CaF 2 - RWTH Aachen University

GTT-Technologies 

Inclusion of CaF 2 and P 2O 5 

in the GTT Oxide database 

GTT-Technologies, Herzogenrath 

Forschungszentrum Jülich 

Klaus Hack, Tatjana Jantzen, Elena Yazhenskikh


Contents of presentation 

• Introduction 

• Addition of CaF2 

• Addition of P 2O 5 

• Conclusions 

• Future developments


Al 2O 3-K 2O-Na 2O-SiO 2 

Elephant’s wedding 

Al 2O 3-CaO-CrO x-FeO-Fe 2O 3- 

MgO-SiO 2


CaF 2 

The addition of CaF 2 

(Fluorspar) to the flux 

decreases melting point. 

Fluorspar decreases the 

viscosity of the slags. 

Fluorspar improves the 

fluidity of molten slags. 

Introduction 

P 2O 5 

The dephosphorization is 

important in the iron and 

steel industry. 

The phospates are of 

interest in connection with 

soil-fertilizer relationships.


Addition of CaF 2 

• The Al 2O 3-CaF 2 binary system 

• The CaF 2-CaO binary system 

• The CaF 2-FeO-Fe system 

• The CaF 2-Fe 2O 3-O 2 system 

• The CaF 2-MgO binary system 

• The CaF 2-SiO 2 binary system 

• The Al 2O 3-CaF 2-CaO ternary system 

• Liquidus surface in Al 2O 3-CaF 2-MgO system 

• Miscibility gaps in Al 2O 3-CaF 2-SiO 2 system 

• Liquidus surface in CaF 2-CaO-MgO system 

• The CaF 2-CaO-SiO 2 ternary system

Ternary stoichiometric phases modelled by GTT 


Name Phase System Description 

C3A3F 3CaO 3Al2O3 

CaF2 

C11A7F 11CaO 7Al2O3 

C3S2F 

Cuspidine 


Al2O3-CaO-CaF2 Ca4Al6F2O12 

3CaO 2SiO2 CaF2 CaF2-CaO-SiO2 

Heat of formation 

[Fukuyama, 

Tabata,2003] is 

Al2O3-CaO-CaF2 Ca12Al14F2O32 

used 

Ca4Si2F2O7 

C4S2F 4CaO 2SiO2 CaF2 CaF2-CaO-SiO2 Ca5Si2F2O8 

C9S3F 9CaO 3SiO2 CaF2 CaF2-CaO-SiO2 Ca10Si3F2O15


Binary Al 2O 3-CaF 2 phase diagram 

A.K. Chatterjee, G.I. Zhmoidin, J. Mater. Sci., 7 [1], 

(1972), pp. 93-97. 

T(C) 

2100 

1920 

1740 

1560 

1380 

Slag 

Slag + Al 2O3 

CaF 2 - Al 2 O 3 

CaF 2 + Al2O3 

[Zhmoidin, Chatterje, 1986] 

[Zhmoidin, 1969] 

[Davies, Wright, 1970] 

[Ries, Schwerdtfeger, 1980] 

1200 

0 0.2 0.4 0.6 0.8 1 

mole CaF 2/(CaF2+Al2O3) 

A,I, Zaitsev, N.V. Korolyov, B.M. Mogutnov, 

Journ. Mater. Scien., 26 (1991), pp.1588-1600.


Binary CaF 2-CaO phase diagram 

A.K. Chatterjee, G.I. Zhmoidin, J. Mater. Sci., 7 [1], 

(1972), pp. 93-97. 

R. Ries, K. Schwerdtfeger, Arch. Eisenhuettenwes., 51 

[4], (1980), pp. 123-129. 

T(C) 

1800 

1700 

1600 

1500 

1400 

1300 

Slag + CaF 2 

Slag 

CaF 2 - CaO 

Slag + MeO 

CaF 2 + MeO 

[Kojima, Mason,1969] 

[Chatterjee, Zhmoidin,1972] 

[Zaitsev, Korolyov, Mogutnov,1989] 

1200 

0 20 40 60 80 100 

wt% CaO/(CaF 2+CaO)

CaF 2-FeO phase diagram for equilibrium with Fe 


Slag Atlas, 2nd Ed., Verlag Stahl-Eisen, Düsseldorf, 1995. 

