360.90 [Mas2] 

1855 - 863 Im3m 

W 

a = 356.8 [V-C2] 

(αZr) hP2 a = 323.16 at 25˚C [Mas2] 

< 863 P63/mmc c = 514.75 

Mg a = 323.2 

c = 514.7 

[V-C2] 

α1,Fe3Si cF16 D03 < 1235 Fm3m a = 565 [V-C2] 

BiF3 11.0 to 30.0 at.% Si [Mas2] 

α2, Fe-Si cP2 B2 

≲ 1280 Pm3m 10.0 to 22.0 at.% Si [Mas2] 

CsCl a = 281 [V-C2] 



MSIT 1 

5 

DOI: 10.1007/978-3-540-70890-2_29 

ß Springer 2009

6 29 

Fe–Si–Zr 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


β, Fe2Si hP6 33.0 to 34.3 at.% Si [Mas2] 

1212 - 1040 P3m1 a = 405.2 ± 0.2 [V-C2] 

Fe2Si c = 508.55 ± 0.03 

η, Fe5Si3 hP16 37.5 at.% Si [Mas2] 

1060 - 825 P63/mcm a = 675.9 ± 0.5 [V-C2] 

Mn5Si3 c = 472.0 ± 0.5 

ε, FeSi cP8 49.6 to 50.8 at.% Si [Mas2] 

< 1410 P213 FeSi 

a = 451.7 ± 0.5 [V-C2] 

ζα, FeSi2(h) tP3 69.5 to 73.5 at.% Si [Mas2] 

1220 - 937 P4/mmm a = 269.01 [V-C2] 

FeSi2 c = 513.4 

ζβ, FeSi2(r) oC48 a = 986.3 ± 0.7 [V-C2] 

< 982 Cmca b = 779.1 ± 0.6 66.7 at.% Si [Mas2] 

FeSi2 c = 783.3 ± 0.6 

Zr3Fe oC16 a = 332 24.6 to 25.2 at.% Fe [2002Ste] 

≤ 851 Cmcm b = 1100 

Re3B c = 882 

α, ZrFe2 cF24 a = 702 to 709 27.5 to 34.4 at.% Zr [2002Ste] 

< 1673 Fd3m 

MgCu2 C15 structure 

(Zr1–xSix)Fe2 a = 702.5 x = 0.2 [1985Tro] 

a = 694.3 x = 0.5 [1987Bla] 

β, ZrFe2 hP24 a = 495 73 to 73.5 at.% Fe [2002Ste] 

1345 - 1240 P63/mmc MgNi2 c = 1614 C36 structure 

ZrSi2 oC12 a = 372.1 [V-C2] 

< 1620 Cmcm b = 1468 

ZrSi2 c = 368.3 

β, ZrSi oC8 - [Mas2] 

2210 - 1460 Cmcm 

CrB 

α, ZrSi oP8 a = 699.5 [V-C2] 

< 1460 Pnma b = 378.6 

FeB c = 529.6 

β, Zr5Si4 2250 - 1860 

- - [Mas2] 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Lattice 

Parameters 


α, Zr5Si4 tP36 a = 712.25 [V-C2] 

< 1860 P41212 Zr5Si4 c = 1300.0 

Zr3Si2 tP10 a = 708.2 [V-C2] 

< 2215 P4/mbm 

Si2U3 c = 371.5 

Zr5Si3 hP16 a = 788.6 [V-C2] 

2180 - 1745 P63/mcm Mn5Si3 c = 555.8 

Zr3Si tP32 a = 1101 [V-C2] 

< 1650 P42/n Ti3P c = 545 

Zr2FexSi1–x tI12 

I4/mcm 

Zr2Fe CuAl2 a = 638.0 at x =1[2002Ste] 

951 - 780 c = 560.0 66.7 to 67.2 at.% Zr [2002Ste] 

C16 structure 

Zr2Si a = 660.9 at x =0[V-C2] 

< 1925 c = 529.8 

* τ1, ZrFeSi oP12 a = 640.50 Pearson symbol [V-C2] 

≲ 1800 Pnma b = 393.50 Space group [1969Jei] 

TiNiSi c = 719.90 Lattice parameter [1969Jei] 

Decomposition temperature [1967Far] 

* τ2, Zr2Fe3Si hP12 Pearson symbol [V-C2] 

P63/mmc At 800˚C, from 45 to 51.5 at.% Fe, from 15.5 to 

MgZn2 20.65 at.% Si, from 32.95 to 34.36 at.% Zr 

[1971Lis]. 

a = 498.90 

c = 811.00 

[1965Mar] 

a = 498.50 

c = 809.60 

[1978Mit] 

* τ3,Zr4Fe4Si7 tI60 Space group [1969Jei]; Pearson symbol [V-C2] 

< above 2000 I4/mmm 

Zr4Co4Ge7 Stoichiometry [1996Eve] 

a = 1298.0 

c = 510.00 

[1967Far] 

a = 1305.6 

c = 509.00 

[1969Jei] 



MSIT 1 

7 

DOI: 10.1007/978-3-540-70890-2_29 

ß Springer 2009

8 29 

Fe–Si–Zr 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


* τ 4, ZrFe 2Si 2 tP10 a = 375.00 [1967Vor] 

I4/mmm c = 966.00 Pearson symbol [V-C2] 

Al 2Ga 2Ge 

* τ 5, 

Zr 6Fe 16Si 7 

* τ6, 

Zr 3Fe 5Si 72 

. Table 3 


cF116 a = 1153.0 [1971Lis] 

Fm3m 

Mg6Cu16Si7 a = 1168.0 [1984Cha] 

- - [1974Lys] 


Fe 


Si Zr 

L Ð(δFe) + (γFe) + β,ZrFe 2 1310 E L 76.15 15.35 8.5 

. Table 4 



Zr(25˚C)+ L (n = ∞, FeSi at 1597˚C) ⇒ 

L(x Zr, 1597˚C) 

Temperature 

[˚C] 

Quantity, per mole 

of atoms 


1597˚C ΔH = –15.3 ± 0.3 (xZr 

= 0.05) 

ΔH = –24.7 ± 0.5 (xZr = 0.10) 

ΔH = –35.0 ± 0.8 (xZr = 0.15) 

ΔH = –49.0 ± 1.0 (xZr = 0.20) 

Drop calorimetry 

[1989Sud1] 



MSIT 1

. Table 5 

Investigations of the Fe-Si-Zr Materials Properties 


[1978Hao] The specimen were oxidized isothermally at 

1150˚C in slowly flowing oxygen under 

1.33·10 4 Pa pressure in a thermobalance. 

Density was measured using water 

displacement method. 

[1985Tro] A PMT-3 metallographic microscope was 

used to determine the microhardness under 

a load of 100 or 200 g. 

[1987Bla] A PMT-3 metallographic microscope was 

used to determine the microhardness under 

a load of 100 g. 

oxidation resistance, density 

microhardness 

microhardness 

[1992Sar] Mössbauer spectroscopy mean value of the hyperfine magnetic 

field, isomer shift, and quadrupole 

splitting 

[2001Ito, 

2002Ito] 



dc method in a flowing argon gas using 

computer-controlled equipment, laser flash 

thermal constant analyzer TC-7000. 

MSIT 1 


thermoelectric power, electrical 

resistivity, thermal conductivity, 

Seebeck coefficient were measured 

from room temperature to 900˚C 

[2001Ito] or to 827˚C [2002Ito] 

9 

DOI: 10.1007/978-3-540-70890-2_29 

ß Springer 2009

10 29 

Fe–Si–Zr 

. Fig. 1 

Fe-Si-Zr. Isothermal section at 800˚C 



MSIT 1

. Fig. 2 

Fe-Si-Zr. Isolines of the enthalpy of mixing (kJ·mol –1 ) of liquid at 1627˚C 



MSIT 1 


11 

DOI: 10.1007/978-3-540-70890-2_29 

ß Springer 2009

12 29 

Fe–Si–Zr 

. Fig. 3 

Fe-Si-Zr. Microhardness along the vertical section ZrFe 2 - SiFe 2 



MSIT 1

. Fig. 4 

Fe-Si-Zr. Lattice parameters of the Zr 2Fe xSi 1–x vs Si content 



MSIT 1 


13 

DOI: 10.1007/978-3-540-70890-2_29 

ß Springer 2009

14 29 

Fe–Si–Zr 

. Fig. 5 

Fe-Si-Zr. Lattice parameter along the vertical section ZrFe 2 - SiFe 2 



MSIT 1

References 


15 

[1963Spi] Spiegel, F.X., Bardos, D., Beck, P.A., “Ternary G and E Silicides and Germanides of Transition 

Elements”, Trans. Metall. Soc. AIME, 227, 575–579 (1963) (Crys. Structure, Experimental, 13) 

[1965Mar] Markiv, V.Ya., Voroshilov, Yu.V., Gladyshevskii, E.I., “Ternary Laves Phases in the Systems Ti-Co-Si(Ge) 

and Zr-Fe-Si(Ge)”, Inorg. Mater., 1(6), 818–821 (1965), translated from Izv. Akad. Nauk SSSR, Neorg. 

Mater., 1(6), 890–893 (1965) (Crys. Structure, Experimental, 5) 

[1966Fre] Freundlich, W., Farrokhi-Mochai, N., “Two Intermetallic Ternary Phases- ZrFeSi and TiFeSi” (in 

French), Compt. Rend. Acad. Sci. Paris, 262C, 1000–1001 (1966) (Crys. Structure, Experimental, 0) 

[1967Far] Farrokhi-Mochai, N., “A Study of the Solid Phases in the Fe-Si-Ti, Fe-Si-Zr, and Fe-Si-V Systems” (in 

French), Rev. Chim. Miner., 4, 1–25 (1967) (Crys. Structure, Experimental, Phase Relations, 23) 

[1967Vor] Voroshilov, Yu.V., Markiv, V.Ya., Gladyshevskii, E.I., “The Zirconium-Nickel-Silicon System”, 

(in Russian), Izv. Akad. Nauk SSSR, Neorg. Mater., 3(8) 1404–1408 (1967) (Crys. Structure, Experimental, 

28) 

[1969Jei] Jeitschko, W., Jordan, A,G., Beck, P.A., “V and E Phases in Ternary Systems with Transition Metals and 

Silicon or Germanium”, Trans. Met. Soc. AIME, 245, 335–339 (1969) (Crys. Structure, Experimental, 27) 

[1969Tes] Teslyuk, M.Yu., “Intermetallic Compounds with Structure of Laves Phases” (in Russian), in “Intermetallic 

Compounds with Structure of Laves Phases”, Nauka, Moscow, 1–136 (1969) (Crys. Structure, Phase 

Diagram, Review, Theory) 

[1969Yar] Yarmolyuk, Y.P., Markiv, V.Y., Hladyshevsky, E.I., “Compounds with the TiNiSi Structure in the 

Systems of Two Transition Metals and Either Si or Ge”, Vestn. L’vov. Univ. Khim., 11, 14–17 (1969) 


[1971Lis] Lisenko, L.A., Ban, Z., Gladisevskii, E.I., “Investigation of the System Zr-Fe-Si”, Croat. Chem. Acta., 43, 

113–118 (1971) (Crys. Structure, Phase Diagram, Experimental, #, *, 20) 

[1974Lys] Lysenko, L.A., Ban, Z., Yarmolyuk, Ya.P., Gladisevskii, E.I., “Reaction of Zr with Fe-Group Transition 

Metals and Si” in “Struktura Faz. Faz. Prevrashcheniya i Diagrammy Sostoyaniya Metal. Sistem”, Nauka, 

Moscow, 21–25 (1974) (Crys. Structure, Review, 20) 


26–32 (1978) (Experimental, Mechan. Prop., Interface Phenomena, Phase Relations, Phys. Prop., 24) 

[1978Mit] Mittal, R.C., Si, S.K., Gupta, K.P., “Si-Stabilised C14 Laves Phases in the Transaction Metal Systems”, 

J. Less-Common Met., 60, 75–82 (1978) (Crys. Structure, Experimental, 12) 

[1981Kot] Kotur, B.Ya., Bodak, O.I., “Characteristics of the Reaction of Sc with Si and Transition Metals of Period 

IV”, Inorg. Mater., 17(2), 185–188 (1981), translated from Izv. Akad. Nauk SSSR, Neorg. Mater., 17(2), 

265–268 (1981) (Phase Diagram, Review, Theory, 27) 

[1984Cha] Chaudouet, P., Lambert, B., Madar, R., Fruchart, R., “Existence of a G-type Phase in the Fe-Zr-Si 

System“ (in French), Ann. Chim. Fr., 9(2), 119–121 (1984) (Crys. Structure, Experimental, 8) 

[1985Tro] Trojko, R., Blazina, Z., “Metal-Metalloid Exchange in Some Friauf-Laves Phases Containing Two 

Transition Metals”, J. Less-Common Met., 106, 293–300 (1985) (Crys. Structure, Experimental, 13) 

[1987Bla] Blazina, Z., Trojko, R., “On Friauf-Laves Phases in the Zr 1–xAl xT 2,Zr 1–xSi xT 2 and Zr 1–xTi xT 2 (T = Mn, 

Fe, Co) Systems”, J. Less-Common Met., 133(2), 277–286 (1987) (Crys. Structure, Mechan. Prop., 


[1988Bie] Biegel, W., Krebs, H.U., Michaelsen, C., Freyhardt, H.C., “Structure Analyses of Amorphous Melt-Spun 

Fe-Zr-(B,Si) Alloys and Mechanically Alloyed Fe-Zr Powders”, Mater. Sci. Eng., 97, 59–62 (1988) (Crys. 


[1989Sud1] Sudavtsova, V.S., Zelenina, L.N., Sharkina, N.O., “Reaction in the System FeSi-Nb(Zr)”, Inorg. Mater., 

25(9), 1330–1331 (1989), translated from Izv. Akad. Nauk SSSR, Neorg. Mater., 25(9), 1569–1570 (1989) 


[1989Sud2] Sudavtsova, V.S, “Termochemical Properties of Liquid Fe-Zr-Si Alloys”, Russ. Metall., 4, 39–40 (1989), 

translated from Izv. Akad. Nauk SSR. Metall., 4, 46–47 (1989) (Experimental, Thermodyn., 5) 

[1990Das] Dasilva, C.M., Dacunha, J.B.M., Livi, F.P., Gomes, A.A., “Ferromagnetic Laves Phase Intermetallics 

Doped with SP Impurities - A Mössbauer Study of Zr(Fe 1–xSi x) 2”, Hyperfine Interactions, 62(3), 199–206 

(1990) (Magn. Prop., Experimental, 21) 

[1991Mic] Michaelsen, C., Schultz, L., “Structural Study of Amorphous Zr-Fe-B and Zr-Fe-Si Alloys by 57 Fe- 

Mössbauer and Magnetization Measurements”, Acta Metall. Mater., 39(5) 987–994 (1991) (Magn. Prop., 




MSIT 1 

DOI: 10.1007/978-3-540-70890-2_29 

ß Springer 2009

16 29 

Fe–Si–Zr 

[1992Sar] Sarzynski, J., Budzynski, M., Wasiewicz, R., Wiertel, M., “The Influence of Silicon on Hyperfine 

Magnetic Fields in Zr(Fe 1–xSi x) 2 measured for x ≤ 0.17 by Mössbauer Spectroscopy”, J. Phys.: Condens. 

Mater., 4, 6473–6478 (1992) 

[1995Gue] Gueneau, C., Servant, C., Ansara, I., “Experimental and Thermodynamic Assessments of Substitutions 

in the AlFeSi, FeMnSi, FeSiZr and AlCaFeSi Systems”, Appl. Thermodyn. Synth. Process. Mater., Proc. 

Symp., 1994 (Pub.1995), Nash, P., Sudman, B. (Eds.), The Mineral. Metal. Mater. Soc., 303–317 (1995) 

(Assessment, Experimental, Morphology, Phase Diagram, Phase Relations,Thermodyn., 19) 

[1996Eve] Evers, Ch.B.H., Jeitschko, W., “Crystal Structure of Tetrazirconium Tetrairon Heptasilicide, Zr 4Fe 4Si 7”, 

Z. Kristallogr., 211, 119 (1996) (Crys. Structure, Experimental, 2) 


Performace of β-FeSi 2”, J. Alloys Compd., 315, 251–258 (2001) (Electr. Prop., Experimental, 18) 

[2002Ito] Ito, M., Nagai, H., Tahata, T., Katsuyama, S., Majima, K., “Effects of Zr Substitution on Phase 

Transformation and Thermoelectric Properties of β-FeSi 2”, J. Appl. Phys., 92(6), 3217–3222 (2002) 

(Electr. Prop., Experimental, Transport Phenomena, 21) 



(2002) (Phase Diagram, Crys. Structure, Experimental, #, *, 88) 


(1990) 





MSIT 1

Iron – Samarium – Titanium 


Natalia Kol’chugina 

Introduction 

The Fe-Sm-Ti system is of interest from the practical viewpoint since the Sm(FeTi) 12 (the τ 1 

ternary phase) compound was found to be a possible candidate for permanent-magnet 

materials. The high anisotropy field of the (the τ 1 phase with the SmTiFe 11 stoichiometry, its 

rather high Curie temperature, and reasonable magnetization have determined the necessity of 

basic understanding of the phase relations in the Fe-Sm-Ti system, in particular, in the range 

of Fe rich alloys. 

Earlier investigations into the Fe-Sm-Ti system [1988Oha], [1988Sin], [1988Yan], and 

[1989Zha] are related to the preparation and study of the τ1 ternary phase. The Fe rich corner 

of the system was studied in [1990Jan] (at 900˚C), [1990Kat], [1991Kim] (at 800 and 1000˚C), 

[1991Nei] (at 1000˚C), [1992Rei] (equilibria between 1000 and 800˚C), [1994Iva] and 

[1995Iva] (a phase close to the phase denoted subsequently 3:29 (τ 2), and [1997Liu] (at 

600˚C). 

The distinctive feature of the most of studies is the use of melt spinning, mechanical 

alloying, cathodic sputtering, powder metallurgy procedures as preparation techniques (thus, 

many investigators dealt with both nonequilibrium states and metastable phases) and magnetic 

measurements as procedures, which allow one to find and identify phases along with the 

investigation of their magnetic properties. 

A review [2000Rag], which summarizes the investigations of the phase equilibria in the 

Fe-Sm-Ti system, is available. 

A review [1995Cad] considers advances in iron based permanent-magnet materials; 

Fe-Sm-Ti compositions are among them. 

In a number of works, hydrogenation and nitrogenation (with the formation of hydrides 

and nitrides, respectively) techniques are used as procedures that allow the magnetic properties 

of Fe-Sm-Ti alloys and compounds to be changed and improved. 

Investigations of the Fe-Sm-Ti phase relations, structure identifications are given in 

Table 1. 


Fe–Sm–Ti 30 

1 

The Fe-Ti binary phase diagram is taken from the critical assessment of [1987Mur]. The 

homogeneity ranges of the TiFe and TiFe2 phases and solubilities of Ti in (γFe) and Fe in (αTi) 

are reported using numerous experimental data. 

The Fe-Sm binary phase diagram is taken from [Mas2]. The maximum solubility of iron 

in (βSm) at the eutectic temperature is shown to be < 0.54 at.% [1982Kub]. 

The phase diagram of the Sm-Ti binary system is taken from [1991Rei], it is shown 

in Fig. 1. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_30 

ß Springer 2009

2 30 

Fe–Sm–Ti 


There are four ternary phases identified in the system. They are designated in the literature as 

1:12 (τ 1), 1:11 (τ 3), 3:29 (τ 2), and 5:17 (τ 4). The crystallographic data of the Fe-Sm-Ti phases 

are listed in Table 2. 

It should be noted that the phases were obtained by both conventional arc and induction 

melting (in as-cast and annealed alloys) and rapid quenching (mechanical alloying) followed 

by annealing. 

The τ 1 phase is formed peritectically from (αFe) and liquid at 1300˚C [1992Rei]. Earlier, 

[1990Jan] reported that the τ 1 phase does not undergo decomposition down to 700˚C. At 

1000˚C, τ 1 ranges from SmTi 0.7Fe 11.3 to SmTi 1.1Fe 10.9 [1992Rei]. [1997Liu] did not find the 

compound at 600˚C. However, the phase may be crystallized from the amorphous phase of the 

Sm 8.3Ti 8.3Fe 83.4 composition upon annealing at 660˚C [1990Wec]. At 900˚C, τ 1 is in equilibrium 

with TiFe2 and Sm(Ti,Fe)2 [1992Rei]. 

The Sm(Ti,Fe)8.5 phase that subsequently was identified as the τ2 phase is stable above 

1000˚C and is not found at 800˚C [1994Iva] and below. The τ 2 phase is formed upon vacuum 

annealing at 1100˚C for 24 h followed by rapid water quenching. The Ti content, which is 

needed to stabilize the τ 2 phase may vary from 5.0 to 6.5 in the Sm 10Ti xFe 100–x compositions 

[1995Yan2]. According to [2000Iva], the τ 2 phase may be obtained by annealing of the mixture 

Sm 2(Ti,Fe) 17 + τ 1 at 1150˚C for 4 h or at 1000˚C for 48 h. According to [2006Sun], the 

structural relationship τ 2 Ð Sm 2Fe 17 + τ 1 is valid. In [1991Rei, 1992Rei], this phase is given as 

Sm(Ti,Fe)9; it disappears at 800˚C. For this phase, [1991Rei] gives the TbCu7 type structure 

and the Curie temperature TC = 209˚C that is close to TC = 200˚C given by [1990Jan] for Sm 

(Ti,Fe) 7, T C = 197˚C given by [1994Iva] for Sm(Ti,Fe) 8.5, and T C = 213˚C and 212˚C given by 

[1995Yan2] and [1996Koy] for Sm 3(Ti,Fe) 29, respectively. According to [1991Rei], the τ 2 phase 

is formed by a peritectic reaction at 1240˚C and subsequently takes part in the formation of 

the τ 3 phase. 

It is likely that a metastable phase with the TbCu 7 structure (space group P6/mmm) that is 

discussed in a number of works (since it exhibits interesting magnetic properties) is similar to 

the τ2 phase. The phase with the TbCu7 structure was obtained in the SmxTi8Fe92–x (6≤x≤15) 

compositions annealed at 600 to 700˚C [1990Din]. At x = 8, 10, 15 at.% Sm, a = 489 pm, 

c = 424 pm; at 10, 15 at.% Sm, the phase becomes dominant. According to [1990Jan], as-cast 

Sm 7.7Ti 4.6Fe 87.7 contains Sm(Ti,Fe) 7 phase. The TbCu 7 type structure was found in 

Sm 10Ti xFe 90–x (x = 4.5 and 6) compositions; for x = 4.5, a = 493.5 pm, c = 420.5 pm and 

for x =6,a = 493.5 pm, c = 422.2 pm [1994Wan]. However, [1994Yan] reported that 

Sm 20Ti 9Fe 71 annealed at 810˚C and Sm 26Ti 9Fe 65 annealed at 810 and 900˚C contain (along 

with other phases) SmTiFe 6 (metastable with a cubic structure, a = 802.3 nm) phase. In 

[1995Xia], ribbons with the composition corresponding to τ1 annealed above 740˚C exhibit 

the transformation Sm(Ti,Fe)7 (TbCu7 type structure, metastable) Ð SmTiFe11 (ThMn12 

type structure). According to [1995Yan1], in SmTi xFe 7+x (x = 0.2-1.5) melt-spun ribbon, 

Sm(Ti,Fe) 7 formed is stable even after annealing at 650-750˚C; however, the hexagonal 

Sm(Fe,Mo) 7 type structure with a = 492.2 pm and c = 424.5 pm, volume of unit cell 

8906.2 ·10 3 pm 3 is reported. 

The τ 3 (with the stoichiometry SmTi 1.5Fe 9.5) phase is found near the tie line (Sm 2Fe 17 - 

TiFe 2) in the isothermal section at 900˚C [1990Jan]. In [1991Kim], τ 3 was not found at 800˚C. 

τ3 is formed peritectically, is found in the isothermal section at 1000˚C [1992Rei], and is stable 



MSIT 1

down to 600˚C [1992Rei], [1997Liu]. According to [1991Rei], the τ3 phase is formed by a 

peritectic reaction at 1100˚C. 

The τ4 phase is found in [1991Sta] (its X-ray diffraction pattern is analogous to the 

Nd5Fe17 phase) and for Sm26TiyFe74–y in the composition range y = 1-17 [1997Yan] in samples 

annealed at 810 and 870˚C, i.e., it is stable at these temperatures. However, the τ4 phase was not 

identified at 800˚C in [1991Kim]. The lattice parameters first are reported in [1994Yan]. 

According to [1991Rei], the τ4 phase is formed by a peritectic reaction at 900˚C. 

Sm2(Fe,Ti)17 is a solid solution of Ti in Sm2Fe17. According to [1990Kat], the Sm2Fe17 

phase with the Th2Zn17 type structure incorporates a small amount of Ti atoms; in this case, 

Sm2(Fe,Ti) 17 (with the rhombohedral Th2Zn17 type structure, a = 856.0 pm, c = 1247 pm) is 

found in Smx(Fe0.875Ti0.125) 100–x (x = 10, 15, 20, 25) compositions. [1990Jan] gives the 

solubility of Ti in Sm2Fe17 up to 3 at.%. According to [1991Nei], 2.59 at.% Ti are present 

in Sm2Fe17. The maximum solubility of Ti in Sm2Fe17 at 1000˚C was found to be 3.7 at.%; at 

800˚C, Sm2Fe17 shows a small homogeneity range and dissolves up to 3.5 at.% Ti [1992Rei]. At 

600˚C, Sm2Fe17 shows a homogeneity range of about 1 at.% Sm and dissolves up to 3.1 at.% Ti 

[1997Liu]. The dependence of the lattice parameter of the solid solution on the Ti content 

is considered in [1998Pao] for Sm2TixFe17–x (x = 0-0.85) and in [2000Pao] for Sm2TixFe17–x (x = 0, 0.4, 0.75) (these compositions cover the aforementioned ranges of solubility of Ti 

in Sm2Fe17). [2000Shc] reported the increase in the lattice parameter for the Sm2(TixFe1–x) 17 

(x = 0.02, 0.03, 0.04) compositions (with the Th2Zn17 type structures) up to x = 0.06; 

the existence of the high-temperature modification with the Th2Ni17 type structure is discussed. 

The existence of the Sm2(TixFe1–x) 17 solid solution up to x = 0.04 is discussed in 

[2004Zha]. 

The Sm2(Ti,Fe)17 phase in the form of low- (Th2Zn17 type) and high- (Th2Ni17 type, 

a = 851 pm, c = 838 pm) temperature modifications was found in Sm(TixFe1–x) y,(x = 0.04- 

0.065, y = 8.0-9.0) [1995Iva]. 

The Ti-containing SmFe2 in the form of Sm(Ti,Fe) 2 with the Cu2Mg type structure with 

a = 742.7 pm in and a = 741.5 pm is reported in [1990Kat] and [1994Yan], respectively. In 

[1997Liu], the solubility range of Ti in SmFe2 is up to 4.7 at.%. The content is higher than the 

value ( 1 at.%) determined from the isothermal section at 800˚C [1992Rei]. [1997Liu] 

deduces that the Ti content in SmFe2 will be reduced as the annealing temperature decreases. 

However, [2006Sun] indicates that, when ingots Sm2Ti1Fe16 are quickly cooled along the 

cooling direction, the Sm-rich phase is not Sm(Ti,Fe) 2 but SmFe2. For the SmFe3 phase in the Fe-Sm-Ti system, the Sm solubility range is from 24.0 to 26.8 

at.% and the maximum solubility of Ti is up to 4.1 at.% [1997Liu], which essentially agrees 

with the result of [1990Jan] who gives 5 at.% solubility in the isothermal section at 900˚C. 

The amount of Sm dissolving in TiFe2 is about 0.6 at.% [1997Liu]. 



3 

The data on the invariant equilibria are available in a partial reaction scheme given in Fig. 2 in 

accordance with [1991Rei]. The τ 2 phase is included in the scheme instead of the Sm(Ti,Fe) 9 

phase. The eutectic temperature in the Fe-Ti binary system was corrected in accordance with 

the accepted phase diagram. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_30 

ß Springer 2009

4 30 

Fe–Sm–Ti 


A partial liquidus projection is given in Fig. 3. It is available in [1992Rei] and [1991Rei] (where 

the liquidus surface was constructed experimentally based on EDX and thermal analyses and 

metallographic data) and corresponds to the Fe-Sm-TiFe 2 field. The Sm(Ti,Fe) 9 phase 

reported by the author is denoted here as τ2 phase (Sm3(Ti,Fe)29). 


Isothermal sections of the Fe-Sm-Ti system were studied in [1990Jan] (at 900˚C), [1991Kim] 

(at 800 and 1000˚C), [1991Nei] (at 1000˚C), [1992Rei] (at 800 and 1000˚C), and [1997Liu] (at 

600˚C). All these works show good agreement. The isothermal sections at 1000 and 800˚C are 

shown in Figs. 4 and 5 from [1992Rei]. The Sm(Fe,Ti)9 phase of [1992Rei] is denoted here 

as τ2, Sm3(Ti,Fe)29. The character of the phase relations at 1000˚C continues down to at least 

900˚C [1990Jan], [1992Rei]. Figure 6 presents the isothermal section at 600˚C from [1997Liu]. 

The homogeneity ranges of the binary phases SmFe 3 and SmFe 2 along the binary axis are ruled 

out since they disagree with the accepted binary diagram Fe-Sm. 


Three compounds τ1, τ2, and τ4 (among four ternary phases formed in the Fe-Sm-Ti system) 

are magnetic phases; τ 3 is a nonmagnetic phase. Their properties and properties of alloys with 

close compositions are given in Table 3. 

The magnetic properties of the metastable phase with the TbCu 7 type structure and 

magnetic properties of Sm 2(Ti,Fe) 17 (that is a solid solution of Ti in the Sm 2Fe 17 compound) 

are also considered in Table 3. 

The effect of hydrogenation and nitrogenation on the magnetic properties of ternary 

phases also is considered in Table 3 in spite of the fact that these compositions are quaternary. 

These procedures allow the Curie temperature to be increased and the magnetocrystalline 

anisotropy type, saturation magnetization, coercivity to be changed. The effect of other 

alloying additions (B, C, Si, metals) is also discussed. 

The possibility of preparation of magnets based on the Fe-Sm-Ti system is discussed in 

[1992Rei]. The authors conclude that the preparation of Fe-Sm-Ti-based sintered magnets is 

restricted by phase relations in the system. 

Miscellaneous 

Mössbauer spectra of amorphous compositions close to τ 1 and annealed (at 650, 700, 800, 

850˚C) Sm 10Ti 8Fe 82 alloys are given in [1990Din]; [1991Qia] performed Mössbauer spectroscopy 

for the melt-spun Sm 20Ti 10Fe 70. NMR spectroscopy for τ 1 was performed in [1996Kap]. 

An enthalpy change during crystallization (in Ar) of melt-spun Sm 0.17Fe 0.83 and 

(Sm 0.17Fe 0.83) 94Ti 3C 3 ribbon alloys was estimated in [1999Shi] based on DTA data; these 

were found to be –28.1 J·g –1 and 36.4 J·g –1 , respectively. These values are normalized to the 

mass of the entire sample (crystalline and amorphous fractions) and not to the amount of 



MSIT 1

material actually transforming. Therefore, this value is directly related to the amount of 

amorphous fraction in each sample. The higher value for (Sm 0.17Fe 0.83) 94Ti 3C 3 indicates 

that the Ti and C additions increase the amorphous phase content (i.e., improve the glass 

formability) as well as its stability that follows from the higher crystallization temperature of 

the alloy (596˚C) as compared to that of Sm 0.17Fe 0.83 (570˚C). The enthalpy change during 

crystallization (in Ar) of melt-spun (Sm 0.11Fe 0.89) 94Ti 3C 3 ribbon is –6.8 J·g –1 . The enthalpy 

changes determined upon crystallization in N2 are lower. 

. Table 1 

Investigations of the Fe-Sm-Ti Phase Relations, Structures and Thermodynamics 


[1988Oha] TEM, EMPA, X-ray diffraction / 

magnetization measurements 

[1988Sin] Arc melting, melt spinning, annealing (at 

700˚C) / DSC, X-ray diffraction, EDXA, 

TEM, magnetic measurements 

(thermomagnetic analysis, hysteresis loop 

measurements) 


Range Studied 

Compositions 7.14 (7.32) at.% Sm-7.14 

(7.55) at.% Ti-85.72 (85.13) at.% Fe / τ 1 

phase. 

Ribbon Sm 8Ti 8Fe 84 annealed at 700˚C 

contains a phase with the ThMn 12 type 

structure. 

[1988Yan] Arc melting / magnetic measurements SmTiFe x with x = 8-11 has the tetragonal 

ThMn 12 type structure. 

[1989Zha] R.f. (radio frequency) induction melting, 

annealing, hydrogenation / X-ray 

diffraction, thermomagnetic analysis, 

magnetic measurements 

[1990Coc] Melt spinning, annealing (at 540, 800˚C) / 

X-ray diffraction, DTA, magnetic 

measurements 

[1990Din] Melt spinning, annealing (at 600, 650, 700, 

750, 800, 850, and 900˚C) / X-ray 

diffraction, SEM, EDAX, Mössbauer 

spectroscopy, magnetization 

measurements 



MSIT 1 


τ 1 (SmTiFe 11); lattice parameters 

5 

Ribbons Sm 17Ti 8 Fe 75 annealed at 540 and 

800˚C / off-stoichiometric phase with the 

ThMn 12 type structure. 

Sm xTi 8Fe 92–x (6≤x≤15). 

The compositions with x = 8, 10, 15 

annealed at 600-700˚C exhibit the 

presence of the TbCu 7 structure 

(metastable), that is a dominant phase at 

x = 10, 15 at.% Sm. 

Ribbons with x = 6, 8 annealed at 800˚C 

and above have the ThMn 12 type 

structure; ribbons with x = 10, 15 have a 

cubic structure. 

DOI: 10.1007/978-3-540-70890-2_30 

ß Springer 2009

6 30 

Fe–Sm–Ti 



[1990Jan] 99.9%Sm, 99%Fe, 99.9%Ti (mass%) Arc 

melting, annealing (at 900˚C for 72 h), 

quenching in water/ X-ray diffraction 

metallography, electron probe analysis, 

magnetic and thermomagnetic analyses. 

[1990Kat] Sm 99.5%, Fe 99.9%, 99.9 mass% purity 

Induction melting, annealing (1000˚C, 1 h 

+ 750˚C, 63 h), water quenching / DTA, 

X-ray diffraction, metallography 

Melt spinning, annealing (between 725 

and 900˚C for 15-60 min) / magnetic 

measurements 

[1990Sch2] Mechanical alloying, annealing (at 800˚C), 

hot pressing (at 725˚C), induction melting 

+ rapid quenching, annealing (at 700- 

850˚C) /X-ray diffraction, magnetic 

measurements 

[1991Cad] Sputtering / X-ray diffraction, magnetic 

measurements 

[1991Kim] 99.9% Sm, 99.7%, Ti, 99.98% Fe; Melting & 

casting, annealing (at 800 and 1000˚C), 

melt spinning + annealing (at 800˚C)/ 

optical microscopy, SEM, X-ray diffraction, 



Range Studied 

Isothermal section at 900˚C/ 

compositions Sm 7.7Ti xFe 92.3–x (x = 2.8, 4.6, 

7.7, 9.2, 18.5). 

τ1 does decompose down to 700˚C but it 

is restricted by the coexistence of 

Sm 2Fe 17 and TiFe 2. 

A new τ3 (SmTi1.5Fe9.5). 

As-cast Sm 7.7Ti 4.6Fe 87.7 contains the Sm 

(Ti,Fe) 7 phase. 

Section Smx(Ti0.125Fe0.875)100–x (x = 10, 15, 

20, 25); samples contain Sm 2(Ti,Fe) 17, Sm 

(Ti,Fe) 2, TiFe 2 Samples with x = 15, 20, 25 

annealed at 750˚C contain Sm 2Fe 17+Sm 

(Ti,Fe) 2; at 855˚C: a peritectic 

decomposition of Sm(Ti,Fe) 2; with x = 10, 

15, 20, 25, a peritectic decomposition of 

Sm 2(Ti,Fe,) 17 into the liquid and τ 1 phase 

at 1260˚C is observed. 

After annealing at 1000˚C for 1 h, τ 1 is not 

observed. 

Sm 20Ti 10–xFe 70+x (x = –2, 0, 2); asquenched 

(at low cooling rates) ribbons 

contain the τ 1 phase. 

In annealed (at 800˚C) ribbons, a phase of 

the Sm 20Ti 10Fe 70 composition is present. 

Sm xTi 10Fe 90–x (x = 16, 18, 20, 22) annealed 

at 800˚C exhibits the presence of a new 

phase of the Sm 20Ti 10Fe 70 composition. 

In sputtered and subsequently 

crystallized films, τ 1 (SmTi 0.5Fe 11.5) phase 

is found. 

Isothermal sections at 800 and 1000˚C; 

Sm xTi yFe 100–x–y (3.8



[1991Nei] 99.9% Sm, 99.7% Ti, 99.98% Fe Arc 

melting, annealing (at 1000˚C for 3 

weeks), water quenching/optical 

metallography, microhardness 

measurements, SEM, EDAX, X-ray 

diffraction, magnetic measurements 

[1991Sta] Cathodic sputtering or mechanical 

alloying 

[1992Rei] Sm > 99.5 mass%, Ti > 99.5 mass%, Fe > 

99.9 mass%, 5-fold arc melting, annealing 

at 1000˚C for 7 d, at 900˚C for 14 d, and at 

800˚C for 45 d, water quenching / optical 

metallography, EDX, thermal and 


[1994Iva] Sm - 99.8%, Ti - 99.95%, Fe - 99.98%. 

Induction melting, annealing at 1150- 

900˚C / X-ray diffraction, magnetic 

measurements 

[1994Wan] Arc melting, annealing (at 1200˚C for 

24 h), high-energy milling, annealing at 

600-900˚C / X-ray diffraction, 


[1994Yan] Mechanical alloying, annealing (at 600- 

900˚C for 5 min to 2 h) / X-ray diffraction, 

TEM, SEM, EDAX, magnetic 

measurements 

[1995Iva] Sm - 99.8%, Fe - 99.98%, Ti - 99.95% 

Induction melting, annealing at 900- 

1250˚C / X-ray diffraction, magnetic 

measurements 

[1995Xia] Induction melting, melt spinning, 

annealing at 580-880˚C for 5 min / X-ray 

diffraction, DTA, magnetic measurements 



MSIT 1 



Range Studied 

Isothermal section at 1000˚C for the 

compositions around τ 1. 

A “Sm(Ti,Fe) 9” phase of the 

Sm 10.44Ti 5.55Fe 84.01 composition is found. 

A phase with the hexagonal Nd 5Fe 17 type 

structure 

Projection of the liquidus surface. 

Equilibria between 1000 and 800˚C. τ 1 is 

in equilibrium with (αFe), TiFe 2, and a Sm 

(Ti,Fe) 9 phase similar to Sm(Ti,Fe) 7. 

Sm(Ti xFe 1–x) y (0.03≤x≤0.08 and 7.0≤≤9.0) 

compositions quenched from 1150 and 

1000˚C exhibit the presence of a new 

phase Sm(Ti 0.065Fe 0.935) 8.5 with an 

orthorhombic structure. 

The TbCu 7 type structure is found in 

Sm 10Ti xFe 90–x (x = 4.5 and 6) 

compositions. 

Compositions Sm xTi 9Fe 91–x (x = 15-30) 

and Sm 26Ti yFe 74–y (y = 0-17) are studied. 

τ 4 is found. 

Sm 20Ti 9Fe 71 annealed at 810˚C comprises 

(Sm,Ti) 2Fe (?) + SmTiFe 6 (metastable, 

cubic) + τ 4 (hcp), + Sm(Ti,Fe) 2. 

Sm 26Ti 9Fe 65 annealed at 810 and 900˚C 

exhibits the presence of analogous 

phases and (Sm,Ti)2Fe17 (?) 

Sm(Ti xFe 1–x) y (0.04≤x≤0.07 and 8.0≤y≤9.0) 

annealed at 1150-1250˚C contains the Sm 

(Ti,Fe)8.5 phase. 

Ribbons corresponding to the τ 1 phase 

composition annealed above 740˚C 

exhibit the transformation Sm(Ti,Fe) 7 

(TbCu 7 type structure (metastable) Ð τ 1 

(ThMn12 type structure). 

7 

DOI: 10.1007/978-3-540-70890-2_30 

ß Springer 2009

8 30 

Fe–Sm–Ti 



[1995Yan1] Induction (repeated) melting, melt 

spinning, annealing at 650 to 750˚C / 

X-ray diffraction, SEM, TEM, EMPA, EDX, 

thermomagnetic analysis, magnetic 

measurements 

[1995Yan2] All components at least 99.9% purity, 

twice arc melting, annealing at 1000- 

1200˚C for 10-60 h, quenching in air or 

water/X-ray diffraction, thermomagnetic 

analysis, magnetic measurements 

[1996Has] R.f. (radio frequency) melting, arc melting, 

powder metallurgical process, annealing 

at 600-1150˚C for 2-100 h / X-ray 

diffraction, SEM/EDX, electron beam 


[1997Liu] 99.95 at.% Sm, 99.9 at.% Fe, 99.5 at.% Ti 

Diffusion triple technique, annealing at 

600˚C for 500 h, quenching in icy salt 

water/electron microprobe analysis 

[1997Yan] Mechanical alloying, annealing at 750- 

870˚C for 30 min / X-ray diffraction, 


[2000Iva] Induction melting, annealing at 1150˚C 

for 4 h or 1000˚C for 48 h / X-ray 

diffraction 

[2000Shc] Induction melting, annealing at 900- 

1450˚C, quenching in water / X-ray 



Range Studied 

In SmTi xFe 7+x (x = 0.2-1.5) melt-spun 

ribbon, Sm(Ti,Fe) 7 formed is stable even 

after annealing. The phase has the 

hexagonal Sm(Mo,Fe)7 type structure. 

In Sm 10Ti xFe 85 (x = 4.2, 4.4, 4.6, 4.8, 5.0, 

6.0, 6.5) annealed at from 1000 to 1200˚C, 

quenched in water, the τ 2 compound 

(Sm 3(Fe 0.933Ti 0.067) 29 stoichiometry) 

(monoclinic Nd3(Ti,Fe)29 type structure is 

found. 

In alloys Sm xTi yFe 100–x–y (x = 6.9-1.17 and 

y = 0-9.7), a nonstoichiometric compound 

R 2(Ti,Fe) 17+δ (δ = 1.0-4.0) with a hexagonal 

structure (space group P62m) exists 

between Sm 2(Ti,Fe) 17 and τ 1. 

Isothermal section at 600˚C 

(compositions (0.08-33.70 at.%) Sm - 

(2.75-85.20 at.%) Ti - (95.98-14.66 at.%) 

Fe). Detected phase regions: 

SmFe 2+TiFe 2+(αSm); TiFe 2+TiFe+(αSm); 

TiFe+(βTi)+(αSm); SmFe 3+SmFe 2+TiFe 2; 

Sm 2Fe 17+TiFe 2+αFe; SmFe 3+TiFe 2+(αFe); 

SmFe 3+Sm 2Fe 17+τ 3;Sm 2Fe 17+TiFe 2+τ 3; 

(αSm)+(αTi)+(βTi). Stoichiometry of τ 3 

from SmTi1.2Fe9.8 to SmTi1.4Fe9.6 

Sm 26Ti yFe 74–y with y = 0, 1, 13, 17 

annealed at 840˚C and with y =3 

annealed at 870˚C contain the mixture of 

phases TiFe 2, SmFe 2,Sm 2(Ti,Fe) 17, τ 4 

Virtually complete solid state 

transformation of the Sm2(Ti,Fe)17+τ1 

mixture into τ 2. 

Sm 2(Ti xFe 1–x) 17 (x≤0.06) with x = 0.02, 

annealed at 1200-1250˚C is a mixture of 

Th 2Zn 17 and Th 2Ni 17 structures; annealed 

at 1200˚C with x = 0.03 and 0.04, both 

structures are observed; after annealing 

at 1250˚C, only the Th 2Ni 17 type structure. 

Monotonic increase in the lattice 

parameters is observed up to x = 0.04. 



MSIT 1



[2004Zha] Arc melting, annealing (at 1100˚C for 

24 h) / X-ray diffraction, scanning electron 

microscopy, magnetic measurements 

[2006Sun] Arc melting, annealing (at 1000˚C for 

48 h), water quenching, HDDR process / 

X-ray diffraction, scanning electron 

microscopy, magnetic measurements 

. Table 2 



Temperature 

Range [˚C] 


Space Group/ 

Prototype 



Range Studied 

In Sm 2(Ti xFe 1–x) 17 (x = 0, 0.02, 0.04, 0.06, 

0.08, 0.1) annealed at 1100˚C with 

x = 0-0.04 Sm 2(Ti,Fe) 17 (Th 2Zn 17 type 

structure) is found; with x = 0.06, - τ 2 

(monoclinic, Nd 3(Ti,Fe) 29 type structure; 

with x = 0.08-0.1 - τ 1 (ThMn 12 type 

structure); with x = 0.08, τ1 coexists with 

τ 2 and Sm(Ti,Fe) 2 

As-cast Sm 2Ti 1Fe 16 consists of τ 2 (the 

main phase) and secondary phases τ1, τ3, 

Sm(Ti,Fe) 2, αFe(Ti) phases; the annealed 

alloy consists of τ 2, τ 1, τ 3, and a few Sm 

rich phases (that depending on the 

cooling direction may be SmFe 2 rather 

than Sm(Ti,Fe) 2). 

Structural relationship τ 2 Ð Sm 2Fe 17 + τ 1 

is valid. 

The τ 3 phase (SmTi 1.5Fe 9.5) 

Lattice 

Parameters 


(δSm) hP4 a = 361.8 at 25˚C, 4.0 GPa [Mas2] 

P63/mmc αLa 

c = 1166 

(γSm) cI2 - [Mas2] 

1074 - 922 Im3m 

W 

(βSm) hP2 a = 366.30 [Mas2] 

922 - 734 P63/mmc Mg 

c = 584.48 

(αSm) hR9 a = 362.90 at 25˚C [Mas2] 

< 734 R3m 

αSm 

c = 2620.7 



MSIT 1 

9 

DOI: 10.1007/978-3-540-70890-2_30 

ß Springer 2009

10 30 

Fe–Sm–Ti 



Temperature 

Range [˚C] 


Space Group/ 

Prototype 

Lattice 

Parameters 


(ωTi) hP3 a = 462.5 at 25˚C, HP → 1 atm [Mas2] 

P6/mmm 

ωTi 

c = 281.3 

(βTi) cI2 a = 330.65 [Mas2] 

1670 - 882 Im3m 

W 

(αTi) hP2 a = 295.06 at 25˚C [Mas2] 

< 882 P63/mmc Mg 

c = 468.35 

(αδFe) cI2 

Im3m 

(δFe) 

1538 - 1394 

W a = 293.15 at 1390˚C [V-C2, Mas2] 

(αFe) 

< 912 

a = 286.65 at 25˚C [Mas2] 

(γFe) cF4 a = 364.67 at 915˚C [V-C2, Mas2] 

1394 - 912 Fm3m 

Cu 

Sm2Fe17 hR57 [Mas2] 

< 1280 R3m a = 857.0 [V-C2] 

Th2Zn17 c = 1244.0 

SmFe3 hR36 [Mas2] 

< 1010 R3m a = 518.7 [V-C2] 

NbB3 c = 2491.0 

SmFe2 cF24 (C15) [Mas2] 

< 900 Fd3m 

Cu2Mg a = 741.6 [V-C2] 

TiFe2 hP12 64.5-72.4 at.% Fe [1987Mur] 

< 1427 P63/mmc a = 477.7 at 64.6 at.% Fe 

MgZn2 c=780.7 

a = 478.1 

c=779.5 

at 71.4 at.% Fe 

TiFe cP2 a = 297.8 ± 0.2 at 50 at.% 

< 1317 Pm3m 47.5-50.3 at.% Fe at 1317˚C 

CsCl 

[1987Mur] 



MSIT 1



Temperature 

Range [˚C] 

* τ1, Sm(Ti,Fe) 12 

(SmTiFe11 stoichiometry) 

1300 - 700 


Space Group/ 

Prototype 

Lattice 

Parameters 


tI26 a = 856 for compositions 7.14 (7.32) at.% 

I4/mmm c = 479 

ThMn 12 


Sm-7.14 (7.55) at.% Ti-85.72 (85.13) 

at.% Fe [1988Oha] 

a = 858 in Sm8Fe84Ti8 annealed at 700˚C 

c = 479 

or 

a = 854 

c = 477 

[1988Sin] 

a = 853.4 for SmTiFe11 c = 477.6 V = 347.832·10 6 pm 3 [1989Zha] 

a = 855.7 for SmTiFe11 b = 480.0 V = 351.4·10 6 pm 3 [1991Yan] 

a = 854 

c = 478 

for SmTiFe11 [1996Kim] 

a = 856.8 for SmTiFe11 c = 479.8 V = 352·10 6 pm 3 [1998Isn] 

a = 843.8 SmFe11.5Ti05 crystallized in 

c = 480.5 sputtered films [1991Cad] 

a = 856.3 for Sm(Fe0.917Ti0.082) 12 

c = 480.2 V = 352·10 6 pm 3 [1996Koy] 

V = 351.1·10 6 pm 3 

a = 856.0 

c = 479.2 

[2001Nik] 

* τ2,Sm3(Ti,Fe) 29 mP* a = 1065 annealing at 1000-1200˚C, 

1240 - 900 P21/c b = 858 quenching from high 

Nd3(Fe,Ti) 29 

c = 972 temperatures, for 

β = 96.98˚ Sm3(Ti0.067Fe0.933) 29 [1995Yan2] 

a = 1063 Sm3(Ti0.06Fe0.94) 29 stoichiometry 

b = 857 V = 881·10 6 pm 3 

c = 974 

β = 97˚ 

[1996Koy] 

a = 1061 

b = 856 

c = 970 

β = 96.9˚ 

[2000Iva] 

a superstructure based on a = 972 1150-1250˚C / Sm(Tix Fe1–x) y 

the CaCu5 type structure b = 856 (0.04≤x≤0.07 and 8.0≤y≤9.0) / Sm 

with a monoclinic cell c = 1063 

β = 96˚50’ 

(Ti,Fe) 8.5 [1995Iva] 



MSIT 1 

11 

DOI: 10.1007/978-3-540-70890-2_30 

ß Springer 2009

12 30 

Fe–Sm–Ti 



Temperature 

Range [˚C] 


Space Group/ 

Prototype 

Lattice 

Parameters 


* τ3, Sm(Ti,Fe) 11 tP24 a = 825.3 SmFe9.5Ti1.5 [1990Jan] 

1100 - 600 P4/mbm 

CeMn6Ni5 or 

c = 482.5 

t* 

Sm(Ti,Fe)11 

[2006Sun] 

* τ4,Sm5(Ti,Fe) 17 hP264 a = 2017.2 in SmxFe91–xTi9 (x = 15-30) and 

870 - 800 P6 3/mcm c = 1237.4 

Nd5Fe17 

. Table 3 

Investigations of the Fe-Sm-Ti Materials Properties 

Sm 26Fe 74–yTi y (y = 0-18) annealed 

at 810 to 870˚C [1994Yan] 


[1987Had] Thermomagnetic analysis / vibratingsample 

magnetometer 

[1988Oha] Magnetization measurements in 

magnetic field applied parallel and 

perpendicular to the c axis 

[1988Sin] Thermomagnetic analysis / vibratingsample 

magnetometer 

[1988Yan] cited from abstract (no experimental 

details are available) 

[1989Had] cited from abstract (no experimental 

details are available) 

For as-cast, melt-spun, crystallized 

ribbons, aligned powders, and sintered 

magnets Sm xTi zFe y (3≤x≤15, 78≤y≤87, 

3≤z≤13), hysteresis loops are measured; 

the maximum anisotropy field is more 

than 18 kOe (14.328 kA·m –1 ). 

Room temperature coercive force 

(0.2-2.5 kOe (0.159 -1.99 kA·m –1 )) and 

hysteresis loops determined for as-cast 

materials, melt-spun ribbons, aligned 

powders, and sintered magnets are given 

Magnetization curve for τ 1; c axis is the 

easy axis of magnetization. 

Room-temperature coercivity of meltspun 

ribbons Sm 8Ti 8Fe 84 crystallized with 

the formation of τ 1 is 2 kOe 

(1.592 kA·m –1 ). 

τ 1 exhibits unusual uniaxial 

magnetocrystalline anisotropy, c-axis is 

the easy magnetization direction, T C = 

337˚C. 

The τ 1 phase coercivity is 7.7 kOe 

(6.13 kA·m –1 ). 



MSIT 1



[1989Str] Thermomagnetic measurements For Fe-Sm-Ti compositions (with the 

ThMn 12 type structure) alloyed with B and 

Si+Al, the possible coercive force is 

> 6.5 kOe (5.174 kA·m –1 ). 

[1989Zha] Faraday balance, vibrating sample 

magnetometer 

Increase in the Curie temperature and 

anisotropy field for τ 1 by hydrogenation: 

T C from 311 to 354˚C and anisotropy field 

H A from 140 (111.44) to 170 kOe 

(135.32 kA·m –1 ). 

[1990Din] Vibriting sample magnetometer The magnetization of Sm 10Ti 8Fe 82 

annealed at 600-700˚C containing the 

metastable phase with the TbCu 7 

structure is 110 Am 2 ·kg –1 . 

[1990Jan] Thermomagnetic analysis, magnetization 

measurements 


13 

Curie temperature of Sm(Ti,Fe) 7 is 200˚C; 

T C of τ 1 is 305˚C. τ 3 has no magnetic 

moment. 

Magnetization curves for Sm7.7Ti9.2Fe83.1 

are given. 

[1990Kat] Vibriting sample magnetometer Magnetization (vs melt-spinning 

parameters), hysteresis loop, coercivity (vs 

annealing temperature of melt-spun 

ribbons), remanence for Sm20Ti10Fe70 quenched from 1400˚C + annealed at 

800˚C for 15 min are given; iHc= 44.5 kOe 

(35.422 kA·m –1 ). 

For Sm25Ti9.4Fe65.6 annealed at 850˚C, 

iHc= 58 kOe (46.168 kA·m -1 ), Br = 2.4 kG. 