F. Koerber, W. Oelsen, Stahl Eisen, 60[42], (1940), pp.921-929. 

T(C) 

1600 

1500 

1400 

1300 

1200 

Slag + Liquid(Fe) 

Slag + BCC_A2 

CaF 2 - FeO 

Slag + Slag#2 + Liquid(Fe) 

Slag + Slag#2 + BCC_A2 

Slag + CaF2 + BCC_A2 

Slag + CaF2 + FCC_A1 

HALITE + CaF2 + FCC_A1 

mass CaF 2/(CaF2+FeO) 

Slag + Liquid(Fe) 

Slag + BCC_A2 

1100 

0 0.2 0.4 0.6 0.8 1


Predicted CaF 2-Fe 2O 3 phase diagram in air 

No experimental data are available for this system. 

T(C) 

1800 

1700 

1600 

1500 

1400 

1300 

1200 

1100 

1000 

900 


Slag 

Fe 2 O 3 - CaF 2 - O 2 

p(O 2 ) = 0.21 bar 

CaF 2 + Fe2O3 

Fe 2O 3/(Fe 2O 3+CaF 2) (g/g) 

Slag + Fe 2O3 

Slag + SPINEL 

800 

0 0.2 0.4 0.6 0.8 1


Binary CaF 2-MgO phase diagram 

P.P. Budnikov, S.G. Tresvyatskii, Ukr. Khim. Zh. 

(Russ. Ed.), 19 [5], (1953), pp.552-555.. 


T(C) 

1600 

1540 

1480 

1420 

1360 

Slag 


CaF 2 - MgO 

HALITE + CaF 2 

Slag + HALITE 

mass MgO/(CaF 2+MgO) 

[E. Schlegel, 1967] 

1300 

0 0.2 0.4 0.6 0.8 1


Binary CaF 2-SiO 2 phase diagram 

L. Hillert, Acta Chem. Scand., 18 [10], (1964), pp. 2411-2411. 


T(C) 

1900 

1760 

1620 

1480 

1340 

Slag + Cristobalite 

Slag 

Slag + Tridymite 

SiO 2 - CaF 2 

Tridymite + CaF 2 

Slag + Slag#2 

mass CaF 2/(SiO2+CaF2) 

[Hillert 1970] 

CaF2-SiO2-TiO2 

CaF2-Na2O-SiO2 

[Hillert 1964] 

CaF2-SiO2, Slag Atlas 

Al2O3-CaF2-SiO2 


1200 

0 0.2 0.4 0.6 0.8 1

Isothermal section at 1100 o C in Al 2O 3-CaF 2-CaO 


C. Brisi, P. Rolando, Ann. Chim. (Rome), 57 [11], (1967), pp.1304-1315. 


C11A7F 

CaF 2 - Al 2O 3 - CaO 


Ca 4Al6F2O12 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

Ca12Al14F2O32 + CaF2 + HALITE 

Ca 12Al14F2O32 

1100 o 

C 

C3A3F 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

0.9 

0.8 Ca3Al2O6 0.7Ca12Al14O33 

0.6 CaAl2O4 0.5 

0.4 CaAl4O70.3 0.2 CaAl12O19 0.1 

CaO Al2O3 mole fraction



R. Ries, K. Schwerdtfeger, Arch. Eisenhüttenwes., 

51, (1980), pp.123-129. 

Slag + MeO 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

CaF 2 - Al 2 O 3 - CaO 

1600 o 

C, 1 atm 


Slag + Slag#2 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

0.9 

0.8 

0.7 

0.6 

0.5 

0.4 

0.3 

0.2 

0.1 

CaO Al 2 O 3 

mole fraction 

Slag + CaAl 4 O 7 

Slag + Al 2O 3 

CaAl 12 O 19 

[Zhmoidin, Chatterjee, 1986] 

[Ries, Schwerdtfeger, 1980]: 

phase boundary 

two liquids 

one liquid



Slag + MeO 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

CaF 2 - Al 2 O 3 - CaO 

1800 o 

C, 1 atm 


Slag + Slag#2 

Slag 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

0.9 

0.8 

0.7 

0.6 

0.5 

0.4 

0.3 

0.2 

0.1 

CaO Al 2 O 3 

mole fraction 


Slag + Al 2 O 3 

[Zhmoidin, Chatterjee, 1986]


Isopleth section C11A7F– C3A3F 

A.K. Chatterjee, G.I. Zhmoidin, Izv. Akad. Nauk SSSR, 

Neorg. Mater., 8 [5], (1972), pp.886-892. 

T(C) 

1600 

1580 

1560 

1540 

1520 

1500 

1480 

1460 

1440 

1420 

Ca 12Al 14O 32F 2 - Ca 2Al 3O 6F 

Slag + Ca 12 Al 14 F 2 O 32 

1 atm 

Ca 12 Al 14 F 2 O 32 + Ca 4 Al 6 F 2 O 12 

wt % Ca 2Al 3O 6F/(Ca 12Al 14O 32F 2+Ca 2Al 3O 6F) 

Slag 

Slag + Ca 4 Al 6 F 2 O 12 

1400 

0 20 40 60 80 100


Isopleth section CaAl 2O 4 –CaF 2 


Neorg. Mater., 8 [5], (1972), pp.886-892. 

A,I, Zaitsev, N.V. Korolyov, B.M. Mogutnov, 

Journ. Mater. Scien., 26 (1991), pp.1588-1600. 

T(C) 

1700 

1600 

1500 

1400 

1300 

1200 


Ca 4 Al 6 F 2 O 12 + CaAl 2 O 4 

Slag 

Ca 4 Al 6 F 2 O 12 

CaAl 2O 4 - CaF 2 

Slag + Slag#2 

Slag + Slag#2 + Ca Al F O 4 6 2 12 

Slag#2 + Ca Al F O 4 6 2 12 

CaF 2 + Ca 4 Al 6 F 2 O 12 

[Gut et.al.,1970] 

Liquid 

Liquid + Solid 

Solid 

1100 

0 20 40 60 80 100 

wt % CaF2/(CaAl2O4+CaF2)


Isopleth section C3A3F – CaAl 4O 7 


Neorg. Mater., 8 [5], (1972), pp.886-892. 

T(C) 

1800 

1750 

1700 

1650 

1600 

1550 

Slag + Ca 4 Al 6 F 2 O 12 

1500 

Slag 

Ca 4 Al 6 O 12 F 2 - CaAl 4 O 7 

1 atm 

Ca 4 Al 6 F 2 O 12 + CaAl 4 O 7 


wt % CaAl 4O 7/(Ca 4Al 6O 12F 2+CaAl 4O 7) 


Slag + CaAl 4 O 7 + CaAl 12 O 19 

1450 

0 20 40 60 80 100


Liquidus surface in Al 2O 3-CaF 2-CaO 


10 20 30 40 50 60 70 80 90 

CaF 2 - Al 2O 3 - CaO 

Projection (Slag), 1 atm 


1207 

1472 


1392 

Ca 12Al 14F 2O 32 

1392 

1383 

Slag#2 

10 20 30 40 50 60 70 80 90 

90 

80 

70 

60 

50 

40 

30 

20 

10 

CaO Ca Al O 3 2 6 CaAl O 2 4 

Al2O3 1419 

1464 

percent by weight 

1464 

1450 

MeO Ca 4 Al 6 F 2 O 12 

1506 

1497 

CaAl 4 O 7 

CaAl 12 O 19 

Al 2 O 3


Liquidus surface in Al 2O 3-CaF 2-MgO 



0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 


2 1343 o 

C 

1379 

1 

o 

C 

0.9 

0.8 

0.7 

MgO - Al 2 O 3 - CaF 2 

Projection (Slag) 

SPINEL 

0.6 

MgO 

HALITE 

0.5 

mass fraction 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

0.4 

0.3 

0.2 

Al 2O3 

0.1 

Al 2 O 3


Miscibility gaps in Al 2O 3-CaF 2-SiO 2 



0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

0.9 

0.8 

0.7 

Al 2 O 3 - SiO 2 - CaF 2 

0.6 

Al 2 O 3 

Slag + Slag#2 

0.5 

mass fraction 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

1380 o 

C 

0.4 

1460 o 

C 

0.3 

0.2 

0.1 

SiO 2

Isothermal section at 1425 o C in Al 2O 3-CaF 2-SiO 2 



0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

0.9 

0.8 

Al2O3 - SiO2 - CaF2 T = 1400 o 

C, 1425 o 

C and 1450 o 

C 

0.7 

0.6 

Al 2 O 3 

Slag + Slag#2 

0.5 

mass fraction 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

0.4 

0.3 

0.2 

[Ueda, Maeda, 1999] 

T = 1400 o 

C 

T = 1425 o 

C 

T = 1450 o 

C 

0.1 

SiO 2 


0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

Slag 

0.9 

Slag + Al2O3 

0.8 

0.7 

Al2O3 - SiO2 - CaF2 1425 o 

C 

0.6 

Al 2 O 3 

Slag + Mullite 

Slag + Slag#2 

0.5 

mass fraction 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

0.4 

0.3 

0.2 

[Ueda, Maeda, 1999] 