[1990Sch1] magnetic hysteresis loop measurements For Sm20Ti10Fe70 mechanically alloyed 

and sintered at 725˚C for 30 min, Hc = 

50.3 kOe (40.04 kA·m –1 ), Br = 3.0 kG, 

(BH) max = 2.2 MG Oe (17.5 kJ·m –3 ), TC = 

380˚C. 

For Sm10Ti10Fe80-based compositions, the 

effect of B, Mo, Co, V, Si, Ga additions is 

discussed. 

[1990Sch2] Vibrating-sample magnetometer Demagnetization curves and Br vs 

composition for SmxTi10Fe90–x (x = 16-22) 

mechanically alloyed (or rapidly 

quenched) and annealed at 800˚C for 30 

min (or hot pressed) are given. TC = 380˚ 

C, Hc = 50.3 kOe (40.038 kA·m –1 ), Br = 3.0 

kG, Ms = 6-7 kG, (BH) max = 2.2 MG Oe (17.5 

kJ·m –3 ); temperature dependence of 

coercivity is given. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_30 

ß Springer 2009

14 30 

Fe–Sm–Ti 



[1990Wan] Thermomagnetic analysis / vibratingsample 

magnetometer 

For Sm 8Ti 9Fe 83 ribbons annealed at 800˚ 

C, iH c = 5.6 kOe (4.46 kA·m –1 ), M s = 806 G. 

V-containing compositions have the 

higher H c, decrease in H c for Nb-, Mo-, Wcontaining 

compositions, increase in Hc 

by Zr (small content) and Ga additions are 

observed; all the additions decrease M s. 

Preparation of sintered magnets is 

discussed, measured hysteresis loop 

shows H c = 2 kOe (1.592 kA·m –1 ). 

[1990Wec] Vibrating-sample magnetometer For Sm8.3Ti8.3Fe83.4 and Sm7.7Ti15.4Fe76.9 

crystallized ribbons, iH c = 3.4 kA·cm –1 

[1991Kim] Ac-susceptibility, measurements / 

Vibrating-sample magnetometer 

[1991Sta] Cathodic sputtering or mechanical 

alloying 

(0.034 kA·m –1 ). 

iH c = 40 (0.40) and 33 kA·cm –1 (0.33 

kA·m –1 ) is observed for a new phase 

found in Sm 20Ti 10Fe 70 mechanically 

alloyed (followed by solid-state reaction 

at 725˚C) and rapidly quenched followed 

by annealing at 800˚C), respectively; T C = 

380˚C. 

Improving properties (coercivity) and 

increase in T C by Zr and Co additions; 

decrease in the anisotropy field, change 

of the anisotropy type from axial to planar 

are observed. 

Magnetization, isocoercivity lines of Fe- 

Sm-Ti (around τ 1) melt-spun samples are 

given. 

SmFe 9Ti 2 (τ 3) is non-magnetic or weakly 

magnetic. 

The possibility to synthesize a 

magnetically hard phase in Fe-Sm-Ti 

compositions is shown; the phase has the 

hexagonal Nd 5Fe 17 type structure. 

[1991Yan] Extracting-sample magnetometer Nitrogenation of τ1 at 500˚C for 2 h 

changes the c-axis plane anisotropy to 

basal-plane one. 

[1991Wec] Rapid solidification The high coercivity more than 40 kA·cm –1 

[1994Iva] Vibrating-sample magnetometer, acsusceptibility 

measurements 

(0.40 kA·m –1 ) can be reached for Fe-Sm-Ti 

compositions with the Sm 5(Ti,Fe) 17 phase 

(named A 2). 

Magnetization curves, specific 

magnetization vs temperature for Sm(Ti, 

Fe) 8.5 are given; it is highly anisotropic 

ferromagnet with T C = 197˚C. 



MSIT 1



[1994Wan] Vibrating-sample magnetometer, 

extracting-sample magnetometer 

[1994Yan] Pulsed magnetometer, ac-susceptibility 

measurements 

Thermomagnetic analysis for 

Sm 10Ti 4.5Fe 85.5 is performed. 

Nitrogenation increases the Curie 

temperature; magnetization curves, 

hysteresis loop, dependence of the Curie 

temperature of nitrides on the annealing 

temperature are given. 

Ac-susceptibility, Curie temperature, 

magnetization curves, coercive force, 

remanence, energy product for 

SmxTi9Fe91–x mechanical alloyed, 

annealed at 810-840˚C for 30 min are 

given. 

T C = 160-180˚C. 

At x = 26, room-temperature iH c = 69.09 

kOe (54.995 kA·m –1 ) (annealing at 840˚C 

for 50 min); the high coercivity is due to 

the Sm 5(Ti,Fe) 17 phase. 

At x = 15, 4πM r =2.98 kG, (BH) max = 2.228 

MG Oe (17.735 kJ·m –3 ). 

[1995Cad] review, no experimental details given A SmFe 5 phase stabilized by Ti has iH c = 

6.2 kOe (4.935 kA·m –1 ), (BH) max = 5.4 MG 

Oe (42.984 kJ·m –3 ), T C = 400˚C. 

Crystal phase connections and 

transformations between 2:17, 1:12, 1:7 

structures that are derivatives from the 

CaCu5 structure, magnetization and 

anisotropy consideration are discussed. 

[1995Iva] Ac-susceptibility measurements / 

vibrating sample magnetometer 

[1995Xia] Pulsed magnetometer, ac-susceptibility 

measurements 



MSIT 1 


15 

Room temperature magnetization curves 

for Sm(Ti0.065Fe0.935)8.5 and Sm2(Ti,Fe)17 

are given. 

For τ 1 ribbons melt-spun and annealed, 

ac-susceptibility vs temperature and 

coercivity vs annealing temperature are 

given. 

The coercivity iH c = 5.8 kOe (4.62 kA·m –1 ) 

is reached for ribbons quenched at 30 m/ 

s + annealed at 820˚C. 

DOI: 10.1007/978-3-540-70890-2_30 

ß Springer 2009

16 30 

Fe–Sm–Ti 



[1995Yan1] Thermomagnetic analysis / vibratingsample 

magnetometer 

[1995Yan2] Magnetically aligned powder, 

thermomagnetic analysis / extracting 

sample magnetometer, SQUID, high-field 

installation 

Curie temperature, hysteresis loops, 

coercive force, remanence, energy 

product are given for SmTi xFe 7+x (x = 0.2- 

2) (repeated induction melting, melt 

spinning, annealing at 650-750˚C): 

at x = 1.5, iH c = 5 kOe (3.98 kA·m –1 ), 

(BH) max = 3.4 MG Oe (27.064 kJ·m –3 ); 

at x = 0.4-1.0, Br = 6-8 kG; at x = 0.8, 

(BH) max = 4.0 MG Oe (31.84 kJ·m –3 ); at 

x = 1.0, T C = 304˚C. 

Curie temperature, magnetization, 

saturation magnetization, anisotropy field 

are given for Sm 3(Fe 0.933Ti 0.067) 29: 

T C = 213˚C, M s = 119 Am 2 ·kg –1 , uniaxial 

anisotropy, H a = 3.4 T, first-order 

magnetization process (FOMP). 

Nitrogenation to 5.0 N per formula unit 

(powder 15 μm size) at N 2 pressure 1 atm, 

500-600˚C for 2 h results in increase in 

both the Curie temperature to 477˚C, M s 

= 140 Am 2 ·kg –1 , uniaxial anisotropy Ha = 

12.8 T; μ 0iH c = 0.83 T, (BH) max = 105 kJ·m –3 

at 293 K 

[1996Has] Magnetization measurements Saturation magnetization, Curie 

temperature (no values are available) for 

Sm xTi yFe 100–x–y (x = 6.9-1.17 and y = 0-9.7) 

for R 2Ti,Fe) 17+δ (δ = 1.0-4.0) 

nonstoichiometric compound are given. 

[1996Kim] Thermomagnetic analysis / vibratingsample 

magnetometer, SQUID, / 

computer calculations 

For τ 1, magnetization vs temperature, 

anisotropy constants K 1 = 9.2 MJ·m –3 ,K 2 = 

0.40 MJ·m –3 , anisotropy field μ 0H A = 19.8 

T, T C = 314˚C, c-axis magnetization 

direction are given. Substitution of other 

rare-earth metals for Sm decreases 

substantially the anisotropy field. 



MSIT 1



[1996Koy] Thermomagnetic analysis / vibratingsample 

magnetometer 

[1997Yan] Pulsed magnetometer, ac-susceptibility 

measurements 

[1998Isn] Thermomagnetic analysis / High Field 

Magnet Facility 

[1998Pao] Thermomagnetic analysis / Singular point 

detection technique 

[1998Ter] Thermomagnetic analysis / vibratingsample 

magnetometer, torque 

magnetometer 

[1999Hu] Thermomagnetic analysis / vibratingsample 

magnetometer, extractingsample 

magnetometer 


For Sm 3(Fe 0.94Ti 0.06) 29, magnetization 

(FOMP), anisotropy field, Curie 

temperature are M s = 98.3-103 Am 2 ·kg –1 , 

μ 0H A =4T,T C = 212˚C. 

Schematic diagram of the formation of τ 2 

structure from CaCu 5 structure is given. 

The use of hydrogenation (cooling to 

room temperature in hydrogen 

atmosphere after heating to 500˚C) and 

nitrogenation (at 475-500˚C for 10-24 h at 

0.1-1 MPa) results in the increase in the 

lattice parameters, T C. 

For Sm 26Ti yFe 74–y, with y =0,1,3,17, 

temperature dependences of acsusceptibility, 

demagnetization curves 

are given. 

17 

For τ 1, Curie temperature magnetization 

curves are given: M s = 17.5 μ B/f.u, 

anisotropy constants K 1 = 3.9 MJ·m –3 , 

K 2 = 0.1 MJ·m –3 ; hydrogenation to about 

1 H per f.u., (initial thermal activation and 

20 bar H 2 pressure) results in the increase 

in the lattice parameters, Curie 

temperature, saturation magnetization. 

For Sm 2Ti xFe 17–x (x = 0-0.85), Curie 

temperature increases with increasing Ti 

content, anisotropy constant and 

anisotropy field decrease; compositional 

dependence of lattice parameters on Ti 

content is shown. 

Compositional dependences of the Curie 

temperature, saturation magnetization, 

and anisotropy constants are given. 

Effect of Co substitution for Fe on the 

parameters is discussed. 

Compositions Sm10Fe85.5Ti4.5 and 

Sm 10Fe 84Ti 6 (with TbCu 7 type structure) 

are discussed. 

Nitrogenation (at 450˚C for 2 h) increases 

the lattice parameters, Curie temperature 

and saturation magnetization. 

[1999Shi] X-ray diffraction, DTA, TEM Compositions Sm-Fe-Ti-C and effect of C 

and Ti on the glassy stability are 

discussed. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_30 

ß Springer 2009

18 30 

Fe–Sm–Ti 



[2000Pao] Thermomagnetic analysis / Singular point 

detection technique 

[2000Shc] Extraction magnetometer, SQUID, 

ac-susceptibility measurements 

For Sm 2Ti xFe 17–x (x = 0, 0.4, 0.75) 

anisotropy constant, anisotropy field (that 

decreases with increasing x) are given, the 

Sm contribution to the anisotropy is 

analyzed. 

For Sm 2(Ti xFe 1–x) 17 (x = 0.02, 0.03, 0.04), 

magnetization curves and ac 

susceptibility vs temperature for samples 

with different (Th 2Zn 17 and Th 2Ni 17) 

structures, Curie temperature, 

magnetization curves, anisotropy 

constants; increase in T C up to x = 0.04 are 

discussed. The type of structure affects 

the magnetic properties. For both 

structure types, the easy magnetization 

direction lies in the basal plane. 

Nitrogenation (at 450-500˚C for 4-12 h) 

allows one to obtain highly anisotropic 

uniaxial ferromagnets. 

[2004Zha] Ac-susceptibility / pulsed magnetometer For Sm 2(Ti xFe 1–x) 17 (x = 0.0, 0.02, 0.04, 

0.06, 0.08, 0.1), the Curie temperature, 

temperature dependence of acsusceptibility 

is given: 

x =0,TC = 125˚C; x = 0.02, TC = 139˚C; x = 

0.04, T C = 174˚C; x = 0.06, τ 2, T C = 210˚C; x 

= 0.08 and 0.1, τ 1, T C = 314˚C. 

Hydrogenation at 300˚C and 800˚C, 1 atm 

for 1 h and nitrogenation at 500˚C for 3h, 

1 atm increase the Curie temperature. iH c, 

B r, (BH) max of hydrides and nitrides, 

hysteresis loops of nitrides are given. 

[2001Che] 

[2001Wan] 

Theoretical estimation Stabilization of the τ 1 compound 

structure by different transition metals 

(T = Ti, V, Cr, Co, Sc, Mn); calculated lattice 

parameters are given. 

[2001Nik] Pendulum and torque magnetometer For τ 1, T C = 325˚C, σ s = 18.5 μ 0/f.u., 

H A = 102 kOe (81.192 kA·m –1 ). 

Transformation of the magnetic structure 

of τ 1 upon hydrogenation and 

nitrogenation is discussed. 



MSIT 1



[2002Sko] Extraction magnetometer, a pulsed field 

facility 


Anisotropy constants of τ 1 and effect of 

hydrogenation on the constants are 

discussed. 

19 

[2006Sun] Vibrating sample magnetometer For Sm 2Fe 16Ti 1, hydrogenation at 800˚C 

for 2 h at 0.12 MPa and nitrogenation at 

500˚C for different time at 0.13 MPa, 

effect of the lattice parameters, coercivity, 

magnetization, remanence. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_30 

ß Springer 2009

20 30 

Fe–Sm–Ti 

. Fig. 1 

Fe-Sm-Ti. The Sm-Ti binary phase diagram 



MSIT 1

. Fig. 2 

Fe-Sm-Ti. Reaction scheme 



MSIT 1 


21 

DOI: 10.1007/978-3-540-70890-2_30 

ß Springer 2009

22 30 

Fe–Sm–Ti 

. Fig. 3 

Fe-Sm-Ti. Partial liquidus surface projection 



MSIT 1

. Fig. 4 

Fe-Sm-Ti. Isothermal section at 1000˚C 



MSIT 1 


23 

DOI: 10.1007/978-3-540-70890-2_30 

ß Springer 2009

24 30 

Fe–Sm–Ti 

. Fig. 5 




MSIT 1

. Fig. 6 




MSIT 1 


25 

DOI: 10.1007/978-3-540-70890-2_30 

ß Springer 2009

26 30 

Fe–Sm–Ti 

References 

[1982Kub] Kubaschewski, O., Iron Binary Phase Diagrams, Springer Verlag, Berlin, Verlag Stahleisen, Düsseldorf, 

152–156 (1982) (Phase Diagram, Review, 26) 

[1987Had] Hadjipanayis, G.C., Aly, S.H., Cheng, S.-F., “Hard Magnetic Properties of R-Fe-Ti”, Appl. Phys. Lett., 51 

(24), 2048–2050 (1987) (Crys. Structure, Magn. Prop., Experimental, 7) 

[1987Mur] Murray, J.L., “The Fe-Ti (Iron-Titanium) System”, Phase Diagrams of Binary Titanium Alloys, ASM 

Inter., Metal Park, Ohio, Murray, J.L. (Ed.), 99–111 (1987) (Experimental, Phase Diagram, Phase 


[1988Oha] Ohashi, K., Tawara, Y., Osugi, R., “Identification of the Intermetallic Compound Consisting of Sm, Ti, 

Fe”, J. Less-Comm. Met., 139, L1–L5 (1988) (Crys. Structure, Magn. Prop., Experimental, 2) 

[1988Sin] Singleton, E.W., Strzeszewski, J., Hadjipanayis, G.C., “Magnetic and Structural Properties of Melt-Spun 

Rare-Earth Transition-Metal Intermetallics with ThMn 12 Structure”, J. Appl. Phys., 64(10), 5717–5719 

(Crys. Structure, Magn. Prop., Experimental, 9) 

[1988Yan] Yang, Y.-C., Kong, L.-S., Cheng, B.-P., “Structural and Magnetic Properties of Sm(Ti,Fe) 12 Intermetallic 

Compounds”, Acta Phys. Sin., 37(9), 1534–1539 (1988) (Crys. Structure, Magn. Prop., Experimental, 5) 


[1989Had] Hadjipanayis, G.S., “A Search for New Phases and Processing Techniques for Permanent Magnet 

Development”, Mater. Sci. Eng. B, B3(4), 431–434 (1989) (Magn. Prop., Experimental, 19) cited from 

abstract 

[1989Str] Strzeszewski, J., Wang, Y.Z., Singleton, E.W., Hadjipanayis, G.C., “High Coercivity in Sm(FeT) 12 Type 

Magnets”, IEEE Trans. Magn., 25(5), 3309–3311 (1989) (Crys. Structure, Magn. Prop., Experimental, 10) 


[1989Zha] Zhang, L.Y., Wallace, W.E., “Structural and Magnetic Properties of RTiFe 11 and their Hydrides (R = Y, 

Sm)”, J. Less-Comm. Met., 149, 371–376 (1989) (Crys. Structure, Magn. Prop., Experimental, 16) 

[1990Coc] Cochet-Muchy, D., Paidassi, “Rapidly Quenched Hard Magnetic Alloys with ThMn 12 Structure”, J. 

Magn. Magn. Mater., 83, 249–250 (1990) (Crys. Structure, Magn. Prop., Experimental, 7) 

[1990Din] Ding, J., Rosenberg, M., “Phase Analysis By X-ray and Moessbauer Spectroscopy of Melt-Spun and 

Subsequently Annealed Sm-(Fe, Co or Ni)-Ti”, J. Less-Comm. Met., 166, 303–311 (1990) (Crys. 


[1990Jan] Jang, T.S., Stadelmaier, H.H., “Phase Equilibria and Magnetic Properties of Iron-Rich Fe-Nd-Ti and Fe- 

Sm-Ti Alloys”, J. Appl. Phys., 67(9), 4957–4959 (1990) (Crys. Structure, Phase Relations, Phase Diagram, 

Magn., Prop., Experimental, *, 15) 

[1990Kat] Katter, M., Wecker, J., Schultz, L., Groessinger, R., “Preparation of Highly Coercive Sm-Fe-Ti by Rapid 

Quenching”, Appl. Phys. Lett., 56(14), 1377–1379 (1990) (Crys. Structure, Phase Relations, Magn. Prop., 


[1990Sch1] Schultz, L., Schnitzke, K., Wecker, J., “Magnetic Hardering of Sm-Fe-Mo, Sm-Fe-V and Sm-Fe-Ti 

Magnets”, J. Magn. Magn. Mater., 83, 254–256 (1990) (Magn. Prop., Experimental, 10) 

[1990Sch2] Schnitzke, K., Schultz, L., Wecker, J., Katter, M., “Sm-Fe-Ti Magnets with Room-Temperature 

Coercivities above 50 kOe”, Appl. Phys. Lett., 56(6), 587–589 (1990) (Magn. Prop., Experimental, 16) 

[1990Wan] Wang, Y., Hadjipanayis, G.C., Kim, A., Liu, N.C., Sellmyer, D.J., “Magnetic and Structural Studies in 

Sm-Fe-Ti Magnets”, J. Appl. Phys., 67(9), 4954–4956 (1990) (Crys. Structure, Magn. Prop., Experimental, 

9) 

[1990Wec] Wecker, J., Katter, K., Schnitzke, K., Schultz, L., “Magnetic Hardening of Sm-Fe-Ti Alloys”, J. Appl. 

Phys., 67(9), 4951–4953 (1990) (Magn., Prop., Experimental, 15) 

[1991Cad] Cadieu, F.J., Hegde, H., Navarathna, A., Rani, R., Chen, K., “High-Energy Product ThMn 12 Sm-Fe-T 

and Sm-Fe Permanent Magnets Synthesized as Oriented Sputtered Films”, Appl. Phys. Lett., 59(7), 


[1991Kim] Kim, Y.B., Sugimoto, S., Okada, M., Homma, M., “Phase Relations of the Sm-Fe-Ti System Around the 

Compound SmFe 11Ti”, J. Alloys Compd., 176(2), 215–224 (1991) (Crys. Structure, Phase Relations, 

Phase Diagram, Magn. Prop., Experimental, #, *, 12) 

[1991Nei] Neiva, A.C., Messell, F.P., Grieb, B., Henig, E.-Th., Petzow, G., “Phase Equilibria Around SmFe 11Ti 

at 1000˚C”, J. Less-Common Met., 170(2), 293–299 (1991) (Assessment, Crys. Structure, Phase Diagram, 

#, *, 23) 



MSIT 1


27 

[1991Qia] Qian, X.R., Chen, M.X., Chen, L., Jin, H.J., Chen, L.J., Xu, G.Q., “Moessbauer Study of Melt-Spun 

Sm 20Fe 70Ti 10 Alloy”, Hyperfine Interactions, 69, 585–588 (1991) (Crys. Structure, Experimental, 6) 

[1991Rei] Reinsch, B., (in German), Constitution of the Fe-Sm-Ti System, Diploma, Uni. Stuttgart, 86 pp. (1991) 

(Crys. Structure, Experimental, Morphology, Phase Diagram, Phase Relations, 43) 

[1991Sta] Stadelmaier, H.H., Schneider, G., Henig, E.-T., Ellner, M., “Magnetic Fe 17R 5 in the Fe-Nd and Fe(-Ti)- 

Sm Systems, and Other Phases in Fe-Nd”, Mater. Lett., 10(7-8), 303–309 (1991) (Crys. Structure, 

Experimental, 30) cited from abstract 

[1991Wec] Wecker, J., Katter, M., Schultz, L., “High Coercivity in Sm-Fe-Ti Alloys by Rapid Solidification”, Mater. 

Sci. Eng. A, A133, 147–150 (1991) (Magn. Prop., Experimental, 17) cited from abstract 

[1991Yan] Yang, Y.-C., Zhang, X.-D., Kong, L.S., Pan, Q., Ge, S.-L., “Magnetocrystalline Anisotropy of RTiFe 11N x 

Compounds”, Appl. Phys. Lett., 58(18), 2042–2044 (1991) (Crys. Structure, Magn. Prop., Experimental, 

4) 

[1992Rei] Reinsch, B., Grieb, B., Henig, E.-T., Petzow, G., “Phase Relations in the System Sm-Fe-Ti and the 

Consequences for the Production of Permanent Magnets”, IEEE Trans. Magn., 28(5), 2832–2834 (1992) 

(Phase Relations, Phase Diagram, Experimental, *, 13) 

[1994Iva] Ivanova, G.V., Makarova, G.M., Sherbakova, E.V., Belozerov, E.V., Ermolenko, A.S., “Structure and 

Magnetic Properties of a Novel Ternary Compound Sm(Fe, Ti) 8.5”, Phys. Met. Metallogr., 78(2), 162–166 

(1994), translated from Fiz. Met. Metalloved., 78(2), 60–65 (1994) (Crys. Structure, Magn. Prop., 


[1994Wan] Wang, K.-Y., Wang, Y.-Z., Hu, B.-P., Lai, W.-Y., “Magnetic Properties of Sm-Fe-Ti and its Nitrides with 

TbCu 7 Structure”, Physica B, 203, 54–58, (1994) (Crys. Structure, Magn. Prop., Experimental, 14) 

[1994Yan] Yang, J., Wang, Q., Sun, X.-K., Zeng, G., Chen, M., Liu, W., Zhao, X., Zhao, T., Zhang, Z., “The 

Structure and Magnetic Hardening in Mechanically Alloyed Sm-Fe-Ti Systems”, J. Magn. Magn. Mater., 

132, 197–206 (1994) (Crys. Structure, Magn. Prop., Experimental, 14) 

[1995Cad] Cadieu, F.J., “Recent Advances in Pseudobinary Iron Based Permanent Magnets”, Int. Mater. Rev., 40(4), 

137–148 (1995) (Crys. Structure, Magn. Prop., Review, 52) 

[1995Iva] Ivanova, G.V., Makarova, G.M., Sherbakova, E.V., Belozerov, E.V., “The Formation of Z-Phase Sm(Fe, 

Ti) 8.5”, J. Alloys Compd., 224, 29–32 (1995) (Crys. Structure, Magn. Prop., Experimental, *, 10) 

[1995Xia] Xiao, Q.-F., Sun, X.-K., Geng, D.-Y., Liu, W., Zhang, Z.-D., Chuang, Y.-C., “Structure and Magnetic 

Properties of Rapidly Quenched Sm-Fe-Ti Alloys”, J. Magn. Magn. Mater., 140–144, 1093–1094 (1995) 


[1995Yan1] Yang, C.J., Park, E.B., Choi, S.D., “Magnetic Hardening of Rapidly Solidified SmFe 7+xM x (0.8≤x≤1.5, 

M = Mo, V, Ti) Compounds”, Mater. Lett., 24, 347–354 (1995) (Crys. Structure, Magn. Prop., Experimental, 

15) 

[1995Yan2] Yang, F., Nasunjilegal, B., Wang, J., Zhu, J., Qin, W., Tang, N., Zhao, R., Hu, B., Wang, Y., Li, H., 

“Formation and Magnetic Properties of Sm 3(Fe, Ti) 29N y Compounds”, J. Phys.: Condens. Matter, 7, 


[1996Has] Hasebe, A., Otsuki, E., “Crystal Structure and Magnetic Properties of R 2(Fe, M) 17+δ”, Mater. Trans., JIM, 

37(4), 870–877 (1996) (Crys. Structure, Phase Relations, Experimental, 12) 

[1996Kap] Kapusta, C., Figiel, H., Lord, J.S., Tomka, G.J., Riedi, P.C., Buschow, K.H.J., Kou, X.C., Wiesinger, G., 

“NMR Study of SmTM 12–xM x (TM = Fe, Co, M = Ti, Mo)”, J. Magn. Magn. Mater., 157/158, 109–110 


[1996Kim] Kim, H.T., Kim, Y.B., Kim, C.S., Kim, T.K., Jin, H., “Magnetocrystalline Anisotropy of (Sm 0.5Re 0.5) 

Fe 11Ti Compounds (Re = Ce, Pr, Nd, Sm, Gd, and Tb”, J. Magn. Magn. Mater., 152, 387–390 (1996) 


[1996Koy] Koyama, K., Fujii, H., Suzuki, S., “Magnetic Properties of Interstitially Modified Compounds Sm 3(Fe, 

M) 29Z x (M = Ti, V, Cr, and Z = H or N)”, J. Magn. Magn. Mater., 161, 118–126 (1996) (Crys. Structure, 

Magn. Prop., Experimental, 38) 

[1997Liu] Liu, Z, Jin, Z., “Determination of Phase Equilibria in the Sm-Fe-Ti System at 600˚C”, Z. Metallkd., 88 

(2), 174–177 (1997) (Phase Relations, Diagram, Crys. Structure, Experimental, Review, #, *, 9) 

[1997Yan] Yang, J., Wang, Q., Sun, X., “The Structures and Magnetic Properties of Mechanically Alloyed Sm-Fe-T 

(T = Ti, Ti+V, V) Systems”, J. Magn. Magn. Mater., 166, 216–222 (1997) (Crys. Structure, Magn. Prop., 


[1998Isn] Isnard, O., Miraglia, S., Guillot, M., Fruchart, D., “Hydrogen Effects on the Magnetic Properties of 

RFe 11Ti Compounds”, J. Alloys Compd., 275–277, 637–641 (1998) (Crys. Structure, Magn. Prop., 




MSIT 1 

DOI: 10.1007/978-3-540-70890-2_30 

ß Springer 2009

28 30 

Fe–Sm–Ti 

[1998Pao] Paoluzi, A., Pareti, L., “Magnetocrystalline Anisotropy of Fe and Sm Sublattices in Sm 2Fe 17: Effects of Ti 

Substitution for Fe”, J. Magn. Magn. Mater., 189, 89–95 (1998) (Crys. Structure, Magn. Prop., Experimental, 

27) 

[1998Ter] Tereshina, I.S., Nikitin, S.A., Ivanova, T.I., Skokov, K.P., “Rare-Earth and Transition Metal Sublattice 

Contribution to Magnetization and Magnetic Anisotropy of R(TM, Ti) 12 Single Crystals”, J. Alloys 

Compd., 275–277, 625–628 (1998) (Crys. Structure, Magn. Prop., Experimental, 14) 

[1999Hu] Hu, J., Wang, K., Wang, Y., Hu, B., Wang, Z., “Volume Expansion and Curie Temperature Enhancement 

in Rare-Iron Based Nitrides with TbCu 7 Structure”, J. Alloys Compd., 292, 233–235 (1999) (Crys. 

Structure, Magn. Prop., Experimental, 9) 

[1999Shi] Shield, J.E., “Phase Formation and Crystallization Behavior of Melt Spun Sm-Fe-Based Alloys”, J. Alloys 

Compd., 291, 222–228 (1999) (Crys. Structure, Thermodyn., Experimental, 7) 

[2000Iva] Ivanova, G.V., Makarova, G.M., Sherbakova, E.V., Teitel, E.I., “Mechanism of the Y 2(Fe, V) 17 → EY 3(Fe, 

V) 29 Phase Transformation”, Phys. Met. Metallogr., 89(5), 501–507 (2000), translated from Fiz. Met. 

Metalloved., 89(5), 82–87 (2000) (Crys. Structure, Magn. Prop., Phase Relations, Experimental, *, 14) 

[2000Pao] Paoluzi, A., Albertini, F., Pareti, L., “Comparison Among the Second-Order Anisotropy Constants of 

RE (Pr, Nd, Sm) and Fe Sublattices in the RE 2Fe 17 Rhombohedral Structure. Effects of Ti Substitution 

for Fe”, J. Magn. Magn. Mater., 212, 183–188 (2000) (Calculation, Magn. Prop., Experimental, 12) 

[2000Rag] Raghavan, V., “Fe-Sm-Ti (Iron-Samarium-Titanium)”, J. Phase Equilib., 21(5), 464–466 (2000) (Crys. 

Structure, Phase Relations, Phase Diagram, Review, #, *, 15) 

[2000Shc] Shcherbakova, Ye.V., Ivanova, G.V., Mushnikov, N.V., Gervasieva, I.V., “Magnetic Properties of Sm 2(Fe, 

Ti) 17 Compounds and their Nitrides with Th 2Zn 17 and Th 2Ni 17 Structures”, J. Alloys Compd., 308, 15–20 

(2000) (Crys. Structure, Magn. Prop., Experimental, 16) 

[2001Che] Chen, N.-X., Hao, S.-Q., Wu, Y., Shen, J., “Phase Stability and Site Preference of Sm(Fe,T) 12”, J. Magn. 

Magn. Mater., 233, 169–180 (2001) (Calculation, Crys. Structure, Magn. Prop., Experimental, 19) 

[2001Nik] Nikitin, S.A., Tereshina, I.S., Verbetsky, V.N., Salamova, A.A., “Transformations of Magnetic Phase 

Diagram as a Result of Insertion of Hydrogen and Nitrogen Atoms in Crystalline Lattice of RFe 11Ti 

Compounds”, J. Alloys Compd., 316, 46–50 (2001) (Crys. Structure, Magn. Prop., Experimental, 14) 

[2001Wan] Wang, Y., Shen, J., Chen, N.X., Wang, J.L., “Theoretical Investigation on Site Preference of Foreign 

Atoms in Rare-Earth Intermetallics”, J. Alloys Compd., 319, 62–73 (2001) (Crys. Structure, Magn. Prop., 

Calculation, Theory, 33) 

[2002Sko] Skourski, Y., Tereshina, I., Wirth, S., Drulis, H., Mattern, N., Eckert, D., Nikitin, S., Mueller, K.-H., 

“Magnetocrystalline Anisotropy of SmFe 11–xCo xTiH y”, IEEE Trans. Magn., 38(5), 2931–2933 (2002) 


[2004Zha] Zhao, X., Zhang, Z., Sun, X.K., Liu, W., Guo, Z., Xiao, Q., Geng, D., “Structural and Magnetic 

Properties of Sm 2(Fe 1–xTi x) 17 (x = 0-0.1) Alloys Prepared by Hydrogenation Processes and Their 

Nitrides”, J. Magn. Magn. Mater., 208, 231–238 (2004) (Crys. Structure, Magn. Prop., Experimental, 17) 

[2006Sun] Sun, J.B., Cui, C.-X., Zhang, Y., Wang, R., Li, L., Yang, W., Liu, Y.-L., “Structural and Nitrogenation of 

Sm 2Fe 16Ti 1 Alloy Prepared by HDDR Process”, Mater. Chem. Phys., 97, 116–120 (2006) (Crys. Structure, 

Magn. Prop., Experimental, 19) 


(1990) 





MSIT 1

Iron – Tin – Zirconium 


Shuhong Liu, Yong Du, Honghui Xu, Baiyun Huang 

Introduction 

Fe–Sn–Zr 31 

1 

The ternary system Fe-Sn-Zr system was investigated by [1960Tan, 1968Kud, 1990Kor, 

2000Nie, 2001Nie, 2006Nie]. Literature data up to 1990 were reviewed by [1992Rag]. The 

phase relations in the Zr rich corner up to βZrFe 2 and Zr 4Sn have been determined by 

[1960Tan] using X-ray diffraction (XRD) and metallography in the temperature range between 

700 and 1100˚C. The alloys were prepared from high purity materials by nonconsumable 

electrode arc melting techniques under an inert atmosphere. Heat treatments were carried 

out in Vycor bulbs either evacuated or under a partial pressure of argon. A ternary phase θ 

with the composition range of Zr-(11.6-13.1) Fe-19.1Sn (in at.%) was found by [1960Tan]. 

Subsequently, the investigators [1990Kwo2, 1999Zav, 2007Cos] determined its crystal structure. 

They verified that θ is a Zr 6Al 2Co type compound of hexagonal structure, with a very 

narrow homogeneity range and a formula of Zr 6Sn 2Fe. [1968Kud] analyzed the Zr rich region 

of the Fe-Sn-Zr system through microstructure studies and measurements of hardness and 

microhardness. Nevertheless, [1968Kud] did not report the presence of the θ phase. By means 

of XRD, electron microscope and the X-ray phase microanalyzer of the “Cameca” system, 

[1990Kor] gave a phase diagram for the ternary system in the concentration region of 

Zr-βZrFe2-Zr5Sn3 and the temperature range from 500 to 1600˚C. The investigation by 

[1990Kor] confirmed the existence of the ternary compound θ reported by [1960Tan]. As 

many as 15 alloys were melted by [1990Kor] from zirconium iodide (erroneously given as 

9.6%), high purity tin (99.9 mass%) and Armco iron in an arc furnace under an argon 

atmosphere using an inconsumable tungsten electrode, with preliminary melting of Zr as a 

getter. Subsequently, a critical review for the Fe-Sn-Zr system was performed by [1992Rag], 

who mainly evaluated the works of [1960Tan], [1968Kud], and [1990Kor]. [1992Rag] presented 

two ‘tentative’ isothermal sections (700 and 1100˚C) based on the reaction scheme from 

[1990Kor], with no details of the Zr rich region. [2000Nie, 2001Nie] analyzed the region of the 

phase diagram located near the composition of a master alloy of Zircaloy-4 [1990Ale, 

2007Ahm], and found two new ternary compounds (N phase and X phase) in the central 

region of the Fe-Sn-Zr Gibbs triangle. [2006Nie] investigated the reported phases and their 

equilibrium relationships at 800 and 900˚C in an extended area of the Gibbs triangle, by 

different complementary techniques: quantitative analysis with electron-probe microanalysis 

(EPMA), qualitative analysis with electron scanning microscopy and X-ray energy dispersive 

spectrometry (EDS), XRD and metallographic examination. The starting materials used for 

the preparation of the alloys were: Zr (99.9%-600 ppm wt. Fe-200 ppm wt. O), Sn (99.999 

mass%) and Fe (99.95 mass%). [2006Nie] confirmed the existence of the formerly reported θ-, 

N- and X phases, and suggested that the θ- and X phases have extended single phase regions. 

The Zr 4Sn and Zr 5Sn 3 phases show low solubility of Fe, and the Zr 2Fe and Zr 3Fe phases show 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_31 

ß Springer 2009

2 31 

Fe–Sn–Zr 

low solubility of Sn. A very ‘sluggish’ behavior in the nucleation and growth processes of Zr 4Sn 

was verified. Information on phase relations, structures and thermodynamics is summarized 

in Table 1. 


The Fe-Sn phase diagram is accepted from [1996Kum]. The Fe-Zr phase diagram is taken from 

[2002Ste], who experimentally redetermined the Fe-Zr phase diagram over the whole composition 

range. The Sn-Zr phase diagram in Fig. 1 is accepted from [1990Kwo1], who constructed 

the phase diagram from their own experimental investigations of the Zr 5Sn 3-Zr 5Sn 4 

region and for the other regions used evaluated diagram of [1983Abr]. 


Table 2 summarizes the crystal structure data for all phases in the ternary Fe-Sn-Zr system. 

A ternary compound θ was first identified by [1960Tan]. [1990Kwo2, 1999Zav, 2007Cos] 

investigated the crystal structure of the θ compound by XRD. [1990Kor, 2006Nie] confirmed 

the existence of the θ compound and suggested that the θ phase has an extended homogeneity 

region. Another compound with the same structure as the θ phase was reported by [1998Mel] 

as Zr6Fe1.5+xSn1.5–x.[2000Nie, 2001Nie] observed two more ternary compounds: N phase and 

X phase at 800˚C and 900˚C by scanning electron microscopy observation (SEM), XRD and 

EPMA. [2000Nie] found that the composition of the N phase at 800˚C was: 35.5±0.3 Fe - 36.6 

±0.6 Sn - 27.9±0.4 Zr (at.%). At 900˚C, the resulting composition of the compound N was 

practically the same. The XRD results by [2006Nie] indicated that some of the peaks that 

would correspond to the N phase are located in 2θ equal to 42.3˚, 43.3˚, 44.8˚, 45.8˚, 46.4˚, 

47.8˚ and 48.7˚. On the other hand, the main peaks that would correspond to the X phase are 

in 2θ equal to 36.6˚, 38.6˚, 39.8˚, 40.8˚, 42.4˚, 43.8˚, 44.3˚, 45.3˚, and 47.3˚. [2000Maz] for the 

first time has obtained and investigated the crystal structure and magnetic properties of the 

RFe6Sn6 compounds by means of microprobe analysis, 57 Fe Mössbauer spectroscopy and 

neutron diffraction technique. A slight under-stoichiometry in Zr content was found 

corresponding to about 20% of empty Zr sites in the lattice. 


According to [1990Kor], a quasibinary eutectic reaction L Ðaffl βZrFe2 +Zr5Sn3 occurred at 

about 1525˚C, but no diagram has been given. However, considering the accepted Sn-Zr phase 

diagram, this section can not be quasibinary because below the critical temperature of the 

miscibility in Zr 5Sn 3 the tie lines are not lying in the section plane. 


Invariant reactions in the region of Zr-βZrFe2-Zr5Sn3 have been reported by [1960Tan, 

1968Kud, 1990Kor, 2006Nie]. Their main discrepancy is that the existence of the Zr rich 



MSIT 1

compounds Zr 2Fe and Zr 3Fe was not recognized by [1960Tan, 1968Kud]. In addition, the 

results of [1990Kor] show that the θ phase is in equilibrium with Zr 4Sn, being in disagreement 

with those [1960Tan]. [1990Kor] presented a reaction scheme based on their own experimental 

results and those of the earlier investigations. This scheme is shown in Fig. 2 with minor 

modifications in the temperatures for some reactions, compared with the experimental data 

after [1990Kor]. The transition reactions U 3 and U 4 and the ternary eutectic reaction E 1 were 

first proposed by [1960Tan] and confirmed by [1990Kor]. The ternary peritectic reaction P1 

was proposed by [1990Kor] for the formation of the ternary compound θ. The remaining 

reactions are essentially those deduced by [1990Kor]. 


No liquidus surface has been reported for this system. According to the reported invariant 

reactions with the participation of liquid [1960Tan, 1990Kor], a schematic liquidus projection 

in the region of Zr-βZrFe2-Zr5Sn3 was proposed by [1992Rag]. However in this projection the 

position of the liquid phase taking part in the P reaction has been shown incorrectly. It was 

located inside the triangle formed by three solid phases. This is corrected in Fig. 3 in the 

present evaluation to ensure that the θ phase is located inside the triangle L-Zr 5Sn 3-βZrFe 2. 

Also the curvature and the band of the monovariant lines have been drawn to eliminate 

violations of the Konovalov rule. 



3 

[1968Kud] determined the isothermal sections at 1000, 900 and 700˚C. Their results do not 

indicate the existence of the ternary compound θ in contradiction to the earlier and later 

works. Five isothermal sections in the Zr-Zr 5Sn 3-ZrFe 2 subsystem at 1100, 1000, 900, 800 and 

700˚C were constructed by [1957Tan, 1960Tan, 1962Tan]. Using the starting materials of the 

purity of 99.95 mass% Fe, 99.997 mass% Sn and 99.98 mass% Zr, [1960Tan] melted about 170 

alloys in an arc furnace under a helium or argon atmosphere. The alloys were annealed at the 

above-mentioned temperatures for durations varying from 5 min to 500 h and water 

quenched. X-ray powder diffraction and metallographic techniques were used to study the 

phase equilibria. The isothermal section at 1100˚C by [1960Tan] is redrawn in Fig. 4, where the 

range of the θ phase is accepted from [2006Nie] because the annealing time of the samples in 

the later was longer and EPMA has been used in the measurements. 

The isothermal sections at 900˚C and 800˚C in the region Zr-Sn-βZrFe 2 determined by 

[2006Nie] are shown in Figs. 5a, 5b and Figs. 6a, 6b, respectively. According to [2006Nie], the 

Zr5Sn4 phase was observed in both as-cast and annealed alloys in the part around the phase, 

which is in agreement with the accepted Sn-Zr binary data [1990Kwo1]. The compound 

ZrFe 6Sn 6, investigated by [2000Maz], is also shown in both Figs. 5a, 5b and Fig. 6a, 6b, because 

it is studied in the samples annealed at 850˚C for 3 weeks. This temperature is obviously very 

close to the solidus, compared with the sections at 800, 900˚C and the Fe-Sn binary system. 

Therefore, it can be considered as a thermodynamically stable phase in both isothermal 

sections. 

Based on the reaction scheme of [1990Kor], a tentative isothermal section at 700˚C has 

been constructed in the review of [1992Rag] and is reproduced in Fig. 7, but the range of the 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_31 

ß Springer 2009

4 31 

Fe–Sn–Zr 

θ phase is shown the same as that at 800˚C (Fig. 6a). The section shows the existence of the 

binary compound Zr 3Fe and the equilibrium between θ and SnZr 4. These assumed equilibria 

are different from the experimental section at 700˚C by [1960Tan]. 


[1960Tan, 1990Kor] presented vertical sections with the constant Zr contents of 90 mass% and 

90 at.%, respectively. Compared with the accepted binary systems, neither of the vertical 

sections is accepted, since [1960Tan] interpreted their results based on a Fe-Zr phase diagram 

with a single intermetallic compound βZrFe 2, and [1990Kor] on a Fe-Zr diagram contradicting 

to the presently accepted diagram from [2002Ste]. Moreover, the phase relationships in 

both vertical sections do not agree with the accepted isothermal sections at 800˚C and 900˚C. 


The Zr based alloys possess three main characteristics: good mechanical properties, low cross 

section of neutron absorption and good resistance to corrosion. They have gained an extended 

application in the nuclear industry. They are used mainly as cladding and structure material in 

light and heavy water nuclear reactors. One alloy type frequently employed in the nuclear field 

is Zircaloy-4 [1990Ale, 2006Nie], with the chemical composition Zr-(1.2-1.7) Sn-(0.18-0.24) 

Fe-(0.07-0.13) Cr-(0.14 max.)O (at.%). In the process of manufacturing, Sn is added by means 

of a master alloy of Fe-Sn-Zr, with a high content of Sn in its composition (usually a 

composition close to 10Fe-70Sn-20Zr (at.%)). 

Zr alloys are also used as a candidate material for the experimental fusion device. In order 

to establish the experimental fusion device, it becomes necessary to raise the thermal stability 

and reduce the erosion of the inner surface of the first wall of the blanket material. Electron 

beam (EB) surface melting of Zircaloy-4, containing SiC, can be carried out to improve the 

surface melting temperature, thermal stability and erosion resistance [2007Ahm]. 

Two ternary compounds of the ternary system present particular properties. Zr6FeSn2 

reveals a large hydrogen storage capacity so that it can be used as hydrogen storage or getter 

material [1999Zav]. HfFe 6Ge 6 type ZrFe 6Sn 6 compound induces a local magnetic disorder due 

to the slight under-stoichiometry in Zr element [2000Maz, 2001Maz]. Information on the 

investigations of materials properties is summarized in Table 3. 

. Table 1 

Investigations of the Fe-Sn-Zr Phase Relations, Structures and Thermodynamics 




[1960Tan] X-ray analysis, metallography the Zr-rich corner up to βZrFe 2 

and Zr 4Sn, 700˚C to 1100˚C 

[1968Kud] Microstructure studies and measurements of 

hardness and micro-hardness 

the Zr-rich region, 1000, 900, 

700˚C 



MSIT 1



[1990Kor] X-ray analysis, electron microscope and X-ray phase 

microanalyzer of the “Cameca” system 



the Zr-Zr 5Sn 3-βZrFe 2 region, 

500 to 1600˚C 

[1990Kwo1] X-ray analysis, SEM-EDX method Zr4Sn, Zr5Sn3,Zr5Sn3-Zr5Sn4 regions, as cast, 800-1700˚C 

[1990Kwo2] X-ray analysis crystal structure of the 

Zr6FeSn2 (θ phase) 

[1998Mel] X-ray analysis, Korringa-Kohm-Rostoker (KKR) 

method with the coherent potential approximation 

(CPA) 

crystal structure of the 

Zr 6Fe 1.5+xSn 1.5–x 

[1999Zav] X-ray analysis, full profile (Rietveld) refinement crystal structure of the 

Zr6FeSn2 (θ phase) 

[2000Maz] Microprobe analysis, neutron diffraction technique 

and 57 Fe Mössbauer measurements 

ZrFe6Sn6, 850˚C 

[2000Nie] SEM, XRD, EPMA, EDX 10Fe-70Sn-20Zr (in at.%); 800, 

900˚C 

[2001Nie] SEM, XRD, EPMA, EDX X phase 

[2006Nie] EPMA, EDX, X-ray analysis and metallographic 

studies 

Zr-βZrFe 2-Sn region, 800, 

900˚C 

[2007Cos] X-ray analysis Zr 6Sn 2Fe (θ phase) 

. Table 2 



Temperature 

Range [˚C] 


Space Group/ 

Prototype 


Lattice 

Parameters [pm] Comments/References 

(αδFe) cI2 

Im3m 

W 

a = 293.15 

(δFe) 

1538 - 1394 

a = 286.65 at 1390˚C [Mas2, V-C2] 

(αFe) 

< 912 

at 25˚C [Mas2, V-C2] 

(γFe) cF24 a = 364.67 at 915˚C [Mas2, V-C2] 

1394 - 912 Fm3m 

Cu 



MSIT 1 

5 

DOI: 10.1007/978-3-540-70890-2_31 

ß Springer 2009

6 31 

Fe–Sn–Zr 



Temperature 

Range [˚C] 


Space Group/ 

Prototype 

Lattice 


(βSn) tI4 a = 583.18 25˚C [Mas2] 

232 - 13 I41/amd 

βSn 

c = 318.18 

(αSn) cF8 a = 648.92 [Mas2] 



Temperature 

Range [˚C] 


Space Group/ 

Prototype 


Lattice 


7 

Zr5Sn3+x a solid solution with a gradually changing 

1988 - 1500 

structure 

0

8 31 

Fe–Sn–Zr 



Temperature 

Range [˚C] 


Space Group/ 

Prototype 

Lattice 


* θ, Zr6Sn2Fe hP9 a = 796.75 ± 0.06 [1990Kwo2] 

P6m2 c = 348.63 ± 0.05 

Zr6Al2Co a = 795.3 ± 0.2 

c = 350.2 ± 0.3 

[1999Zav] 

a = 799.4 

c = 346.5 

[2007Cos] 

a = 799.3 ± 0.3 at x = 0.15 [1998Mel] 

Zr6Fe1.5+xSn1.5–x c = 346.7 ± 0.2 

*N - - [2000Nie, 2001Nie, 2006Nie] 

*X - - [2000Nie, 2001Nie, 2006Nie] 

* ZrFe6Sn6 hP13 a = 532.4 ± 0.1 [2000Maz] 

P6/mmm 

HfFe6Ge6 c = 887.0 ± 0.2 

. Table 3 

Investigations of the Fe-Sn-Zr Materials Properties 


[1990Ale] Mass spectrometry Thermodynamic activities of Sn in 

Zircaloy-4 

[1999Zav] Measurements of the crystal structure and 

thermal behavior of the hydrides and the 

hydrogen storage capacity of Zr6FeSn2 Hydrogenation of Zr6FeSn2 [2001Maz] Susceptibility and magnetization measurements Magnetic properties of the RFe 6Sn 6 

[2007Ahm] Electron beam surface melting technique, SEM, 

EDS, microhardness measurements 

Surface melting temperature, 

thermal stability and erosion 

resistance 



MSIT 1

. Fig. 1 

Fe-Sn-Zr. The Sn-Zr binary system 



MSIT 1 


9 

DOI: 10.1007/978-3-540-70890-2_31 

ß Springer 2009

10 31 

Fe–Sn–Zr 

. Fig. 2 

Fe-Sn-Zr. Partial reaction scheme for the βZrFe 2-Sn-Zr 5Sn 3 region 



MSIT 1

. Fig. 3 

Fe-Sn-Zr. Schematic partial liquidus surface projection 



MSIT 1 


11 

DOI: 10.1007/978-3-540-70890-2_31 

ß Springer 2009

12 31 

Fe–Sn–Zr 

. Fig. 4 

Fe-Sn-Zr. Partial isothermal section at 1100˚C 



MSIT 1

. Fig. 5a 




MSIT 1 


13 

DOI: 10.1007/978-3-540-70890-2_31 

ß Springer 2009

14 31 

Fe–Sn–Zr 

. Fig. 5b 

Fe-Sn-Zr. Partial isothermal section at 900˚C. Details of the Zr rich region 



MSIT 1

. Fig. 6a 




MSIT 1 


15 

DOI: 10.1007/978-3-540-70890-2_31 

ß Springer 2009

16 31 

Fe–Sn–Zr 

. Fig. 6b 

Fe-Sn-Zr. Partial isothermal section at 800˚C. Details of the Zr rich region 



MSIT 1

. Fig. 7 




MSIT 1 


17 

DOI: 10.1007/978-3-540-70890-2_31 

ß Springer 2009

18 31 

Fe–Sn–Zr 

References 

[1957Tan] Tanner, L.E; Levinson, D.W., “The System Zr-Fe-Sn”, U.S. At. Energy Comm. Publ., ARF-2068, (1957) 

as quoted by [1992Rag] 

[1960Tan] Tanner, L.E., Levinson, D.W., “The System Zr-Fe-Sn”, Trans. ASM, 52, 1115–1136 (1960) (Experimental, 

Morphology, Phase Diagram, Phase Relations, Thermodyn., 11) 

[1962Tan] Tanner, L.E., Levinson, D.W., “Structures in the Zr-Fe-Sn System”, U.S. At. Energy Comm. Publ., T1D- 

7625, (1962) as quoted by [1992Rag] 

[1968Kud] Kudryatsev, D.L., Tregubov, I.A., “The Zr corner of the Phase Diagram and Properties of Alloys in the 

Zr-Fe-Sn System”, Fiz.-Khim. Splavov Tsirkoniya, 133 (1968) as quoted by [1992Rag] 

[1983Abr] Abriata, J.P., Bolcich, J.C., Ari, D., “The Sn-Zr(Tin-Zirconium) System”, Bull. Alloy Phase Diagrams, 

4(2), 147–154 (1983) (Crys. Structure, Phase Diagram, Review, Thermodyn., 38) 

[1990Kor] Korotkova, N.V., “The Zirconium Corner of the Phase Diagram Zr-Sn-Fe”, Russ. Metall., 5, 201–208 

(1990), translated from Izv. Akad. Nauk SSSR, Met., 5, 206-213 (1990) (Experimental, Phase Diagram, 


[1990Kwo1] Kwon, Y.-U., Corbett, J.D., “The Zirconium-Tin System, with Particular Attention to the Zr 5Sn 3- 

Zr 5Sn 4 Region and Zr 4Sn”, Chem. Matter., 2(1), 27–33 (1990) (Experimental, Crys. Structure, Phase 


[1990Kwo2] Kwon, Y.-U; Sevov, S.C., Corbett, J.D., “Substituted W 5Si 3- and Zr 6Al 2Co Type Phase Formed in the 

Zirconium-Antimony and Zirconium-tin Systems with Iron Group Metals”, Chem. Matter., 2(5), 

550–556 (1990) (Crys. Structure, Morphology, 75) 

[1990Ale] Alexander, C.A., Ogden, J.S., “Thermodynamic Activities in Zircaloy-4 by Mass-Spectrometry”, J. Nucl. 

Mater., 175(3), 197–202 (1990) (Experimental, 9) 


Alloy Systems (Zr 1–xTi x) 2Fe and (Zr 1–xTi x) 3Fe in the Range 0 ≤ x ≤ 0.2”, Scripta Metall. Mater., 25(6), 


abstract 

[1992Rag] Raghavan, V., “The Fe-Sn-Zr (Iron-Tin-Zirconium) System” in “Phase Diagrams of Ternary Iron Alloys”, 

Indian Inst. Metals, Calcutta, Vol. 6B, 1199–1204 (1992) (Crys. Structure, Phase Diagram, Phase 


[1996Kum] Kumar, K.C. Hari, Wollants, P., Delaey, L., “Thermodynamic Evaluation of Fe-Sn Phase Diagram”, 

Calphad, 20(2), 139–149 (1996) (Assessment, Phase Relations, Phase Diagram, Thermodyn., 55) 

[1998Mel] Melnyk, G.A., Fruchart, D., Romaka, L.P., Stadnyk, Ju.V., Skolozdra, V., Tobola, J., “Crystal Structure of 

New M’ 6M’’ 1.5+xX 1.5–x Compounds (M’= Zr, Hf; M’’= Fe, Co, Ni; X = Sn, Sb) and Electronic Structure 

of Zr 6Co 1.65Sn 1.35”, J. Alloys Compd., 267, L1-L3 (1998) (Crys. Structure, Electronic Structure, Experimental, 

6) 

[1999Zav] Zavaliy, I.Yu., Pecharsky, V.K., Miler, G.J., Akselrud, L.G., “Hydrogenation of Zr 6MeX 2 Intermetallic 

Compounds (Me=Fe, Co, Ni; X=Al, Ga, Sn): Crystallographic and Theoretical Analysis”, J. Alloys 

Compd., 283, 106–116 (1999) (Crys. Structure, Experimental, 31) 

[2000Maz] Mazet, T., Malaman, B., “Local Chemical and Magnetic Disorder within the HfFe 6Ge 6 Type RFe 6Sn 6 

Compounds (R = Sc, Tm, Lu and Zr)”, J. Magn. Magn. Mater., 219, 33–40 (2000) (Crys. Structure, 

Experimental, Magn. Prop., 18) 

[2000Nie] Nieva, N., Arias, D., “A New Ternary Compound in the Zr-Sn-Fe System”, J. Nucl. Mater., 277, 120–122 

(2000) (Crys. Structure, Experimental, Phase Relations, 5) 

[2001Maz] Mazet, T., Malaman, B., “Macroscopic Magnetic Properties of the HfFe 6Ge 6 Type RFe 6X 6 (X = Ge or 

Sn) Compounds Involving a Non-Magnetic R Metal”, J. Alloys Compd., 325, 67–72 (2001) (Experimental, 


[2001Nie] Nieva, N., Arias D., presented at CALPHAD XXX, York, England (2001) 



(2002) (Experimental, Phase Diagram, Phase Relations, 88) 

[2006Nie] Nieva, N., Arias, D., “Experimental Partial Phase Diagram of the Zr-Sn-Fe System”, J. Nucl. Mater., 359 

(1-2), 29–40 (2006) (Experimental, Morphology, Phase Diagram, Phase Relations, #, 22) 



MSIT 1


19 

[2007Ahm] Ahmad, M., Akhter, J.I., Ali, G., Akhtar, M., Choudhry, M.A., “Erratum to (Characterization of 

Electron Beam Modified Surface of Zircaloy-4) {J. Alloys Compd., 426 (2006) 176-179}”, J. Alloys 

Compd., 428(1-2), 362 (2007) (Experimental, Morphology, 1) 

[2007Cos] Costa, B.F.O., Greneche, J.M., Fruchart, D., Alberto, H.V., Skryabina, N.E., Romaka, L.P., Stadnyk, Yu. 

V., “Structural Analysis and 57 Fe Mössbauer Spectrometry of Zr 6FeSn 2 and Related Compounds”, 

J. Alloys Compd., 438(1-2), 88–91 (2007) (Crys. Structure, Electronic Structure, Experimental, 11) 


(1990) 





MSIT 1 

DOI: 10.1007/978-3-540-70890-2_31 

ß Springer 2009

Iron – Titanium – Vanadium 


Lesley Cornish, Andy Watson 

Introduction 

The Fe-Ti-V system is important for steels, both Ti and V forming very stable carbides, and 

thus suppressing the stability of cementite. Both Ti-carbides and V-carbides are useful in 

controlling grain size. Both Ti and V can also form nitrides and carbonitrides, which can pin 

grain boundaries, and hence produce steels with a finer grain size. The control of grain size is 

vital in production, especially rolling, and knowledge of the effects of additions to steels is vital 

for improved quality and productivity. Vanadium is beneficial in promoting fine, mainly 

nitride, precipitates which give dispersion strengthening. The Laves phase is also formed, 

and depending on morphology, these can be detrimental to mechanical properties. Some 

vanadium alloys, such as V-5Fe-3Ti, show potential as structural materials for fision power 

plants because of their resistance to swelling after neutron irradiation. Both the TiFe 2 Laves 

phase and (βTi,V) have been identified as having potential hydrogenation capability, and work 

is ongoing to characterize and enhance this. It has been postulated that alloys based on the 

Laves phase could have potential as neutron radiation shielding applications. 

Although there are experimental data for the system, they are fairly limited, and mostly 

confined to the Fe rich compositions, and the purity of Fe in the earlier work was 99 mass%. 

The Fe rich corner was studied by [1954Luc] using samples prepared from Armco iron ( 99% 

purity), sponge titanium and high (although unspecified) purity vanadium. 

[1993Rag] cites thermodynamic calculation of (γFe)/((γFe)+(αFe)) and ((γFe)+(αFe))/ 

(αFe) phase boundaries at 950˚C, 1050˚C, 1150˚C and 1250˚C undertaken by [1988Kum]; they 

were found to be linear. 

The system has been reviewed by [1987Rag1, 1987Rag2, 1993Rag]. The experimental work 

is summarized in Table 1. 

There are a number of references that seem to be by the same authors although the name of 

the primary author has been spelled in different ways. These are [1959Cin, 1960Tsi, 1961Cin, 

1961Chi]. 


Fe–Ti–V 32 

1 

The Fe-Ti binary system is accepted from [Mas2]. 

The Fe-V system has been assessed by [1991Hua]. Although [2006Oka] reported recent 

experimental work by [2005Ust] who used XRD and electron microscopy to investigate the 

extent of the sigma phase in the binary Fe-V system, this is not accepted here. The suggestion 

was that the sigma phase decomposes below about 650˚C accompanied by phase separation of 

the bcc phase. The phase diagram shown by [2005Ust] shows a narrow strip of single-phase 

bcc between the sigma phase and the region of phase separation. As pointed out by [2006Oka], 

this feature of the phase diagram would seem to be unlikely, the sigma phase most probably 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_32 

ß Springer 2009

2 32 

Fe–Ti–V 

decomposing eutectoidally to give Fe rich and V rich bcc phases, as in the Cr-Fe system. As this 

aspect of the phase diagram is uncertain, it has been ignored in the present work. 

The Ti-V phase diagram as shown in [Mas2], exhibits a stable miscibility gap with a critical 

temperature of 850˚C and a monotectoid reaction taking place at 675˚C. Earlier assessments of 

this system (e.g. [1981Mur]) do not show this miscibility gap, which is based on experimental 

work by [1981Nak]. However, experimental studies by [1989Wei] would seem to suggest that 

the miscibility gap is indeed metastable. Later, the system was assessed by [1998Sau] showing 

the low temperature equilibria of the system expressed as a simple two-phase (αFe) + (αTi) 

region. It is this version of the phase diagram that is accepted here. 


Table 2 shows details of stability ranges and crystallography of the solid phases. [1960Tsi] 

reported the possible presence of a ternary phase in the system, but this was subsequently 

confirmed as contiguous with the binary λ,TiFe 2 phase [1987Pri, 1987Rag1]. [1954Sto] was 

the only other work to report on the presence of a ternary phase occurring in the system; at 14 

at.% (14 mass%) V; 28 at.% (31 mass%) Fe. Since only commercial purity Ti was used in the 

preparation of the samples and no other workers have reported this phase, it is generally 

ignored [1987Rag1, 1987Rag2]. [1987Pri] showed that the solubility of V in FeTi is small, 

whereas up to 30 at.% V dissolves in λ (TiFe 2) at 1200˚C. The Laves phase is of type C14, with 

12 atoms per unit cell [1958Ell]. 


In a pair of articles, [1959Cin, 1960Tsi] presented quasibinary sections for TiFe-Vand TiFe 2-V. 

A combination of hardness measurement, thermal analysis, XRD and metallography were 

used to determine the phase diagrams. [1987Rag1, 1987Rag2] queried the quasibinary nature 

of these sections as the melting points of the TiFe and TiFe2 end members are given as 

considerably higher than shown in the accepted Fe-Ti binary system [Mas2]. The large 

terminal solubilities of V in the compounds would make the three phase equilibria between 

the compounds, α(V) and and liquid in each quasibinary system unlikely to occur at a 

single temperature. Moreover, the TiFe compound melts incongruently making it impossible 

for the TiFe-V section to be quasibinary. For these reasons, these sections have not been 

reproduced here. 


[1961Chi] reported a solid state reaction, FeTi + (βTi,V) Ð (αTi) + λ. Using the limited 

experimental data available, [1987Rag1, 1987Rag2] postulated a reaction scheme using their 

own tentative liquidus, and assumed that the solid state transition reaction from [1961Chi] 

occurred at a temperature just below 590˚C, Table 3. They also assumed the presence of a 

ternary eutectic reaction, but there has been no experimental evidence of this. The reaction 

scheme from [1987Rag1] is reproduced in Fig. 1. 



MSIT 1


No experimental study of the liquidus surface has been undertaken, although [1987Rag1, 

1987Rag2] drew a tentative liquidus projection using the adjoining binary phase diagrams and 

the two vertical sections of [1959Cin, 1960Tsi]. This is shown in Fig. 2 with amendments to the 

isotherms in order to maintain consistency with the accepted binary phase diagrams. It is 

speculated that there is a ternary eutectic reaction occurring at about 1350˚C, and each of the 

monovariant lines exhibits a maximum. Alternatively, a liquidus projection can be predicted 

by thermodynamic calculation by combining the thermodynamic descriptions of the three 

binary systems [1998Ran, 1991Hua, 1998Sau]. The resulting liquidus (Fig. 3) shows a transition 

reaction taking place at 1164˚C. However, it must be stressed that there is no experimental 

justification for either of these liquidus surfaces. 



3 

[1961Chi] argon-arc melted 99% Fe and V, and sponge Ti (99.67%) to produce alloys at 93 

compositions along sections at a number of different Fe:Ti ratios. The starting materials and 

their impurities were: vanadium powder (0.9% O and 0.09% N), Armco iron (0.11% Al, 

0.34% Si, 0.22% Mn and a trace of C), and TG-O titanium (0.04% Fe, 0.04% Mg, 0.03% Si, 

0.03% Cl, 0.05% C, 0.02% N, 0.11% O and 0.006% H). The resulting alloys were annealed at 

1000˚C for 48 h or 800˚C for 248 h before quenching into water, and resulted in the 

construction of partial isothermal sections for Fe-V-TiFe for 1000 and 800˚C. A partial section 

for 25˚C showing a much restricted solubility of (βTi,V) was produced by [1961Cin]. In each 

of these works [1961Chi, 1961Cin], two Laves phases were reported; the binary λ,TiFe 2 phase 

and a distinct ternary phase of roughly equiatomic stoichiometry, denoted as γ in the article; 

although their experimental work was concentrated on Ti-rich alloys. However, [1984Ere] 

postulated that these two Laves phase fields were contiguous, and [1987Pri] undertook 

experiments to verify this. Using iodide titanium, type VNM-1 vanadium and carbonyl 

iron, [1987Pri] prepared samples along vertical sections at 33.3 at.% Ti and 50 at.% Ti by 

arc-melting under argon using an oxygen getter. The weight losses after melting were less than 

1 mass%. Using metallography, XRD and local X-ray spectral and hardness techniques, 

investigations of alloys annealed at 1000 and 1200˚C (for between 50-110 h) lying at compositions 

along the TiFe 2-V section indicated that the binary Laves phase can dissolve V up to 

between 30 and 33 at% suggesting that the composition of the ternary Laves phase as given by 

[1961Chi] coincides with the solubility limit of V in the binary λ,TiFe 2 Laves phase. A plot of 

lattice parameter against V content along the TiFe 2-V section shows a steady increase on 

adding the larger atom, and thus V can replace both Ti and Fe atoms, at least to some extent, as 

had been demonstrated earlier by [1958Ell]. In this work, it was shown that slightly more than 

half the Fe atoms in TiFe2 can be substituted by V. It is interesting to note that the composition 

limit of the λ phase with respect to V lies at the edge of the partial section investigated by 

[1961Chi], which goes some way to explaining their erroneous conclusion regarding the 

presence of a ternary phase. Through XRD studies of as-cast ternary alloys, [1997Miy] also 

confirmed that Vegard’s law was obeyed as V atoms were dissolved into the binary λ phase. 

Taking this phase extension into account, and extrapolating from the binary data, as well as 

assuming a nominal solubility of 1 at.% Ti in the σ phase (FeV), [1987Rag1, 1987Rag2] 

extended the partial isothermal sections to cover the whole composition range, and these form 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_32 

ß Springer 2009

4 32 

Fe–Ti–V 

the basis of Figs. 4 to 6. Although a diagram produced by [1997Miy] suggested that the range 

of the λ phase was actually greater, this is not reflected in Figs. 4 to 6 as no further details were 

given. 


The (γFe)-loop in the ternary system was studied by [1954Luc] using dilatometry. 23 alloys 

with compositions ranging between 0-1.12 mass% Ti and 0.11-1.34 mass% V were heated over 

the (γFe) to (αFe) transformation at a heating rate between 2 and 3˚C per minute. In some of 

the samples (especially Fe-V), the furnace temperature was held constant, even for several 

hours, until no further transformation occurred. Sudden changes in slope of the heating curve 

were taken as the beginning and the end of the transformation, indicating the phase boundary 

between the α/α+γ/γ phase regions. In the same work, they report on a study of the γ-loop in 

the Fe-V system, but they indicate a minimum in the phase boundaries, which have since been 

discounted by other researchers. [1987Rag1] noted that previous work on the Fe-Ti system 

was found to disagree with the later versions of the phase diagram [Mas2], and so [1954Luc]is 

considered to be unreliable. For this reason, the ternary work is not discussed further here. 

The FeTi-V vertical section was studied by [1960Tsi]. 22 alloys of mass of 20 g were used 

for thermal analysis studies using a contact method to determine incipient melting, i.e. onset 

of melting, for determination of the solidus (the liquidus was not determined). Metallography 

was used to study samples in the as-cast, annealed (under vacuum, 800˚C for 100 h, 600˚C for 

200 h, or 550˚C for 1000 h, then furnace-cooled) and quenched states. Four groups of water 

quenched alloys were studied: heat treated at 1200˚C for 6 h, 1000˚C for 48 h, 800˚C for 200 h 

or 600˚C for 548 h. Powder XRD with vanadium radiation was used to investigate the phase 

assemblages in annealed samples. [1961Chi] determined vertical sections for TiFe-V and 

TiFe 2-V, which they maintain were quasibinary; this is dealt with above. However, owing to 

errors in the melting points of the TiFe and TiFe 2 indicated on the sections they have not been 

considered here. A vertical section was determined by [1961Chi] for the 84Ti16Fe-V. This is 

not shown here as it includes equilibria with a ternary compound, which they denote as γ, that 

has since been correctly identified as the limiting composition of the extension of the binary 

TiFe 2 compound into the ternary system. 


Hardness measurements across the TiFe 2-V section showed a maximum of above 800H V, 

corresponding to the maximum extent of the λ phase [1959Cin], i.e. the maximum V content 

of the phase. A study by [1960Tsi] of the hardness across the TiFe-V section showed the 

maximum hardness being obtained for their ‘ternary’ γ phase at about 750H V, without any 

apparent effect due to the phase composition. However, the consistency between the hardness 

measurements of the binary λ phase and the apparent ternary γ phase was explained by 

[1984Ere], and confirmed by [1987Pri], in that the two phases are actually contiguous. 

In a study involving different steel additions, [2004Li] showed the beneficial affects of both 

Ti and V additions in controlling the grain size, and the increased solution temperature of 

carbonitrides in the austenite matrix. However, the amount of Ti addition is limited because it 



MSIT 1

forms nitrides in austenite, and this reduces the Vand N available for subsequent precipitation 

in ferrite; both effects which can lead to a reduction in yield strength. 

The swelling behavior after neutron irradiation was investigated using TEM by [1998Fuk]. 

The alloys were made from high purity components (99.9% V, 99.999% Fe and 99.99% Ti), arc 

melted under argon. TEM foils were prepared from rolled sheet (0.25mm), annealed at 1100˚C 

for 2 h, and irradiated at 380˚C, 519˚C and 615˚C up to a neutron fluence of 1.6 · 10 26 n·m –2 . 

The void growth rate was found to be linearly dependent on Fe content, but Ti additions 

reduced this effect, and increasing the Ti additions caused precipitation of titanium oxide 

precipitates. 

[1997Miy] studied the effect of phase structure in the selection of Fe-Ti-V alloys for 

hydrogenation. Confirming the phases before hydrogenation studies, [1997Miy] prepared 

samples by arc melting of “high purity” components under argon, then pulverizing the ingots 

to obtain powders with average particle size of less than 100 μm. X-ray diffraction was 

undertaken using CuK α radiation with a carbon monochromator. 

The TiFe2 Laves phase was identified as having the potential as a hydrogenation material 

owing the suitability of its component atoms for the hydrogenation reaction, and it was 

thought that this could be increased by the addition of V. However, experimental results from 

a number of alloys showed that the initial hydrogenation of Fe-Ti-V alloys was less than for 

rare earth metals, which are usually employed commercially. Maximum hydrogen storage 

occurred at a composition of TiFeV 0.7 at 60˚C. Further work on this topic was undertaken by 

[1999Ver], in an experimental study of the reaction of Fe-Ti-Valloys with hydrogen. [1999Ver] 

also predicted that the alloys could have potential for neutron radiation shielding materials. 

Another potentially useful phase for hydrogen storage is the bcc vanadium phase. Here 

(βTi,V), on absorbing hydrogen, becomes VH or V2H and then VH2. While the first phases are 

stable, the last phase undergoes hydrogen desorption and absorption processes at around 

room temperature, and so shows potential for hydrogen storage. This was the rationale for 

[2004Ito] to undertake comparative work on Valloys with various additions, including Fe and 

Ti, up to 1 mol. [1995Sin] evaluated the performance of the V 0.85-Fe 0.05-Ti 0.15 alloy manufactured 

by a powder route (from 99.99% pure components) for hydrogen storage, and found 

that good hydrogen absorption and desorption occurred at room temperature. 

The Laves phase, λ,TiFe2, is antiferromagnetic with a Néel temperature of about 12˚C. 

Using magnetization and V-NMR spin-echo spectra, [2003Yam] demonstrated that V additions 

cause a change to ferromagnetism at (0.15 < x < 0.4). The predicted magnetic phase 

diagram for Ti(Fe 1-xV x) 2 was derived and regions of paramagnetism, antiferromagnetism and 

ferromagnetism were shown. The transformations were deduced to be due to the changes in 

lattice parameter and d-electron number density. 

Details relating to properties studied and techniques employed are listed in Table 4. 

Miscellaneous 


5 

Nuclear magnetic resonance (NMR) experiments were undertaken by [1967Mas] on(βTi,V) 

in the Ti-V and Fe-V binary systems, using arc melted samples made from V of 99.8% purity 

and Ti and V of 99.9% purity. Nuclear spin-lattice relaxation times, T 1, were measured, 

together with the low temperature specific heats, and it was found that the T 1T product 

(T = temperature) was strongly dependent on composition. The relaxation behavior was 

correlated with the low temperature specific heat. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_32 

ß Springer 2009

6 32 

Fe–Ti–V 

[2002Boz] undertook calculations for a number of phases, including TiFe, to calculate the 

site preferences of a number of alloying additions, including V, using the Bozzolo-Ferrante- 

Smith (BFS) calculation method, but as yet, there are no experimental data with which to 

compare these results. 

. Table 1 

Investigations of the Fe-Ti-V System Phase Relations, Structures and Thermodynamics 



Range Studied 

[1954Luc] Dilatometry, chemical analysis Prior annealing at 950˚C to 1000˚C for 1 or 

2 h; experiments at 970 - 1120˚C; 0- 

1.12 mass% Ti and 0.11-1.34 mass% V; 

(γFe)-loop 

[1959Cin] Metallography, thermal analysis, hardness 20 - 1700˚C; across TiFe2-V section 

[1960Tsi] Metallography, XRD, thermal analysis, 

hardness 

20 - 1900˚C; across TiFe-V section 

[1961Chi] Metallography, XRD, differential thermal 

analysis using a Kurnakov pyrometer, 

manufacture via a TiFe master alloy 

800˚C and 1000˚C; partial diagram from Ti 

up to TiFe 

[1961Cin] Metallography, XRD Ambient T; partial diagram from Ti up to 

TiFe 

[1967Mas] Heat pulse method for heat capacities 5-20 K; up to 84 at.% Ti in V, and up to 

30 at.% Fe in V; (βTi,V) 

[1987Pri] Metallography, XRD, local X-ray 

spectroscopy and hardness 

1000 and 1200˚C; 33.3 and 50 at.% Ti 

isoconcentrate lines; λ phase 

[1995Sin] XRD 700-900˚C; V 0.85-Fe 0.05-Ti 0.15 

[1997Miy] XRD Unspecified; wide range of alloys; 

homogeneity range of λ 



MSIT 1

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Lattice 

Parameters 


α, (δαFe,βTi,V) cI2 

(δFe) Im3m a = 293.15 pure Fe at 1390˚C [V-C2, Mas2] 

1538 - 1394 W 

(αFe) a = 286.65 pure Fe at 25˚C. 

< 912 Dissolves 10 at.% Ti at 1289˚C [Mas2] 

(βTi) a = 330.65 

1670 - 882 pure Ti at 900˚C [Mas]. 

Dissolves 22 at.% Fe at 1085˚C [Mas2]. 

(V) a = 302.40 

< 1910 [Mas2] 

(γFe) cF4 a = 364.67 at 915˚C [V-C2, Mas2]. 

1394 - 912 Fm3m Dissolves 1.4 at.% V at 1160˚C [1991Hua]. 

Cu 

Dissolves 1.3 at.% V at 1150˚C [1998Ran]. 

(αTi) hP2 a = 295.06 dissolves 2.7 at.% V at 675˚C [Mas2]. 

P63/mmc c = 468.35 dissolves 1.6 at.% V at 612˚C. 

Mg [1998Sau] 

λ, Ti(Fe1–xVx) 2 hP12 a = 488.0 at x = 0.5, [1960Tsi]. Dissolves 30 at.% 

P63/mmc MgZn2 c = 796.0 V at 1200˚C [1987Pri]. 

TiFe2 a = 479.0 at x =0 

< 1427 c = 781.1 [V-C2] [Mas2] 

TiFe cP2 a = 297.6 [V-C2] 

< 1317 Pm3m 

CsCl 

σ, FeV tP30 a = 886.5 to 901.5 [1987Rag1, 1987Rag2] 

P42/mnm σCrFe 

c = 460.5 to 464.2 

a = 896.5 at V0.5Fe0.5 [V-C2]. 

c = 463.3 29.6 - 60.1 at.% V [Mas2]. 



MSIT 1 

7 

DOI: 10.1007/978-3-540-70890-2_32 

ß Springer 2009

8 32 

Fe–Ti–V 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


Metastable / high pressure phases 


P63/mmc Mg 

c = 396.0 

Martensite tI4 

I4/mmm 

- [Mas2] 

α’ cP2 

Pm3m 

CsCl 

- - 

. Table 3 



Fe 


Ti V 

L Ð FeTi + λ + α 1350 E1 L 36 38 28 

FeTi + (βTi,Fe) Ð (αTi) + λ > 590 U1 - - - - 

. Table 4 

Investigations of the Fe-Ti-V Materials Properties 

Reference 



[1959Cin] Hardness Hardness 

[1960Tsi] Hardness Hardness 

[1967Mas] NMR Nuclear spin-lattice relaxation times, specific heat 

measurements 

[1987Pri] Hardness Hardness 

[1995Sin] XRD, hydrogen adsorption and 

desorption 

Hydrogenation characteristics 

[1997Miy] Hydrogen dissociation pressure Hydrogenation characteristics 

[1998Fuk] TEM Swelling behavior on neutron irradiation 

[1999Ver] Hydrogen absorption Hydrogenation characteristics 



MSIT 1


Reference 



[2003Yam] Torsion magnetic balance and 

NMR studies 


Magnetic phase diagram of Ti(Fe 1–xV x) 2,Néel 

temperature 

[2004Ito] Hydrogen absorption Hydrogenation characteristics 

[2004Li] TEM and tensile and charpy tests Mechanical properties in relation to 

microstructure 



MSIT 1 

9 

DOI: 10.1007/978-3-540-70890-2_32 

ß Springer 2009

10 32 

Fe–Ti–V 

. Fig. 1 

Fe-Ti-V: Tentative reaction scheme 



MSIT 1

. Fig. 2 

Fe-Ti-V. Tentative liquidus surface projection 



MSIT 1 


11 

DOI: 10.1007/978-3-540-70890-2_32 

ß Springer 2009

12 32 

Fe–Ti–V 

. Fig. 3 

Fe-Ti-V. Calculated liquidus surface projection 



MSIT 1

. Fig. 4 

Fe-Ti-V. Isothermal section at 25˚C 



MSIT 1 


13 

DOI: 10.1007/978-3-540-70890-2_32 

ß Springer 2009

14 32 

Fe–Ti–V 

. Fig. 5 




MSIT 1

. Fig. 6 




MSIT 1 


15 

DOI: 10.1007/978-3-540-70890-2_32 

ß Springer 2009

16 32 

Fe–Ti–V 

References 

[1954Luc] Lucas, W.R., Fishel, W.P., “γ Loop Studies in the Iron-Vanadium and the Iron-Vanadium-Titanium 

Systems”, Trans. ASM, 46, 277–291 (1954) (Phase Relations, Experimental, 9) 

[1954Sto] Stone, L., Margolin, H., “The Ti-V-Fe and Ti-Al-Fe Systems”, U.S. At. Energy Comm. Pub. AD-43730, 

1–72 (1954), Nucl. Sci. Abst., No. 172, 10, 23–24 (1956) as quoted by [1987Rag1, 1987Rag2] 

[1958Ell] Elliott, R.P., Rostoker, W., “The Occurrence of Laves-Type Phases Among Transition Elements”, Trans. 

ASM, 50, 617–633 (1958) (Phase Relations, Calculation, Review, 27) 

[1959Cin] Cin-Hua, B., Kornilov, I.I., “Phase Diagram of the TiFe 2-V System”, Izv. Akad. Nauk SSSR, Otdel. Tekh. 

Nauk, Met. i Toplivo, 6, 110–112 (1959) (in Russian) (Phase Diagram, Phase Relations, Experimental, 

Mechan. Prop., Morphology, 6) 

[1960Tsi] Tsin-Kua, Bi, Kornilov, I.I., “The Phase Diagram of the TiFe-V System”, Russ. J. Inorg. Chem., 5(4), 

434–436 (1960) (Phase Diagram, Phase Relations, Experimental, 5) 

[1961Chi] Ch’ing-hua, Pi, Kornilov, I.I., “Equilibrium Diagram of the Ti-V-TiFe Ternary System”, Russ. J. Inorg. 

Chem., 6(6), 694–696 (1961) translated from Zh. Neorg. Khim., 6(6), 1351–1354 (1961) (Phase Diagram, 

Phase Relations, Experimental, 5) 

[1961Cin] Cin-Hua, P., Kornilov, I.I., “Phase Diagram of the Ti-V-Fe System”, Trudy. Inst. Metall. A.A. Baikova, 

Akad. Nauk SSSR, 8, 54–57 (1961) (in Russian) (Phase Diagram, Phase Relations, Experimental, 12) 

[1967Mas] Masuda, Y., Nishioka, M., Watanabe, N., “Nuclear Magnetic Resonance and Specific Heat 

Measurements of Transition Metals and Alloys - Ti-V-Fe and Zr-Nb-Mo Systems”, J. Phys. Soc. Jpn., 

22(1), 238– (1967) (Experimental, Magn. Prop., Thermodyn., 33) 

[1981Mur] Murray, J.L., “The Ti-V (Titanium-Vanadium) System”, Bull. Alloy Phase Diagrams, 2(1), 48–55 (1981) 

(Crys. Structure, Phase Diagram, Phase Relations, Review, Thermodyn., 80) 

[1981Nak] Nakano, O., Sasano, H., Suzuki, T., Kimura, H., (in Japanese), Nippon Kinzoku Gakkaishi, 45, 653–660 

(1981) (Phase Diagram, Phase Relations) as quoted in [Mas2] 

[1984Ere] Eremenko, V.N., Tretiyachenko, L.A., “Ternary Systems with Titanium and Transitions Metals of IV-VIII 

Groups of the Periodic Table” (in Russian), Diag. Sost. Mat., Eremenko, V.N. (Ed.), Naukova Dumka, 

Kiev, 3–20 (1984) (Experimental, Phase Diagram, Phase Relations, Review, 63) 

[1987Pri] Prima, S.B., Tretiyachencko, L.A., “Area of Homogeniety of Laves Phase in the Ti-V-Fe Ternary System”, 

Powder Metall. Met. Ceram., 5, 414–415 (1987), translated from Poroshk. Metall., 5(293), 76–77 (1987) 

(Phase Relations, Phase Diagram, Experimental, Thermodyn., 3) 

[1987Rag1] Raghavan, V., “The Fe-Ti-V (Iron-Titanium-Vanadium) System” in “Equilibria in Iron Ternary Alloys”, 

Institute of Metals, London, 73–84 (1988) (Review, Phase Relations, Phase Diagram, #, 10) 

[1987Rag2] Raghavan, V., “Section I. The Fe-Ti-V (Iron-Titanium-Vanadium) System” in “Phase Diagrams of 

Ternary Iron Alloys”, Ind. Inst. Techn. Delhi, 1, 73–84 (1987) (Crys. Structure, Phase Diagram, Phase 


[1988Kum] Kumar, K.C. Hari, Raghavan, V., “Fcc-Bcc Equilibrium in Ternary Iron Alloys”, J. Phase Diagrams, 4(1), 

53–71 (1988) (Review, Phase Relations, Calculation) as quoted by [1993Rag] 

[1989Wei] Wei, F., Flower, H.M., “Phase Separation Reactions in Ti-50V Alloys”, Mater. Sci. Technol., 5(12), 

1172–1177 (1989) (Phase Relations, Experimental, 15) 

[1991Hua] Huang, W., “A Thermodynamic Evaluation of the Fe-V-C System”, Z. Metallkd., 82(5), 391–401 (1991) 


[1993Rag] Raghavan, V., “Fe-Ti-V (Iron-Titanium-Vanadium)”, J. Phase Equilib., 14(5), 632–633 (1993) (Phase 


[1995Sin] Singh, Ar.K., Singh, Aj.K., Srivastava, O.N., “On the Synthesis, Characterisation and Hydrogenation 

Behaviour of V-Ti-Fe Alloy”, Int. J. Hydrogen Energy, 20(8), 647–651 (1995) (Experimental, Phys. 

Prop., 3) 

[1997Miy] Miyamura, H., Sakai, T., Kuriyama, N., Tanaka, H., Uehara, I., Ishikawa, H., “Hydrogenation and Phase 

Structure of Ti-Fe-V Alloys”, J. Alloys Compd., 253–254, 232–234 (1997) (Experimental, Phys. Prop., 6) 

[1998Fuk] Fukumoto, K., Kimura, A., Matsui, H., “Swelling Behavior of V-Fe Binary and V-Fe-Ti Ternary Alloys”, 

J. Nucl. Mater., 258–263(2), 1431–1436 (1998) (Crys. Structure, Experimental, Morphology, Phase 

Relations, 8) 

[1998Ran] Rand, M.H., “System Fe-Ti” in “Thermochemical Database for Light Metal Alloys”, Ansara, H., Dinsdale, 

A.T., Rand, M.H., (Eds.), Vol. 2, European Commission, Brussels and Luxembourg, 205–207 (1998) 




MSIT 1


17 

[1998Sau] Saunders, N., “System Ti-V” in “Thermochemical Database for Light Metal Alloys”, Ansara, H., Dinsdale, 

A.T., Rand, M.H., (Eds.), Vol. 2, European Commission, Brussels and Luxembourg, 297–298 (1998) 


[1999Ver] Verbetsky, V.N., Mitrokhin, S.V., Movlaev, E.A., “Synthesis and Properties of Multicomponent 

Hydrides with High Density”, J. Alloys Compd., 293–295, 421–425 (1999) (Experimental, Phys. Prop., 8) 


Intermetallics, 10, 149–159 (2002) (Calculation, Crys. Structure, Theory, 27) 

[2003Yam] Yamada, Y., Masuda, M., Ishitani, S., Nakamura, T., “Magnetic Properties of C14 Laves Phase Ti 

(Fe 1–xV x) 2 and Ti(Fe 1–xCr x) 2 with x < 0.5”, J. Magn. Mag. Mater., 265, 321–330 (2003) (Experimental, 


[2004Ito] Ito, S., Yamashita, D., Komiya, K., Yukawa, H., Morinaga, M., “Compositional Dependence of Phase 

Stability of γ Phase Formed in Vanadium Alloys”, J. Alloys Compd., 364(1–2), 137–140 (2004) (Crys. 

Structure, Experimental, Interface Phenomena, Kinetics, Phase Diagram, Phase Relations, 7) 

[2004Li] Li, Z., Wilson, J.A., Crowther, D.N., Mitchell, P.S., Craven, A.J., Baker, T.N., “The Effects of Vanadium, 

Niobium, Titanium and Zirconium on the Microstructure and Mechanical Properties of Thin Slab Cast 

Steels”, ISIJ Int., 44(6), 1093–1102 (2004) (Crys. Structure, Experimental, Morphology, 35) 

[2005Ust] Ustinovshikov, Y., Pushkarev, B., Sapegina, I., “Phase Transformations in Alloys of the Fe-V System”, 

J. Alloys Compd., 398, 133–138 (2005) (Crys. Structure, Phase Diagram, Phase Relations, Experimental, 

9) 

[2006Oka] Okamoto, H., “Fe-V (Iron-Vanadium)”, J. Phase Equilib. Diff., 27(5), 542 (2006) (Review, Phase 



(1990) 





MSIT 1 

DOI: 10.1007/978-3-540-70890-2_32 

ß Springer 2009

Iron – Titanium – Yttrium 


Natalia Kol’chugina 

Introduction 

In searching for new materials for permanent magnets, the Fe-Ti-RE systems, and, in particular, 

Fe rich rare-earth intermetallic compounds R(Ti,Fe) 12 and R 3(Ti,Fe) 29 are of interest. 

Thus, the studies of the systems are focused to the compounds. They are promising materials 

for powerful (and relatively cheap because of the low rare-earth content) permanent magnets 

and, therefore they have been extensively studied in the last two decades. The aforementioned 

compounds have specific features of crystal and magnetic structures and are convenient 

subject for the investigation of fundamental problems in the physics of magnetic phenomena. 

RTiFe11 (τ1 phase with R = Y) series is of interest as candidates for high-temperature 

permanent magnets owing to the high Curie temperatures, saturation magnetization and 

magnetocrystalline anisotropy. Recently, the study on R 3(Ti,Fe) 29 (τ 2 phase with R =Y) 

intermetallics attract more attention due to the discovery of favorable magnetic properties 

of Sm 3(Ti,Fe) 29N x. This new family of intermetallic compounds has attracted a special 

attention because the introduction of the interstitial atoms H, N and C led to remarkable 

improvements in their magnetic properties. 

The compounds with Y are of practical importance from the fundamental point of view 

since Y being non-magnetic, allows the properties of Fe sublattice to be directly isolated. 

A number of studies was performed for single-crystal samples to assess properties, namely, the 

anisotropy of iron sublattice. Thus, most works done on the Fe-Ti-Y system concern structural 

properties of the alloys motivated by research in magnetic properties. 

There are only two articles on the phase equilibria in the Fe-Ti-Y system in which the 

isothermal sections at 500˚C [1994Lin] and 600˚C [1997Liu] were constructed. These works 

have been reviewed by [2000Rag, 2001Rag]. 

In a number of works, hydrogenation and nitrogenation (with the formation of hydrides 

and nitrides, respectively) techniques are used as procedures that allow the magnetic properties 

of Fe-Ti-Y alloys and compounds to be changed and improved. 

Investigations of the Fe-Ti-Y phase relations, structure identifications are given in Table 1. 


Fe–Ti–Y 33 

1 

The binary Fe-Ti, Fe-Y and Ti-Y systems are accepted from [Mas2]. The lattice parameters 

were taken from [1987Mur] for the binary Fe-Ti compounds and from [1992Zha] for the 

binary Fe-Y compounds. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_33 

ß Springer 2009

2 33 

Fe–Ti–Y 


There are two ternary phases established in the system. They are designated in the literature 

as 1:12 (τ 1) and 3:29 (τ 2). The crystallographic data of the Fe-Ti-Y phases are listed in Table 2. 

Theτ 1 phase exists up to 1200˚C [1994Lin]. It exhibits ferromagnetic ordering at T C = 

247˚C and uniaxial magnetic anisotropy. 

For the τ2 phase, [1994Li] have reported that it crystallizes in the monoclinic symmetry 

with alternate staking of Th 2Zn 17 (rhombohedral) and ThMn 12 (tetragonal) type segments. 

Based on T C and magnetization measurements, the authors have supposed that the 3 : 29 type 

structure is intermediate between 2 : 17 and 1 : 12 type structures. Based on measurements of 

magnetic properties, [1996Tel] supposed that the τ 2 phase transforms into the τ 1 and Y 2Fe 7 

phases with decreasing temperature. In [1997Liu], the τ 2 phase was not found at 600˚C. 

According to [2000Kim], the phase is formed at a high temperature, above at least 950˚C. 

Thus, the τ2 phase exists within a narrow high-temperature range. The compound is ordered 

magnetically at 115˚C. 

The existence of another ternary phase (YTi 1.1Fe 8.6) was found in [1993Rev]. The authors 

showed that the phase has a defect CeMn 6Ni 5 type structure; however, this phase displays a 

substantial deviation from the stoichiometric 1 : 11 composition. 

The substitution of Ti for Fe in Y 2Fe 17 (to the formation of the Y 2TiFe 16 stoichiometry) 

and in YFe 3 (to the formation of the YTi 0.5Fe 2.5 stoichiometry) is considered in [2001Ell] and 

[2006Sor], respectively. According to [1994Lin], the solubility of Ti in Y 2Fe 17 is 1.5 at.%. 


Isothermal sections of the Fe-Ti-Y system were studied in [1997Liu] (at 600˚C) and [1994Lin] 

(at 500˚C). The triangulations at 500 and 600˚C are identical. Figure 1 shows the isothermal 

section at 600˚C with some corrections according to the accepted binary systems. 


Two compounds τ 1 and τ 2 are magnetic phases; their properties and properties of alloys with 

close compositions are given in Table 3. 

Compositions subjected to hydrogenation and nitrogenation also indicated in Table 3 

since these procedures may be of importance when forming the magnetic properties of 

materials based on these compounds. 

Miscellaneous 

Pure RFe 12 compounds do not exist. The substitution of a Telement (T = transition metal) for 

Fe stabilizes the ThMn 12 structure. The stabilizing effect of Ti doping on the formation of the 

1:12 phase is considered in [2005Qia]. Calculations and simulation of the YTiFe 11 crystal 

structure are performed on the basis of interatomic pair potentials (calculated lattice parameters 

are given in Table 2); for the YTi4Fe8 stoichiometry, local magnetic moments for Fe and 

Y atoms in different sites were calculated. The site preference of foreign atoms in τ1 and τ2 is 



MSIT 1

considered in [2000Gir] and [2001Wan1], respectively. According to a thermodynamic model 

suggested in [2000Gir] and calculations [2001Wan1] (performed using the cohesive energy 

as a criterion), Ti atoms occupy 8i sites; calculated lattice parameters of τ 1 are also given in 

Table 3. For Ti in τ 2,4i and 4g sites are preferential [2001Wan1]. 

Substitution of Co for Fe in τ 1 increases its magnetization and T C at the expense of the 

anisotropy; the effect of other substations (V, Mo, Ni, Cu) for Fe is considered using a lattice 

inversion method and acquiring the effective interatomic potentials [2001Wan1]. 

Interstitial atoms are introduced into the crystals to modify the magnetic properties. An 

increase in the saturation magnetization upon hydrogenation results from the volume expansion. 

Moreover, the hydrogenation enhances the easy c-axis anisotropy. Hydrogenation 

increases the magnetization and Curie temperature of τ 1 [2001Ter], [2005Ter]. 

The insertion of nitrogen (at 500˚C) in τ 1 (to 0.5 N atoms per f.u.) does not change the 

tetragonal structure, slightly increases the unit cell volume [1991Yan]. 

Interstitial modification of τ 2 by H, N, and C is reported to increase its magnetization and 

Curie temperature. The nitrogenation of the phase increases the magnetic properties and 

decreases the anisotropy field [2000Kim]. 

. Table 1 

Investigations of the Fe-Ti-Y Phase Relations, Structures and Thermodynamics 


[1988Moo] Arc melting of at least 99.9% purity 

components, annealing at 850˚C for 2-3 

weeks / XRD / magnetization 

measurements 

[1988Moz] Arc melting, annealing at 950˚C for 72 h / 

XRD, neutron diffraction, magnetic 

measurements 

[1988Obb] Levitation melting 99.9% Y, 99.5 Ti and Fe, 

annealing at 850˚C for 2 weeks / XRD, TGA 

[1989Zha] R.f. (radio frequency) induction melting of 

99.95% Y, 99.95% Ti, and 99.99% Fe, 

annealing, / X-ray diffraction, 


measurements, hydrogenation 

[1993Rev] Arc melting of 99.9% purity components, 

annealing at 1050˚C for 3 weeks, water 

quenching/XRD, neutron diffraction, 

magnetic measurements, hydrogenation 



MSIT 1 



Studied 

YTi xFe 12–x with x = 1.2 corresponds to the 

correct stoichiometry of the ThMn 12-type 

structure, space group I4/mmm; for 

YTi 1.2Fe 10.8 the lattice parameters were 

determined, TC = 247˚C. 

YTiFe 11 and YTiFe 10 stoichiometries have 

the ThMn 12 type structure. 

For YTiFe 10, and YTiFe 11 stoichiometries, 

the lattice parameters were determined. 

3 

τ1 (with the YTiFe11 stoichiometry) with 

the ThMn 12 type structure was prepared; 

the lattice parameters were determined. 

YTi 0.5Fe 9.5 (1:12 + 2:17), YTi 2Fe 9 (1:11 + 

TiFe2), YTiFe9 (1:12 + 1:11), YTi1.5Fe8 (1:11), 

YTi 1.7 Fe 7.5 (1:11 + TiFe 2 + YFe 3), YTi 2Fe 7 

(TiFe 2 +Y 6Fe 23 + YFe 3); for YTi 1.1Fe 8.6, a 

defect CeMn 6Ni 5 type structure, space 

group P4/mbm, a = 820.9 pm, 

c = 481.4 pm. 

DOI: 10.1007/978-3-540-70890-2_33 

ß Springer 2009

4 33 

Fe–Ti–Y 



[1994Li] Arc melting of ≥99.9% purity 

components, annealing at 960˚C for 3 

days, water quenching / XRD, SEM, TGA in 

the presence of magnetic field, 


[1994Lin] High-frequency induction melting of 

99.9% Fe, 99.8 Ti, and 99,9% Y, annealing 

at 900˚C for 30 days, cooling to 500˚C and 

annealing for 5 days, ice-water quenching 

/ XRD of powders annealed at 500˚C for 5 

days and quenched in liquid nitrogen, 

DTA to 1200˚C (for samples annealed at 

500 and 1050˚C), SEM, EDX 

[1996Has] Arc melting of 99.9% purity components, 

annealing at 600-1150˚C for 2-100 h (for 

different rare-earth metals) 

[1996Tel] Induction melting of Y, Ti, and Fe of 99.9% 

purity, annealing at 900˚C for 2 weeks / 

XRD, magnetic measurements 

[1996Val] Arc melting, annealing at 1100-1200˚C for 

3 days, quenching in water / XRD, 


measurements 


Studied 

τ 2 was successfully prepared from the 

Y 9Ti 5Fe 86 composition (20% of τ 1 impurity 

phase); the lattice parameters were 

determined. 

Isothermal section at 500˚C. Only one 

ternary τ1 phase with the ThMn12-type 

structure is observed. Isothermal section 

consists of ten single-phase, eighteen 

two-phase, and nine three-phase regions. 

The maximum solubility of Ti in-Fe and 

Y 2Fe 17 at this temperature is 3.0 and 1.5 

at.%, respectively. The lattice parameters 

were determined; the phase is stable to 

1200˚C. 

A nonstoichiometric compound R 2(M, 

Fe) 17+δ (δ = 1.0-4.0) can be formed for 

R = Y and M = Ti with a hexagonal 

structure, space group P62m that exists in 

the intermediate region between 2:17 

and 1:12. The nonstoichiometry of this 

compound can be attributed to the 

diversity in the atomic orders in the c 

planes. 

Y 3Ti 1.6Fe 27.4 (single-crystal) powder 

(20 μm) with the monoclinic R3(Ti,Fe)29 

type structure, space group P2 1/c or A2/m 

was prepared. The lattice parameters 

were determined. The formation of the 

compound can be understood by τ 2 + 

Y 2Fe 17 + τ 1 the transformation. 

For Y 3TiFe 29–x stoichiometry with x =1 

and 2 (containing a secondary phase), the 

lattice parameter were determined. 



MSIT 1



[1997Liu] 99.95% ingot Y, 99.9 electrolytic Fe, and 

99.5 industrial grade Ti / diffusion couple 

technique (annealing at 600˚C for 500 h) 

and equilibrium alloying method (arc 

melting) + annealing at 600˚C for 500-700 

h + quenching into liquid nitrogen / 

optical microscopy, EPMA, XRD 

[1997Yan] Fourfold arc melting of 99.9% purity 

components, annealing at 960˚C for 3 

days, water quenching/magnetic 

measurements/XRD, magnetic 

measurements 

[1998And] Induction melting of 99.8% purity Y and 

99.99% purity Fe and Ti, remelting in 

resistance furnace / XRD dilatometer, 

metallography, thermomagnetic analysis 

[1999Pao] Threefold arc melting, annealing at 950˚C 

for 4 d, water quenching/magnetic 

measurements 

[1999Sha] Arc melting, annealing at 960-1075˚C, 

quenching in ice water/magnetic 

measurements, Mössbauer spectroscopy 

[2001Ell] Induction melting of > 99% purity 

components, annealing at 1150˚C for 20 d 

/ XRD, SEM, magnetic measurements 



MSIT 1 



Studied 

YTi xFe 12–x Isothermal section at 600˚C 

(studied compositions (7.2, 22. 73 at.%) 

Y - 79, 76.2, 61.2 at.%) Fe – (1.8, 1.8, 3.8 at. 

%) Y; coexisting phases Fe 3Y+Fe 23Y 6 + 

Fe 2Ti YTiFe 11 +Y 2Fe 17 + -Fe; YFe 2 +-Y+ 

TiFe 2; Section consists of 11 single-phase, 

20 two-phase, and 10 three-phase 

regions. τ 1 with the YTi 1.2Fe 10.8 

stoichiometry is stable at 900˚C, does not 

decompose down to 600˚C. τ2 is not 

observed at 600˚C. 

τ 2 ternary phase with the Nd 3(Ti,Fe) 29 type 

structure, A2/m space group. Lattice 

parameters were determined for the 

Y 3Ti 1.4Fe 27.6 stoichiometry; ρ = 7.22 

g·cm –3 . Based on magnetic measurement 

data, the decomposition of the phase is 

likely to occur at 550-800˚C. 

Single-crystal τ 1 phase; temperature 

dependence of the lattice parameters was 

determined. 

3 : 29 monoclinic cell is formed by 

alternate stacking of the tetragonal 1 : 12 

and hexagonal or rhombohedral 2 : 17 

units, real composition of the compound 

should actually correspond to the 

Y 3TiFe 28 stoichiometry. 

The τ 2 phase with the Y 3Ti 1.5Fe 27.9 

stoichiometry was synthesized and the 

lattice parameters were determined. 

Y2TiFe16 has a hexagonal structure of 

Th 2Ni 17 type with the lattice parameters 

a = 848.1 pm and c = 837.40 pm, 

V = 521.62·10 6 pm 3 

5 

DOI: 10.1007/978-3-540-70890-2_33 

ß Springer 2009

6 33 

Fe–Ti–Y 



[2000Kim] Arc melting, annealing at 950-1150˚C for 

72 h, waster quenching / XRD, magnetic 

measurements 

[2004Tel] XRD, Mössbauer spectroscopy, magnetic 

measurements / nitrogenation 

[2006Sor] Arc melting, annealing at 950-1050˚C for 

10 d/ XRD, Mössbauer spectroscopy 

. Table 2 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Studied 

τ 2 (Y 3(Ti 0.04Fe 0.96) 29 stoichiometry) has the 

Nd 3(Ti,Fe) 29 type structure (P2I/c space 

group); the sample was not single-phase. 

The lattice parameters were determined 

for the Y 3Ti 1.6Fe 27.4N 2.6 stoichiometry. 

For the YTi 0.5Fe 2.5 stoichiometry, Ti 

substitutes for Fe at 6c sites. 

Lattice 

Parameters 


(ωTi) hP3 a = 462.5 at 25˚C, HP > 1 atm [Mas2] 

P6/mmm 

ωTi 

c = 281.3 

(βTi) cI2 a = 330.65 [Mas2] 

1670 - 882 Im3m 

W 

(αTi) hP2 a = 295.06 at 25˚C [Mas2] 

< 882 P63/mmc Mg 

c = 468.35 

(αδFe) cI2 

Im3m 

(δFe) 

1538 - 1394 

W a = 293.15 at 1390˚C [V-C2, Mas2] 

(αFe) 

< 912 

a = 286.65 at 25˚C [Mas2] 

(γFe) cF4 a = 364.67 at 915˚C [V-C2, Mas2] 

1394 - 912 Fm3m 

Cu 

(βY) cI2 a = 407 [Mas2] 

1522 - 1478 Im3m 

W 

(αY) hP2 a = 364.82 at 25˚C [Mas2] 

< 1478 P63/mmc Mg 

c = 573.18 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Lattice 

Parameters 


βY2Fe17 hP38 a = 846.3 [1992Zha] 

1400 - ? P63/mmc Th2Ni17 c = 828.2 

αY2Fe17 hR57 a = 846.0 [1992Zha] 

8 33 

Fe–Ti–Y 



Temperature 

Range [˚C] 

* τ1, Y(Ti,Fe) 12 

(YTiFe11 stoichiometry) 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


tI26 a = 850.9 YTi 1.2Fe 10.8 

I4/mmm c = 475.7 [1988Moo] 

ThMn 12 

> 1200 a = 850.93 V = 347.37·10 6 pm 3 

c = 479.74 [1988Moz] 

a = 852.2 for YTiFe10 

c = 479.6 [1988Obb] 

a = 851.8 for YTiFe 11 

c = 479.7 [1988Obb] 

a = 848.6 [1988Yan] 

c = 478.4 

a = 849.6 V = 345.246·10 6 pm 3 

c = 478.3 [1989Zha] 

a = 850.3 V = 347·10 6 pm 3 

c = 480 [1991Yan] 

a = 851.4 [1994Lin] 

c = 479.8 

a = 847.97 V = 343.08·10 6 pm 3 

c = 477.13 [1997Obb] 

a = 850.9 V = 346.6·10 6 pm 3 

c = 478.3 [1998Nik2], [1999Nik], [2001Nik] 

[2001Ter] 

a = 864.9 calculated for YTiFe 11 

c = 480.5 [2001Wan1] 

a = 849.3 to 851.8 V = 344.8-348.1·10 6 pm 3 

c = 478.0 to 479.8 for YTi xFe 12-x with x = 0.85-1.30 

[2001Wan2] 

a = 853.6 calculated for YTiFe 11 [2005Qia] 

c = 481.4 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


τ 2,Y 3(Ti,Fe) 29 mP* a = 1060.68 for Y 3(Ti xFe 1–x) 29 [1994Li] 

950 - 1050 P2 1/c b = 852.24 

or c = 969.26 

A2/m β = 97.153˚ 

Nd 3(Fe,Ti) 29 

a = 1059.3 for Y 3Ti 1.6Fe 27.4 [1996Tel] 

b = 850.2 

c = 966.6 

β = 97.153˚ 

a = 1060 for Y 3Ti 1Fe 28 [1996Val] 

b = 851 

c = 971 

β = 97.2˚ 

a = 1062 for Y 3Ti 2Fe 27 [1996Val] 

b = 850 

c = 973 

β = 97.1˚ 

a = 1056 for Y 3Ti 1.4Fe 27.6 [1997Yan] 

b = 850 

c = 968 

β = 96.76˚ 

a = 1058.0 for Y3Ti1.5Fe27.5 [1999Sha] 

b = 850.81 

c = 967.61 

β = 97.052˚ 

. Table 3 

Investigations of the Fe-Ti-Y Materials Properties 


[1988Moo] Faraday method For YTi1.2Fe10.8 stoichiometry, TC = 247˚C. 

[1988Moz] Thermomagnetic analysis, singular point 

detection 

[1988Obb] Faraday torque, axial extraction 

magnetometer / hydrogenation 



MSIT 1 


9 

YTiFe 11: T C = 245˚C, H a = 37 kOe (29.45 

kA·m –1 ); YTiFe 10: T C = 238˚C, H a = 21 kOe 

(16.7 kA·m –1 ); temperature dependence 

of magnetic anisotropy field is available. 

YTiFe 10: T C = 257˚C, YTiFe 11: T C = 262˚C; 

Increase in the Curie temperature and Fe 

moment upon hydrogenation is 

observed. 

DOI: 10.1007/978-3-540-70890-2_33 

ß Springer 2009

10 33 

Fe–Ti–Y 



[1988Yan] Neutron diffraction, electron microscopy, 


[1989Zha] Faraday balance, vibrating-sample 

magnetometer 

[1992Szy] Bridgman technique / XRD, magnetooptic 

polar Kerr effect, Bitter technique 

[1993Kou] Ac susceptibility measurements, singular 

point technique, high-field 

magnetization 

[1993Rev] SQUID magnetometer, home-built 

magnetometer based on Faraday 

method 

Y(Ti,Fe) 12 is ferromagnetic at room 

temperature with T C = 252˚C; K 1 = 

0.908 ·10 7 erg·cm –3 

Increase in the Curie temperature and 

anisotropy field for τ 1 by hydrogenation: 

T C from 247 to 294˚C and anisotropy field 

H a from 45 (35.82 kA·m –1 ) to 60 kOe 

(47.76 kA·m –1 ) at room temperature and 

increase on the saturation magnetization 

as well. 

Single-crystal YTi1.2Fe0.8, TC = 251˚C, Ms 

= 890 G (0.089 T), domain wall energy 

γ th = 7.5 erg·cm –2 . 

τ1, temperature dependence of the 

anisotropy field, H a = 4.05 T (at 4.2 K) and 

2.23 T (at room temperature). 

YTi1.1Fe8.6 is non-magnetic (very low 

spontaneous magnetization), 

temperature dependence of magnetic 

moment (in the presence of 1% of Y6Fe23 

impurity is available. 

[1994Li] TGA in the presence of magnetic field For τ2, TC = 113˚C; the average Fe 

magnetic moment is 1.3 μB. [1996Cou] XRD, TGA Model for prediction of the easy 

magnetization direction in the R3(Fe,M) 29 

compounds based on the XRD data for 

Y3(Ti5.2Fe94.8) 29. 

[1996Tel] Pulsed-field magnetometry / singular 

point detection, spinning-samplemagnetic-alignment 

method 

[1996Val] Thermomagnetic analysis, magnetic 

measurements 

[1997Obb] Neutron diffraction, Mössbauer 

spectroscopy / magnetization and ac 

magnetic susceptibility measurements, 

hydrogenation 

Temperature dependence of ac 

susceptibility, temperature dependence 

of the anisotropy field from 4.2 to 

T C = 115˚C; EMD is in the monoclinic 

(204) plane has an angle of 60˚ to the 

c-axis. 

For Y 3TiFe 28, T C = 102˚C and 

M s = 51.52 μ B/f.u. For Y 3Ti 2Fe 27, T C = 

125˚C, M s = 45.90 μ B/f.u. 

Magnetization curves, H a = 5.7 T at 4.2 K 

and 4.8 T at room temperature. Changes 

in the magnetic anisotropy upon 

hydrogenation are considered. 



MSIT 1



[1997Yan] Thermomagnetic analysis, vibratingsample 

magnetometer 

For Y 3Ti 1.4Fe 27.6, the ordering 

temperature is 127˚C; the saturation 

magnetization at 4.2 K and room 

temperature is 52.1 and 38.0 μ B/f.u., 

respectively. H a = 5.2 T (at 4.2 K). 

Temperature dependence of 

magnetization, isotherms of 

magnetization and SPD signal were 

measured; saturation magnetization was 

also calculated. 

[1998And] Thermomagnetic analysis For τ1, spontaneous volume 

magnetostriction at 5 K is 9.4 ·10 –3 ; 

temperature dependences of linear 

magnetostriction strain and volume 

magnetostriction strain were 

determined. 

[1998Nik1] XRD / X-ray Laue method/vibratingsample 

magnetometer, torque and 

magnetization measurements 

[1998Nik2] XRD, Laue X-ray technique / vibratingsample 

magnetometer, torsion 

magnetometer, magnetization 

measurements, hydrogenation 

[1999Nik] XRD/ torque and pendulum 

magnetometer, hydrogenation 

[1999Pao] Thermomagnetic analysis, singular point 

technique 



MSIT 1 


Temperature dependences of magnetic 

anisotropy constants for τ 1 are 

considered; EMD is parallel to the 

tetragonal c-axis. 

11 

For single-crystal τ 1, temperature 

dependences of the magnetic anisotropy 

constants K 1 and K 2, torque curves, 

magnetization curves, temperature 

dependences of saturation 

magnetization, are given; 

K 1 = 0.85 · 10 7 erg·cm –3 and 

K 2 = 0.032 · 10 7 erg·cm –3 . 

Temperature dependences of saturation 

magnetization and anisotropy constants 

K 1 and K 2, torque curves are given; T C = 

265˚C, K 1 = 0.85 · 10 7 erg·cm –3 , and σ s = 

120 emu·g –1 . 

For YTi xFe 12–x with 0.8 ≤ x ≤ 1.2, T C = 

245˚C. EMD of Y 2Ti xFe 17–x lies in the basal 

plane. For Y3(Ti,Fe)29, the {201} direction 

being the easy magnetization direction 

lies in the a-c plane of the monoclinic 

structure; temperature dependence of 

the second-order anisotropy constant 

was measured. 

DOI: 10.1007/978-3-540-70890-2_33 

ß Springer 2009

12 33 

Fe–Ti–Y 



[1999Sha] SQUID magnetometer For Y 3Ti 1.5Fe 27.9, T C = 113˚C; 

magnetization curves were measured 

and saturation magnetization was 

measured and calculated. M s = 178 (5 K) 

and 138 (at room temperature) emu·g –1 . 

[2000Kim] Ac susceptibility measurements, 

vibrating-sample magnetometer 

[2001Ell] Vibrating-sample magnetometer, 

thermomagnetic analysis by Faraday 

balance. A new method of 

hydrogenation 

[2001Kam] Magnetization measurements under 

hydrostatic pressure, SQUID 

magnetometer 

[2001Nik] XRD, Laue X-ray technique/pendulum 

and torque magnetometer, 

hydrogenation, nitrogenation 

[2001Ter] XRD/ Mössbauer spectroscopy, 

magnetization measurements, 

hydrogenation 

[2001Wan2] XRD / vibrating-sample magnetometer, 

extracting-sample magnetometer, 


[2002Wan] XRD / thermomagnetic analysis, 

vibrating-sample magnetometer, SQUID 

magnetometer/thermal expansion 

measurements by ‘push-rod’ linear 

differential transformer method 

For Y 3(Ti 0.04Fe 0.96) 29, easy-cone type 

anisotropy, T C = 130˚C, iron 

magnetization is 1.87 μB at 4.2 K; σs = 

155 Am 2 ·kg –1 ,M s = 52.1 μ B/f.u., H a = 9.0 T. 

T C = 127˚C, M s = 105.7 emu·g –1 for 

Y2TiFe16. 

For τ1, the saturation magnetization up to 

9 kbar at 5-300 K was measured. 

Single-crystal τ1, Ms = 18.8 (at 4.2 K) and 

16.1 (at room temperature) μ B f.u. –1 , H a = 

4 kOe (3.184 kA·m –1 ) (at 4.2 K) and 20 kOe 

(15.92 kA·m –1 ) (at room temp.). 

Single-crystal τ 1,M s = 19.3 μ B f.u. –1 (at 4.2 

K); temperature dependence of secondorder 

magnetic anisotropy constant, field 

dependence of magnetization, 

temperature dependence of 

spontaneous magnetization were 

measured. 

For YTi xFe 12–x with x = 0.85, 1.0, 1.1. 1.2, 

1.3, EMD is along the c-axis; T C is almost 

independent on the Ti content, M s and 

anisotropy field decrease and the 

lattice parameter increases with 

increasing Ti content. 

τ 1 exhibits pronounced positive 

spontaneous volume magnetostriction 

below Curie temperature. 

Temperature dependences of the linear 

thermal expansion and LTE coefficient 

were measured. 



MSIT 1



[2004Tel] Singular point detection / SQUID 

magnetometer, nitrogenation 

[2005Sko] Optical microscopy, thermomagnetic 

analysis, magnetic susceptibility 

measurements 

[2005Ter] X-ray Laue method / torque and 

capacitance magnetometry, 

hydrogenation 



MSIT 1 


13 

Temperature dependences of the 

saturation magnetization and magnetic 

anisotropy constant were determined for 

the Y 3Ti 1.6Fe 27.4 stoichiometry and 

Y 3Ti 1.6Fe 27.4N 2.6. 

Alloys Y 3TiFe 28, Y 3Ti 2Fe 27, and Y 3Ti 3Fe 26 

are two-phase; single crystals Y 3Ti 3Fe 33–x 

have the tetragonal structure of the 

ThMn 12 type. Temperature dependences 

of the magnetic susceptibility and Curie 

temperatures for Y3TixFe29–x and Y3Ti3Fex 

were measured. 

For YTiFe 11–xCo x (0 ≤ x ≤ 3) single crystals, 

magnetization and torque curves, 

temperature and compositional 

dependences of magnetic anisotropy 

constant are given. 

DOI: 10.1007/978-3-540-70890-2_33 

ß Springer 2009

14 33 

Fe–Ti–Y 

. Fig. 1 

Fe-Ti-Y. Isothermal section at 600˚C 



MSIT 1

References 


15 

[1987Mur] Murray, J.L., “The Fe-Ti (Iron-Titanium) System” in “Phase Diagram of Binary Titanium Alloys”, ASM 

Inter., Metal Park, Ohio, Murray, J.L., (Ed.), 99–111 (1987) (Experimental, Phase Diagram, Phase 

Relations, Thermodyn., #, 112) 

[1988Moo] De Mooij, D.B., Buschow, H.J., “Some Novel Ternary ThMn 12-Type Compounds”, J. Less-Common 

Met., 136, 207–215 (1988) (Crys. Structure, Experimental, *, 5) 

[1988Moz] Moze, O., Pareti, L., Solzi, M., David, W.I.F., “Neutron Diffraction and Magnetic Anisotropy Study of 

Y-Fe-Ti Intermetallic Compounds”, Solid State Commun., 66(5), 465–469 (1988) (Experimental, Crys. 


[1988Obb] Obbade, S., Miraglia, S., Fruchart, D., Pre, M., L´Heritier, P., Barlet, A., “Structural and Magnetic 

Properties of the ThMn 12 Type Iron Alloys: Effects of Hydridation”, Compt. Rend. Acad. Sci. Paris, Ser. 2, 

307, 889–895 (1988) (Crys. Structure, Magn. Prop., Experimental, 11) 

[1988Yan] Yang, Y., Sun, H., Kong, L., Yang, J., Ding, Y., Zhang, B., Ye, C., Jin, L., Zhou, H., “Neutron Diffraction 

Study of Y(Ti,Fe) 12”, J. Appl. Phys., 64(10), 5968–5970 (1988) (Experimental, Magn. Prop., 10) 

[1989Zha] Zhang, L.Y., Wallace, W.E., “Structural and Magnetic Properties of RTiFe 11 and their Hydrides (R =Y, 

Sm)”, J. Less Common Met., 149, 371–376 (1989) (Experimental, Crys. Structure, Magn. Prop., 16) 

[1991Yan] Yan, Y.-C., Zhang, X.-D., Kong, L.-S., Ran, Q., “Magnetocrystalline Anisotropies of RTiFe 11N x 

Compounds”, Appl. Phys. Lett., 58(18), 2042–2044 (1991) (Crys. Structure, Experimental, 4) 

[1992Szy] Szymczak, R., Zawadzki, J., Manh, D.H., Slepowronski, M., “Domain-Structure in Y(Fe,T)12 (T = Ti, 

Cr, Si) Compounds”, J. Magn. Magn. Mater., 104(1), 321–323 (1992) (Experimental, Magn. Prop., 10) 

[1992Zha] Zhang, W., Liu, G., Han, K., “The Fe-Y (Iron-Yttrium) System”, J. Phase Equilib., 13(3), 304–308 

(1992) (Phase Diagram, Phase Relations, #, Review, 29) 

[1993Kou] Kou, X.C., Zhao, T.S., Groessinger, R., Kirchmayr, H.R., Li, X., de Boer, F.R., “Magnetic Phase- 

Transitions, Magnetocrystalline Anisotropy, and Crystal-Field Interactions in the RFe 11Ti Series 

(where R = Y, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, or Tm)”, Phys. Rev. B, 47(6), 3231–3242 (1993) 

(Calculation, Experimental, Magn. Prop., 52) 

[1993Rev] Revel, R. Tomey, E. Soubeyroux, J.L. Fruchart, D. Jacobs, T.H. Buschow, K.H.J., “Crystal Structure and 

Magnetic Properties of the Ternary Compound YFe 8.6Ti 1.1 and its Hydride”, J. Alloys Compd., 202(1-2), 


[1994Li] Li, H.-S., Courtois, D., Cadogan, J.M., Xu, J.-M., Dou, S.X., “Structural and Magnetic Properties of the 

Novel Ternary Compound Y 3(Fe,Ti) 29”, J. Phys.: Condens. Matter, 6(49), L771–L775 (1994) (Crys. 

Structure, Experimental, Magn. Prop., *, 16) 

[1994Lin] Lingmin, Z., Junqin, J., Xianji, S., Yinghong, Z., “Phase Equilibria in the Y-Ti-Fe System at 500˚C”, Z. 

Metallkd., 85(9), 625–627 (1994) (Experimental, Phase Diagram, *, #, 15) 

[1996Cou] Courtois, D., Li, H.-S., Cadogan, J.M., “Determination of the Easy Magnetisation Direction by X-ray 

Diffraction Analysis at Room Temperature in the R 3(Fe,M) 29 Compounds: R=Pr, Nd, Sm, Gd, Tb, Dy 

and Y; M=Ti and V”, Solid State Commun., 98(6), 565–570 (1996) (Crys. Structure, Experimental, 12) 

[1996Has] Hasebe, A., Otsuki, E., “Crystal Structure and Magnetic Properties of R 2(Fe,M) 17+δ”, Mater. Trans., 

JIM, 37(4), 870–877 (1996) (Crys. Structure, Experimental, 12) 

[1996Tel] Tellez-Blanco, J.C., Kou, X.C., Groessiger, R., “Magnetocrystalline Anisotropy of Y 3Fe 27.4Ti 1.6”, J. Magn. 

Magn. Mater., 164(1-2), L1–L6 (1996) (Experimental, Magn. Prop., Phase Relations, 23) 

[1996Val] Valeanu, M., Plugaru, N., Galateanu, A., Burzo, E., Laforest, J., “Magnetic Study of R 3Fe 29–xM x, with 

R=Y,Gd and M=V,Ti”, J. Magn. Magn. Mater., 157–158, 383–384 (1996) (Crys. Structure, Experimental, 


[1997Liu] Liu, Z., Jin, Z., Xia, C., “873 K Isothermal Section of Phase Diagram for Y-Fe-Ti Ternary System”, Scr. 

Mater., 37(8), 1129–1134 (1997) (Experimental, Phase Relations, *, #, 7) 

[1997Obb] Obbade, S., Fruchart, D., Bououdina, M., Miraglia, S., Souberyroux, J.L., Isnard, O., “About Hydrogen 

Insertion in ThMn 12 Type Alloys”, J. Alloys Compd., 253–254, 298–301 (1997) (Crys. Structure, Magn. 


[1997Yan] Yang, F.M., Xiu-Feng, Han, de Boer, F.R., Li, H.S., “Analyses of the Magnetic Properties of Y 3Fe 29–xTi x 

and Other Associated Compounds”, J. Phys. Condens. Matter, 9, 1339–1346 (1997) (Crys. Structure, 

Experimental, Magn. Prop., Calculation, 24) 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_33 

ß Springer 2009

16 33 

Fe–Ti–Y 

[1998And] Andreev, A.V., Zadvorkin, S.M., “Thermal Expansion Anomalies and Spontaneous Magnetostriction 

in RFe 11Ti Single Crystals”, Philos. Mag. B, 77(1), 147–161 (1998) (Crys. Structure, Magn. Prop., 


[1998Nik1] Nikitin, S.A. Ivanova, T.I., Tereshina, I.S., “Effect of Rare-Earth Sublattice on the Magnetic Anisotropy 

of RFe 11Ti (R = Y, Sm, Tb) Single Crystals”, Inorg. Mater. (Engl. Trans.), 34(5), 458–461 (1998) (Crys. 

Structure, Magn. Prop., Experimental, 12) 

[1998Nik2] Nikitin, S.A., Tereshina I.S., Verbetskii, V.N., Salamova, A.A., “Magnetic Anisotropy of YFe 11Ti and its 

Hydride”, Phys. Solid State, 40(2), 258–262 (1998) (Crys. Structure, Experimental, 20) 

[1999Nik] Nikitin, S.A., Tereshina, I.S., Verbetsky, V.N., Salamova, A.A., “Magnetic Anistropy of YFe 11Ti Single 

Crystal and its Hydride”, Int. J. Hydrogen Energy, 24, 217–219 (1999) (Crys. Structure, Experimental, 


[1999Pao] Paoluzi, A., Pareti, L., “Magnetocrystalline Anisotropy in Iron-Rich Rare-Earth Intermetallics. 

A Phenomenological Approach for the Comparison of the Overall and Fe Sublattice Anisotropies in 

RE(FeTi) (12), RE 2(FeTi) (17) and RE 3(FeTi) (29) Related Compounds (RE = Y,Sm)”, J. Phys.: Condens. 

Matter, 11(29), 5613–5621 (1999) (Calculation, Crys. Structure, Experimental, Magn. Prop., 32) 

[1999Sha] Shan, V.R., Markandeyulu, G., Rama Rao, K.V.S., Huang, M.Q., McHenry, M.E., “Study of Structural 

and Magnetic Properties and Exchange Interactions in (Y 1–xGd x) 3Fe 27.5Ti 1.5 {x = 0,0.2, 0.5, 0.8, 1.0}”, 

Solid State Commun., 112, 161–166 (1999) (Crys. Structure, Experimental, Magn. Prop., Calculation, 

17) 

[2000Kim] Kim, H.-T., Kim, T.-K., Kim, M.-J., Song, M.-S., Yang, J.-H., Kim, C.-S., Kim, Y.-B., Xiao, Q.-F., Lui, 

W., Zhang, Z.-D., “Structural and Intrinsic Magnetic Properties of Y 3(Fe 0.96Ti 0.04) 29 and Its Nitride”, 

IEEE Trans. Magn., 36, 3339–3341 (2000) (Crys. Structure, Experimental, Magn. Prop., 14) 

[2000Gir] Girt, E., Altounian, Z., “Model for Predicting Atomic Substitutions in Intermetallic Compounds”, 

J. Appl. Phys., 87(9), 4747–4749 (2000) (Calculation, Crys. Structure, 19) 

[2000Rag] Raghavan, V., “Fe-Ti-Y (Iron-Titanium-Yttrium)”, J. Phase Equilib., 21(5), 467 (2000) (Phase Relations, 

Review, #, 3) 

[2001Ell] Ellouze, M., l’Heritier, Ph., Cheikh-Rouhou, A., Joubert, J.C., “New Method of Insertion of Hydrogen 

of Hydrogen in R 2Fe 16Ti Alloys with R = Y and Nd”, J. Alloys Compd., 322, 211–213 (2001) (Crys. 

Structure, Experimental, Magn. Prop., 11) 

[2001Kam] Kamarad, J., Garcia-Landa, B., Mikulina, O., Arnold, Z., Ibarra, M.R., Algarabel, P.A., “Pressure Effects 

on Magnetic Properties of R(Fe,M) 12 Single Crystals (R = Rare Earth, M = Ti, Mo)”, J. Magn. Magn. 

Mater., 226(2), 1446–1448 (2001) (Experimental, Magn. Prop., 10) 

[2001Nik] Nikitin, S.A. Tereshina, I.S. Verbetsky, V.N. Salamova, A.A., “Transformations of Magnetic Phase 

Diagram as a Result of Insertion of Hydrogen and Nitrogen Atoms in Crystalline Lattice of RFe 11Ti 

Compounds”, J. Alloys Compd., 316, 46–50 (2001) (Crys. Structure, Experimental, Magn. Prop., 14) 

[2001Rag] Raghavan, V., “Fe-Ti-Y (Iron-Titanium-Yttrium)”, J. Phase Equilib., 22(5), 577 (2001) (Phase Relations, 

Review, *, 3) 

[2001Ter] Tereshina, I.S., Gaczynski, P., Rusakov, V.S., Drulis, H., Nikitin, S.A., Suski, W., Tristan, N.V., Palewski, 

T., “Magnetic Anisotropy and Moessbauer Effect Studies of YFe 11Ti and YFe 11TiH”, J. Phys.: Condens. 

Matter, 13(35), 8161–8170 (2001) (Crys. Structure, Experimental, Magn. Prop., 20) 

[2001Wan1] Wang, Y., Shen, J., Chen, N.X., Wang, J.L., “Theoretical Investigation on Site Preference of 

Foreign Atoms in Rare-Earth Intermetallics”, J. Alloys Compd., 319, 62–73 (2001) (Calculation, Crys. 


[2001Wan2] Wang, W.Q., Wang, J.L., Tang, N., Fuquan, B., Wu, G.H., Yang, F.M., Jim, H.M., “Structural and 

Magnetic Properties of RCo 12–xTi x (R = Yand Sm) amd YFe 12–xTi x Compounds”, J. Phys. D: Appl. Phys., 

34, 307–312 (2001) (Crys. Structure, Experimental, Magn. Prop., 9) 

[2002Wan] Wang, J.L., Marquina, C., Garcia-Landa, B., Ibarra, I., Yang, F.M., Wu, G.H., “Magnetovolume Effect 

in ThMn 12-Type Fe-Rich R(Fe, Nb) 12-Based Compounds”, Physica B, 319(1-4), 73–77 (2002) (Experimental, 

Magn. Prop., Phys. Prop., 14) 

[2004Tel] Tellez-Blanco, J.S., Groessinger, R., Wiesinger, G., Levitschnig, H., Hilscher, G., “Untrinsic Properties 

of Y 3Fe 27.4Ti 1.6 and its Interstitial Nitride”, J. Magn. Magn. Mater., 272–276(2), 802–803 (2004) 

(Experimental, Magn. Prop., 6) 

[2005Qia] Qian, P., Chen, N.-X., Shen, J., “Atomistic Simulation for the Phase Stability, Site Preference and 

Thermal Expansion of YFe 12–xT x (T = Ti, V, Cr, Mn, Zr, Nb, Mo,W)”, Solid State Commun., 134(11), 

771–776 (2005) (Calculation, Crys. Structure, Electronic Structure, Magn. Prop., 42) 



MSIT 1


17 

[2005Sko] Skokov, K., Grushishev, A., Khokholkov, A., Pastushenkov, Yu., Pankratov, N., Ivanova, T., Nikitin, S., 

“Structural and Magnetic Properties of R 3Fe (29–x)Ti (x) Alloys and R 3Fe (33–x)Ti 3 Single Crystals, R=Y, 

Gd, Tb, Dy, Ho, Er”, J. Magn. Magn. Mater., 290–291(1), 647–650 (2005) (Crys. Structure, Experimental, 


[2005Ter] Tereshina, E., Telegina, I., Palewski, T., Skokov, K., Tereshina, I., Folcik, L., Drulis, H., “The 

Magnetocrystalline Anisotropy in Y(Fe,Co) 11TiH Single Crystals”, J. Alloys Compd., 404–406, 208–211 

(2005) (Crys. Structure, Experimental, Magn. Prop., 16) 

[2006Sor] Sorescu, M., Diamandescu, L., Valeanu, M., “Substitutional Effects in RFe 3 Intermetallics (R=Dy, Sm, 

Y)”, Intermetallics, 14(3), 332–335 (2006) (Crys. Structure, Experimental, 9) 


(1990) 





MSIT 1 

DOI: 10.1007/978-3-540-70890-2_33 

ß Springer 2009

Iron – Titanium – Zirconium 


Tamara Velikanova, Kostyantyn Korniyenko 

Introduction 

Phase relationships in the Fe-Ti-Zr ternary system are of great interest, in the first instance, 

because this system contains two Laves phases with a component of the iron triad (iron, 

cobalt, nickel). Metallides of this type are used as components of heat-resistant alloys and 

austenitic steels owing to their influence on mechanical properties (hardness, tensile strength, 

improved plasticity at high temperatures etc). Studies of (Zr 1–xTi x)Fe 2 ternary alloys are of 

great technological importance because their magnetic and structural properties can be 

tailored by changing the zirconium and titanium concentration. 

Another important aspect is related to applications of alloys based on the intermetallic 

compound TiFe with a partial substitution of iron by zirconium with a view to increasing its 

potential for use in hydrogen storage and purification applications [1988Nag, 1999Sin, 

2000Nis]. The Fe-Ti-Zr system is also interesting as it contains titanium and a 3d transition 

metal forming quasicrystals. 

However, information about the constitution of the Fe-Ti-Zr system is incomplete. 

Experimental studies of the alloy system have dealt with the temperature-composition section 

ZrFe 2-TiFe 2 [1963Pie, 1971Pet, 1973Sve, 1987Bla, 2001Bud, 2003Sur] and an isothermal 

section at 900˚C [2007Zho]. It should be noted that the reported data for as-cast alloys 

[1963Pie, 1987Bla, 2001Bud, 2003Sur] and phase equilibria at 900˚C [2007Zho] on the one 

hand and in the ZrFe 2-TiFe 2 section after [1971Pet, 1973Sve] on the other, seem to be in 

conflict. The effect of titanium on the stabilization of the body-centered cubic (βZr) phase was 

considered in [1982Sil]. 

Publications devoted to the experimental study of phase relations, crystal structures and 

thermodynamics are listed in Table 1 together with the techniques used. Alloys based on Zr 3Fe 

were studied by [1991Ard]. Rapidly quenched alloys containing icosahedral and related phases 

were studied by [1995Kim, 1998Kim1, 1998Kim2]. The crystal structures of the phases in Fe- 

Zr alloys with titanium additions as well as the Zr 0.2Ti 1.3Fe 0.8 alloy are reported in [1982Sil] 

and [1999Sin], respectively. Results of calculations of site occupancy of the added zirconium in 

the TiFe-based alloys are reported by [2002Boz]. Experimental studies of thermodynamic 

properties are focused on the determination of the mixing enthalpies of liquid Fe-Ti-Zr alloys 

[1999Thi]. A review of the literature concerns information on phase equilibria in the Fe-Ti-Zr 

system and the crystal structures of the phases [1992Rag]. 


Fe–Ti–Zr 34 

1 

The Fe-Zr boundary binary system is accepted from [2002Ste]. The Ti-Zr system is accepted 

from [1994Kum] (Fig. 1), which is essentially the same as in [Mas2]. The Fe-Ti boundary 

system is accepted from [1987Mur, Mas2]. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_34 

ß Springer 2009

2 34 

Fe–Ti–Zr 


No stable ternary phases have been found in this system. Crystallographic data on the solid 

phases of the Fe-Ti-Zr system are listed in Table 2. 

High mutual solubilities exist between the TiFe 2 (λ 1) and ZrFe 2 (λ 2) Laves phases. 

[1963Pie] found that as-cast alloys of compositions along with the ZrFe2-TiFe2 section lay 

in the two-phase ZrFe2 + TiFe region in the range of compositions from 60 to 80 mol% of 

ZrFe 2 (6.7 to 13.3 at.% Ti). The wide TiFe 2 and ZrFe 2 solubility ranges at high temperatures 

are supported by studies of as-cast alloys [1987Bla, 2001Bud, 2003Sur]. A TiFe 2 solubility in 

ZrFe 2 of about 23 mol% (7.7 at.% Ti), close to that found for as-cast alloys, was reported by 

[1971Pet] for 900˚C, based on XRD data from alloys annealed for 200 h. These findings have 

not been confirmed. A solubility of about 8.1 at.% Zr (corresponding to 25.2 at.% Ti) was 

reported by [2007Zho]. They determined an isothermal section for the whole system at 900˚C 

using the diffusion-triple technique, employing an annealing time of 1440 h (compared with 

200 h as used by [1971Pet]) that was sufficient to allow complete equilibrium being achieved. 

Therefore, the data of [2007Zho] for 900˚C are preferable. The solubility of titanium in the 

λ 2 phase at 900˚C is approximately 11.3 at.%, according to the data of [2007Zho]. 

Figure 2 presents the concentration dependences of the lattice parameters of the λ 1 and λ 2 

Laves phases in the ZrFe 2-TiFe 2 quasibinary system derived by [1963Pie] from studies of ascast 

specimens. The a and c parameters for the λ 1 phase increase continuously with decreasing 

titanium content to 8.3 at.% Ti. The same tendency was reported by [1987Bla]. [2001Bud, 

2003Sur] reported the a and c lattice parameters for the λ1 phase present in alloys of 

composition (Zr1–xTix)Fe2 with x from 0.2 to 1. The reported values agree well with the 

data of [1963Pie, 1987Bla], but both Laves phases (λ 1 and λ 2) were observed simultaneously in 

alloys over a wider composition range as compared with the work of [1963Pie] - from 40 to 80 

mol% ZrFe 2 (correspond to the range 6.7 to 20 at.% Ti). This could be due to the partial 

decomposition of the λ 1 phase during cooling of the as cast specimens after arc melting. 

The solubilities of titanium in Zr 2Fe and of zirconium in the TiFe phase at 900˚C were 

reported by [2007Zho] as about 26.9 and 7.2 at.%, respectively. 

A phase with the Ti2Ni type crystal structure was found in rapidly quenched Zr15Ti60Fe25 

and Zr10Ti65Fe25 alloys by [1995Kim, 1998Kim1, 1998Kim2]. A phase with the same structure 

was obtained in a Zr 0.2Ti 1.3Fe 0.8 alloy that had been prepared by induction melting and 

subjected to a hydrogenation treatment [1999Sin]. This phase is denoted in Table 2 as the 

τ phase. It should be thermodynamically unstable. 

The icosahedral, I (ZrTiFe) and 1/1 bcc (labeled as M (ZrTiFe)) approximant phases are 

reported by [1995Kim, 1998Kim2]. The icosahedral quasicrystal phase was observed in rapidly 

quenched Fe-Ti-Zr ternary alloys with a titanium content between 45 to 70 at.%, zirconium 

from 5 to 25 at.% and iron from 20 to 30 at.% [1995Kim, 1998Kim1]. TEM studies indicate 

the crystal structure of the I phase to be strongly disordered. The quasilattice constant is given 

in Table 2. 

Studies of melt spun arc melted Zr 15Ti 60Fe 25 and Zr 10Ti 65Fe 25 alloys revealed three 

metastable ternary phases [1998Kim1]. The Zr 15Ti 60Fe 25 alloy contained the τ phase (Ti 2Ni 

type, fcc with a ≈ 1150 pm) and an ordered bcc TiFe-based solid solution (CsCl type) 

as dominant phases along with small amounts of the I phase. At the same time, in the 

Zr 10Ti 65Fe 25 alloy, the I phase was dominant while the τ phase was the secondary 

phase. Additionally, the M (ZrTiFe) 1/1 approximant (bcc, a = 1330 pm), the face-centred 



MSIT 1

orthorhombic (a = 3200 pm, b = 2660, c = 1040 pm) and the λ 1 Laves phase (hcp; a = 515, 

c = 837 pm) were found in both of these alloys. 

The addition of Ti was found to stabilize a (βZr) solid solution containing 4 at.% Fe 

[1982Sil]. This effect was observed during investigations of ternary alloys of composition 

Zr 1–xTi xFe 0.04 that had been prepared by arc melting followed by homogenizing for 6 days at 

1000˚C before quenching into cold water; even with only a 1 at.% titanium addition. Two 

phases, namely the β and α2 phases have been identified in all samples containing up to 7 at.% 

Ti, while only the β phase was seen in the sample with the Zr0.89Ti0.08Fe0.04 composition and 

for those of higher titanium contents. It was postulated that short-range ordering produced by 

the formation of Ti-Fe pairs in the lattice inhibits the β → α 2 transformation on quenching to 

room temperature. 

The substitutional site preference of ternary alloying additions to B2 compounds (stable at 

room temperature and with stoichiometry 1:1) was determined by [2002Boz] using the 

Bozzolo-Ferrante-Smith (BFS) method. This quantum approximate method was applied, in 

particular, to the study of zirconium additions to the TiFe based phase. The energy of 

formation per atom in the perfectly ordered B2 TiFe 72-atom cell is –0.7149 eV·atom –1 . The 

energy of formation per atom of a 72-atom cell with one Zr (Ti) substitution is –0.6808 

eV·atom –1 ; slightly higher than that of the ground state. In the case of Fe rich TiFe alloys, 

Zr prefers to occupy Fe sites, with the energy of formation of a 72-atom cell being in this 

case –0.5341 eV·atom –1 . 



3 

The quasibinary temperature-composition section ZrFe 2-TiFe 2 has been established in the 

ternary system [1971Pet]. The section is given in Fig. 3, based on the data of [1963Pie, 1971Pet, 

1987Bla, 2007Zho]. The system is of peritectic type with considerable mutual solubility of the 

components. Direct experimental evidence of the λ 2 phase boundary at the peritectic temperature 

is absent in the work of [1971Pet] but is presumed to be present and is indicated in the 

diagram. Obviously, the value of Zr solubility in TiFe 2 reported by [1971Pet], namely 16-17 

at.% Zr at 900-1470˚C, cannot be considered as reliable because of uncertainty in the 

concentration dependence of the lattice periods of the λ1 phase; only one specimen was 

prepared in the single-phase region. Moreover, the alloys were not fully equilibrated owing 

to the short annealing time employed; as is now clear taking into account the results of 

[2007Zho]. The solubility range of the λ 1 phase at 900˚C as given by [1971Pet] is too high in 

comparison with the data of [1963Pie] determined for as-cast alloys and with the data of 

[1987Bla] obtained from annealed (at 800-1500˚C) and quenched specimens. In Fig. 3, the 

phase boundaries λ 2/λ 2+λ 1 and λ 2+λ 1/λ 1 are drawn by taking into account the wide extension 

of λ1 and λ2 homogeneity ranges at high temperatures deduced by [1963Pie, 1987Bla] (see the 

“Solid Phases” section) and the reduction in their extensions at 900˚C after [2007Zho]. It can 

be seen that the solubilities of the λ 1 and λ 2 phases given by [1971Pet] correspond to 

temperatures of about 1300˚C and the solidus temperature, respectively. Thus, the constitution 

of the investigated alloys corresponded to the high-temperature state because the annealing 

time was not sufficient. Therefore, the low-temperature solubility data of [1971Pet] cannot 

be accepted. 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_34 

ß Springer 2009

4 34 

Fe–Ti–Zr 


The existence of the three-phase invariant equilibrium L + λ 2 Ð λ 1 of incongruent type follows 

from quasibinarity of the ZrFe 2-TiFe 2 section [1971Pet]. Temperature of the above equilibrium 

was determined as 1470±10˚C on the basis of differential thermal analysis data. Compositions 

of the phases taking part in this reaction are shown in Table 2. 


A complete isothermal section for 900˚C was constructed by [2007Zho] who used a diffusiontriple 

method with EMPA to study the equilibria. The section is presented in Fig. 4. The tielines 

across two-phase fields are drawn with solid lines while the positions of three-phase fields 

are marked by dashed lines based on the tendencies of directional changes of the boundary 

binary tie-lines. 


The mixing enthalpies of liquid Fe-Ti-Zr alloys were calculated by [1996Wan] from enthalpy 

data for the three boundary binary systems. The enthalpies of mixing of liquid ternary 

Fe-Ti-Zr alloys at 1600˚C were obtained using the Hillert-2 interpolation algorithm 

[1980Hil] using suitable interpolation geometry. 

Enthalpies of mixing of ternary liquid alloys have been presented by [1999Thi]. Measurements 

were performed along the ZrFe 2-Ti, TiFe 2-Zr and Zr 37Ti 63-Fe sections using a levitation 

alloying calorimeter (LAC), as described by [1994Qin]. The experimental data obtained were 

in a good agreement with calculations carried out using a regular associate model. Figure 5 

shows the mixing enthalpy of liquid Fe-Ti-Zr alloys for 1879˚C in the form of isoenthalpy 

curves. The extreme value of the mixing enthalpy, of about –23 kJ·mol –1 , is located in the 

Fe-Zr binary system at 45 at.% Zr. The excess heat capacities of liquid Fe-Ti-Zr alloys at 1879˚ 

C presented in [1999Thi], calculated using the regular associate model, are shown in Fig. 6. 


The Fe-Ti-Zr and related alloys are of great interest for practical applications in modern 

technology owing to their valuable electrical, magnetic, optical and structural properties. 

Moreover, TiFe-based alloys with a partial substitution by iron are promising materials for 

the storage and purification of hydrogen [1988Nag, 1999Sin, 2000Nis]. 

The properties of the Fe-Ti-Zr alloys investigated and experimental techniques used are 

listed in Table 3. 

Magnetic property investigations of alloys in the ZrFe 2-TiFe 2 section carried out by 

[1963Pie] demonstrated that the TiFe 2-based phase behaves as a strongly paramagnetic 

material with a susceptibility that is practically temperature independent, whereas the 

ZrFe 2-based phase is ferromagnetic with a Curie temperature of 355˚C. The effective moment 

per iron atom, obtained from the observed saturation magnetization at 4 K, is 1.62 μB. The 

reduced moment of the iron atoms in both the TiFe2 and ZrFe2 phases as compared to that of 



MSIT 1

elemental iron was attributed by the authors to a transfer of charge from Ti or Zr to iron. Later, 

the magnetic behavior of ZrFe 2-TiFe 2 alloys was studied in more detail by [2001Bud] and 

[2003Sur]. Both the Zr 2Fe and Zr 3Fe compounds demonstrated paramagnetic properties at 

room temperature [1991Ard]. 

The hydrogen behavior characteristics of zirconium-substituted TiFe and Zr 0.2Ti 1.3Fe 0.8 

alloys were studied by [1988Nag, 2000Nis] and [1999Sin], respectively. In particular, the 

structural and microstructural characteristics of the hydrogen storage material Zr0.2Ti1.3Fe0.8 

revealed that this alloy is multiphase [1999Sin]. The storage capacity for this material was 

found to be about 1.2 mass% at 200˚C and the desorption kinetics were found to be two times 

higher than the native material, Ti 1.3Fe. The improved activation process and faster kinetics 

were thought to arise from the presence of a higher density of interfaces and volume expansion 

induced cracking of (βTi) facilitating hydrogen absorption and desorption in the lattice. 

It was shown by [1987Bla] that Vickers microhardness values of the λ 1 phase in the ZrFe 2- 

TiFe 2 quasibinary system decrease linearly with increasing titanium content, from 13.3 up to 

33.3 at.% (Fig. 7). 

. Table 1 

Investigations of the Fe-Ti-Zr Phase Relations, Structures and Thermodynamics 


[1963Pie] Levitation melting, X-ray diffraction (GE XRD-3 

diffractometer) 

[1971Pet] Arc melting, annealing in evacuated ampoules 

with quenching in cold water, differential 

thermal analysis, X-ray diffraction, chemical 

etching, optical microscopy 

[1973Sve] Arc melting, differential thermal analysis, X-ray 

diffraction, optical microscopy, microprobe 

analysis 

[1982Sil] Arc melting, annealing in evacuated ampoules 

with quenching in cold water, Mössbauer 

spectroscopy, X-ray diffraction 

[1987Bla] Arc melting, annealing in vacuum, quenching, 

slow cooling, X-ray diffraction (Philips 

PW1050diffractometer), optical microscopy 



Zr 1–xTi xFe 2,0

6 34 

Fe–Ti–Zr 



[1998Kim1] 

[1998Kim2] 

Arc melting, high speed crystallization, TEM 

(JEOL 2000FX transmission electron 

microscope), energy-dispersive X-ray 

spectrometry, X-ray diffraction, Archimedes 

weighing technique, neutron powder 

diffraction 

[1999Sin] Induction melting, X-ray diffraction (PW-1710 

diffractometer), scanning electron microscopy 

(SEM) 



Zr 15Ti 60Fe 25 (at.%) 

Zr0.2Ti1.3Fe0.8 

[1999Thi] Levitation alloying calorimetry The ZrFe2-Ti, TiFe2-Zr and 

Zr37Ti63-Fe sections 

[2001Bud] 

57 

Fe Mössbauer spectroscopy, X-ray diffraction The ZrFe2-TiFe2 section 

[2003Sur] Arc melting, X-ray diffraction, 57 Fe Mössbauer 

spectroscopy, neutron diffraction 

[2007Zho] Diffusional welding, annealing, quenching, 

EPMA (JX-8800R apparatus) 

. Table 2 

Crystallographic Data of Solid Phase 


Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

The ZrFe 2-TiFe 2 section (0 to 6.7 

and 23.3 to 33.3 at.% Ti) 

900˚C (annealing for 1440 h); the 

whole range of compositions 

Lattice 

Parameters 


β, Zr1–x–yTixFey cI2 

Im3m 

W 

y =0,0 882˚C [Mas2, V-C2] 

1670 - 882 dissolves 22 at.% Fe at 1085˚C 

[1987Mur, Mas2] 

α1,ZrxTiyFe1–x–y x =0,0



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 


Lattice 

Parameters 


7 

(γFe), cF4 a = 364.68 x =0,y =0,T = 912˚C [V-C2] 

ZrxTiyFe1–x–y Fm3m x =0,0

8 34 

Fe–Ti–Zr 



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


λ2, (Zr1–xTix)Fe2 cF4 0 < x ≲ 0.339, T = 900˚C [2007Zho] 

Fd3m C15 structure 

MgCu2 a=706 to 699.5 0 ≤ x ≤ 0.2, in the as-cast alloys [1963Pie] 

a=705.4 0.25 ≤ x ≤ 0.37, in the alloys annealed at 900˚C 

and quenched in cold water [1971Pet] 

a=702.7 x = 0.2, together with the λ1 phase [1987Bla] 

a=699.2 x = 0.6, together with the λ1 phase [1987Bla] 

a=708 to 704 0 ≤ x ≤ 0.4, in the as-cast samples [2001Bud] 

x = 0.1, as-cast sample: 

a=709.9 T = 397˚C 

a=707.7 T = 97˚C 

a=705.4 T = 17˚C [2003Sur] 


a=708.2 T = 397˚C 

a=704.5 T = 127˚C 

a=705.0 T = 17˚C [2003Sur] 


a=704.5 T = 377˚C 

a=704.4 T = 127˚C and 17˚C [2003Sur] 

βZrFe2 a=702 to 709 27.5 to 34.4 at.% Zr in the binary Zr-Fe system 

< 1673 

[2002Ste] 

a=706.5 at 66.7 at.% Fe [V-C2] 

λ3, αZrFe2 hP24 26.5 to 27 at.% Zr [2002Ste] 

1345 - 1240 P63/mmc C36 structure 

MgNi2 a=495.34 in the alloy Zr25Fe75 (at.%) annealed at 1290˚C 

c = 1614.3 for 7.5 h, together with (αFe) and Zr6Fe23 phase 

[2002Ste] 

a=498.8 

c = 1632 

at 1100˚C [V-C2] 

Zr2Fe tI12 66.7 to 67.2 at.% Zr [2002Ste] 

951 - 780 I4/mcm C16 structure 

CuAl2 a=641 

c = 556 

in the alloy Zr69Fe31 [1991Ard] 

without visible solubility of titanium [1991Ard] 

a=637.9 

c = 559.4 

in the alloy Zr40Fe60 (at.%) annealed at 800˚C for 

500 h, together with the βZrFe 2 and Zr 3Fe phases 

[2002Ste] 

dissolves 26.9 at.% Ti at T = 900˚C [2007Zho] 



MSIT 1



Temperature 

Range [˚C] 

Pearson 

Symbol/ 

Space 

Group/ 

Prototype 

Lattice 

Parameters 


Zr3Fe oC16 74.8 to 75.4 at.% Zr [2002Ste] 

< 851 Cmcm 

Re3B without visible solubility of titanium [1991Ard] 

a = 332.16 in the alloy Zr60Fe40 (at.%) annealed at 700˚C for 

b = 1096.4 1000 h, together with the βZrFe2 phase and 

c = 882.3 traces of the Zr2Fe phase [2002Ste] 

a = 333 

b = 1095 

c = 882 

at 75 at.% Zr [1991Ard] 

Zr6Fe23 cF116 20.6 to 21.6 at.% Zr; metastable; an oxygen- 

Fm3m 

stabilized phase [2002Ste] 

Th6Mn23 a = 1172 in the alloy Zr30Fe70 (at.%) annealed at 1000˚C 

for 200 h, together with the βZrFe2 phase 

[2002Ste] 

a = 1169 [V-C2] 

τ, (Zr xTi 1–x) 2Fe cF96 a ≈ 1150 metastable, in the Zr 15Ti 60Fe 25 and Zr 10Ti 65Fe 25 

Fd3m 

Ti 2Ni 

alloys produced by high speed crystallization 

[1998Kim1] 

M (ZrTiFe) cI146 a = 1330.7 1/1 bcc, approximant, metastable 

Im3 Zr11Ti64Fe25 [1995Kim, 1998Kim2] 

I (ZrTiFe) c** a = 485 quasicrystal, metastable, composition is closed 

to M (ZrTiFe) [1995Kim, 1998Kim2] 

. Table 3 

Investigations of the Fe-Ti-Zr Materials Properties 


[1963Pie] Faraday method: dynamic measurements 

(thermomagnetic analyses, TMA) and 

static measurements 

[1987Bla] PMT-3 mechanical tests Microhardness 

[1988Nag] Energy dispersive X-ray analysis (EDX), 

volumetric method (Sievert’s apparatus 

measurements), SEM 

Magnetization, magnetic susceptibility, 

saturation magnetization at 4 to 650 K, 

Curie temperature 

Hydriding rate, pressure-composition 

isotherms 

[1991Ard] Magnetic properties tests Quadrupole splitting, isomer shift 

[1999Sin] Volumetric method (Sievert’s apparatus 

measurements) 



MSIT 1 


Hydriding rate, pressure-composition 

isotherms 

9 

DOI: 10.1007/978-3-540-70890-2_34 

ß Springer 2009

10 34 

Fe–Ti–Zr 



[2000Nis] Hydriding using a conventional pressureproof 

vessel 

[2001Bud] 

[2003Sur] 

Desorption and adsorption isotherms, 

pressure-composition isotherms 

57 Fe Mössbauer spectroscopy Hyperfine interaction, quadrupole 

splitting, isomer shift dependences on 

concentration 

57 Fe Mössbauer spectroscopy Magnetic structure, hyperfine interaction, 

quadrupole splitting, isomer shift 

dependences on concentration 



MSIT 1

. Fig. 1 

Fe-Ti-Zr. The Ti-Zr phase diagram 



MSIT 1 


11 

DOI: 10.1007/978-3-540-70890-2_34 

ß Springer 2009

12 34 

Fe–Ti–Zr 

. Fig. 2 

Fe-Ti-Zr. Lattice parameters of the Laves phases in the quasibinary system ZrFe 2-TiFe 2 



MSIT 1

. Fig. 3 

Fe-Ti-Zr. Quasibinary system ZrFe 2-TiFe 2 



MSIT 1 


13 

DOI: 10.1007/978-3-540-70890-2_34 

ß Springer 2009

14 34 

Fe–Ti–Zr 

. Fig. 4 

Fe-Ti-Zr. Isothermal section at 900˚C 



MSIT 1


15 

. Fig. 5 

Fe-Ti-Zr. Mixing enthalpy of liquid Fe-Ti-Zr alloys at 1879˚C. Values denote the mixing enthalpies 

in kJ·mol –1 



MSIT 1 

DOI: 10.1007/978-3-540-70890-2_34 

ß Springer 2009

16 34 

Fe–Ti–Zr 

. Fig. 6 

Fe-Ti-Zr. Excess heat capacity of liquid Fe-Ti-Zr alloys at 1879˚C. Values denote the excess heat 

capacities in J·mol –1 ·K –1 



MSIT 1


. Fig. 7 

Fe-Ti-Zr. Vickers microhardness values of the λ 1 phase in the ZrFe 2-TiFe 2 quasibinary system 



MSIT 1 

17 

DOI: 10.1007/978-3-540-70890-2_34 

ß Springer 2009

18 34 

Fe–Ti–Zr 

References 

[1963Pie] Piegger, E., Craig, R.S., “Structural and Magnetic Characteristics of TiFe 2-ZrFe 2 and ZrCo 2-ZrFe 2 

Alloys”, J. Chem. Phys., 39(1), 137–145 (1963) (Crys. Structure, Experimental, Magn. Prop., 15) 

[1971Pet] Pet’kov, V.V., Kocherzhinskiy, Yu.A., Markiv, V.Ya., “Investigation of the Polythermal Sections ZrFe2- 

TiFe 2 and ZrCo 2-TiCo 2” (in Ukrainian), Dop. Akad. Nauk Ukr. RSR, Ser. A, (10), 942–944 (1971) (Crys. 

Structure, Phase Diagram, Phase Relations, Experimental, #, 6) 

[1973Sve] Svechnikov, V.N., Kocherzhinsky, Yu.A., Markiv, V.Ya., Pet’kov, V.V., “Laves Phases in Transition Metal 

Systems of the IV-VIII Groups of Periodic System” (in Russian), Akad. Nauk Ukr. SSR, Metallofizika, 

46, 35–45 (1973) (Phase Diagram, Phase Relations, Experimental, Review, #, 74) 

[1980Hil] Hillert, M., “Empirical Methods of Predicting and Representing Thermodynamic Properties of Ternary 

Solution Phases”, Calphad, 4, 1–12 (1980) (Thermodyn., Calculation) as quoted by [1996Wan] 

[1982Sil] da Silva, E.G., Coelho, J.S., Mansur, R.A., “The Effect of Titanium on the Stabilization of the β-Zr (Fe) 

Phase”, Acta Metall., 30, 1829–1833 (1982) (Crys. Structure, Morphology, Phase Relations, Experimental, 

*, 8) 

[1987Bla] Blazina, Z., Trojko, R., “On Friauf-Laves Phases in the Zr 1–xAl xT 2,Zr 1–xSi xT 2 and Zr 1–xTi xT 2 (T = Mn, 

Fe, Co) Systems”, J. Less-Common Met., 133(2), 277–286 (1987) (Crys. Structure, Morphology, Experimental, 

Electronic Structure, Mechan. Prop., 10) 

[1987Mur] Murray, J.L., “Fe-Ti” in “Phase Diagrams of Binary Titanium Alloys”, Springer Verlag, Berlin (1987) 

(Crys. Structure, Phase Diagram, Review, 117) 

[1988Nag] Nagai, H., Kitagaki, K., Shoji, K.-I., “Hydrogen Storage Characteristics of FeTi Containing Zirconium”, 

Trans. JIM, 29(6), 494–501 (1988) (Morphology, Phase Diagram, Phase Relations, Experimental, Phys. 

Prop., 8) 


Alloy Systems (Zr 1–xTi x) 2Fe and (Zr 1–xTi x) 3Fe in the Range 0 ≤ x ≤ 0.2”, Scr. Met. Mater., 25(6), 


abstract 

[1992Rag] Raghavan, V., “The Fe-Ti-Zr (Iron-Titanium-Zirconium) System” in “Phase Diagrams of Ternary Iron 

Alloys”, Indian Institute of Metals, Calcutta, 6B, 1223–1224 (1992) (Crys. Structure, Phase Diagram, 

Phase Relations, Review, #, 4) 

[1994Kum] Kumar, H., Wollants, P., Delaey, L., “Thermodynamic Assessment of the Ti-Zr System and Calculation 

of the Nb-Ti-Zr Phase Diagram”, J. Alloys Compd., 206(1), 121–127 (1994) (Phase Diagram, Thermodyn., 

Assessment, Calculation, 32) 

[1994Qin] Qin, J., Roesner-Kuhn, M, Schaefers, K., Frohberg, M.G., “Consideration of the Excess Heat Capacity 

for the Evaluation of Mixing Enthalpies Measured by Levitation Alloying Calorimetry”, Z. Metallkd., 

85(10), 692–695 (1994) (Thermodyn., Calculation, Experimental, 12) 

[1995Kim] Kim, W.J., Kelton, K.F., “Icosahedral and Related Phase Formation in Rapidly Quenched Ti-Zr-Fe 

Alloys”, Philos. Mag. A, 72(5), 1397–1408 (1995) (Crys. Structure, Morphology, Experimental, 17) 

[1996Wan] Wang, H., Lueck, R., “Mixing Enthalpy of Liquid T-Ti-Zr (T = Fe, Co, Ni) Alloys”, J. Non-Cryst. Solids, 

205–207, 417–420 (1996) (Thermodyn., Calculation, Experimental, 23) 

[1998Kim1] Kim, W.J., Gibbons, P.C., Kelton, K.F., “Icosahedral Quasicrystal Formation in Ti-Zr-Based Alloys and 

a New Classification Technique”, Philos. Mag. A, 78(5), 1111–1124 (1998) (Crys. Structure, Experimental, 

Review, 37) 

[1998Kim2] Kim, W.J., Gibbons, P.C., Kelton, K.F., Yelon, W.B., “Structural Refinement of 1/1 bcc Approximants to 

Quasicrystals: Bergman-Type W (TiZrNi) and Mackay - Type M (TiZrFe)”, Phys. Rev. B, 58(5), 


[1999Sin] Singh, B.K., Singh, A.K., Pandey, C.S., Srivastava, O.N., “Investigation on Synthesis, Characterization 

and Hydrogenation Behaviour of Hydrogen Storage Material: Fe 1–xZr xTi 1.3 (x = 0.2)”, Int. J. Hydrogen 

Energy, 24(11), 1077–1082 (1999) (Crys. Structure, Morphology, Phase Relations, Experimental, Phys. 

Prop., 10) 

[1999Thi] Thiedemann, U., Roesner-Kuhn, M., Drewes, K., Kuppermann, G., Frohberg, M.G., “Mixing Enthalpy 

Measurements of Liquid Ti-Zr, Fe-Ti-Zr and Fe-Ni-Zr Alloys”, Steel Res., 70(1), 3–8 (1999) (Thermodyn., 




MSIT 1


19 

[2000Nis] Nishimiya, N., Wada, T., Matsumoto, A., Tsutsumi, K., “Hydriding Characteristics of Zirconium- 

Substituted FeTi”, J. Alloys Compd., 313, 53–58 (2000) (Phase Relations, Thermodyn., Experimental, 


[2001Bud] Budzyn’ski, M., Sarzyn’ski, J., Surowiec, Z., Wiertel, M., “Moessbauer and X-Ray Diffraction Studies of 

Zr 1–xTi xFe 2 Laves Phase Compounds”, Acta Phys. Pol. A, 100(5), 717–722 (2001) (Crys. Structure, 

Experimental, Magn. Prop., 8) 


Intermetallics, 10, 149–159 (2002) (Crys. Structure, Calculation, Electronic Structure, 27) 



(2002) (Crys. Structure, Morphology, Phase Diagram, Phase Relations, Assessment, Experimental, 

Review, 88) 

[2003Sur] Surowiec, Z., Wiertel, M., Beskrovnyi, A.I., Sarzyn’ski, J., Milczarek, J.J., “Investigations of Microscopic 

Magnetic Properties of the Pseudo-Binary System (Zr 1–xTi x)Fe 2”, J. Phys.: Condens. Matter, 15(37), 


[2007Zho] Zhou, G., Jin, S., Liu, L., Liu, H., Jin, Z., “Determination of Isothermal Section of Fe-Ti-Zr Ternary 

System at 1173 K”, Trans. Nonferrous Met. Soc. China, 17, 963–966 (2007) (Experimental, Morphology, 



(1990) 





MSIT 1 

DOI: 10.1007/978-3-540-70890-2_34 

ß Springer 2009

Ternary Alloy Systems Phase Diagrams, Crystallographic and ...

Create successful ePaper yourself

Delete template?

Save as template?