0.1 

Slag + Tridymite 

SiO 2

Predicted isothermal sections in Al 2O 3-CaF 2-SiO 2 



0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

0.9 

Slag + Al2O3 

Slag 

0.8 

0.7 


C 

0.6 

Al 2 O 3 


Slag + Slag#2 

0.5 

mass fraction 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

0.4 

0.3 

0.2 

0.1 



SiO 2 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

0.9 

0.8 

Slag 

0.7 


C 

Slag + Al2O3 

0.6 

Al 2 O 3 


Slag + Slag#2 

0.5 

mass fraction 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

0.4 

0.3 

0.2 

0.1 


SiO 2 


0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

0.9 

0.8 

0.7 


C 

Slag + Al2O3 

0.6 

Al 2 O 3 

0.5 

mass fraction 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 


Slag 

Slag + Slag#2 

0.4 

0.3 

0.2 

0.1 

SiO 2


Predicted liquidus surface in Al 2O 3-CaF 2-SiO 2 

Four-Phase Intersection Points with Slag 

1: Al2O3_alpha(s) / CaF2_s1(s) / MULLITE 

2: MULLITE / MULLITE / SiO2_cristobalite_be(s5) 

3: MULLITE / SiO2_cristobalite_be(s5) / Slag#2 

4: CaF2_s1(s) / MULLITE / SiO2_cristobalite_be(s5) 

1: 

2: 

3: 

4: 

A = Al2O3, B = CaF2, C = SiO2 

W(A) W(B) W(C) o C 

0.04896 0.89898 0.05207 1349.38 

0.04509 0.15403 0.80088 1334.48 

0.05441 0.77990 0.16569 1334.46 

0.04204 0.82168 0.13629 1315.41 


10 20 30 40 50 60 70 80 90 

90 

80 

Cristobalite 

70 

Al 2O 3 - CaF 2 - SiO 2 


60 

Al 2 O 3 

Al 2 O 3 (s) 

MULLITE 

50 

percent by weight 

10 20 30 40 50 60 70 80 90 

1 3 

4 

2 

CaF 

Two liquids 

2 

40 

T(min) = 1315.41 o 

C, T(max) = 2053.83 o 

C 

30 

20 

Cristobalite 

10 

SiO 2


Liquidus surface in CaF 2-CaO-MgO 


E. Schlegel, Z. Chem., 5 [8], (1965), pp.316. 

HALITE 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

CaF 2 - CaO - MgO 




1335 o 

C 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

0.9 

0.8 

0.7 

0.6 

0.5 

0.4 

0.3 

0.2 

0.1 

CaO MgO 

mass fraction 

HALITE

Isothermal section at 1000 o C in CaF 2-CaO-SiO 2 


System CaF2-CaO-SiO2; compatibility triangles. 

C. Brisi, J. Am. Ceram. Soc., 40 [5] 174-178 (1957). 

Temperature missing 


0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

0.9 

0.8 

0.7 

CaF2 - CaO - SiO2 1060 o 

C 

CaF 2 + MeO + Ca 2SiO 4(s3) 

0.6 

CaO 

Ca 5 Si 2 F 2 O 8 

0.5 

mole fraction 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

Ca 10 Si 3 F 2 O 15 

Ca Si F O 4 2 2 7 

(Cuspidine) 

0.4 

Ca 2 SiO 4 (s3) 

0.3 

Ca 3 Si 2 O 7 

Cristobalite + CaF 2 + CaSiO 3 (s) 

CaSiO 3 (s) 

0.2 

0.1 

SiO 2 

Cuspidine - from the Greek cuspis, for a spear, the 

characteristic shape of the twinned crystals.

Isopleth section Cuspidine – CaF 2 


(B) pseudobinary phase diagram for cuspidine-CaF2 

system; Cuspidine = Ca4Si2O7F2 

H. Fukuyama, T. Watanabe, M. Susa, and K. Nagata, 

"Pseudo-binary Phase Diagram of the Cuspidine - 

CaF2 System - Relating to Mold Flux for Continuous 

Casting of Steel -"; pp. 61-75 in EPD Congr. 1999, 

Proc. Sess. Symp., TMS Annual Meeting, San Diego, 

California, February 28-March 4, 1999. Edited by B. 

Mishra, Minerals, Metals & Materials Society, 

Warrendale, Pennsylvania, 1999. 

T(C) 

1600 

1480 

1360 

1240 

1120 

Slag + Ca 4Si2F2O7 

Ca 4Si 2F 2O 7 - CaF 2 

Slag 

CaF 2 + Ca4Si2F2O7 

[Watanabe, Fukuyama]: 

Liquidus temperature 

Eutectic temperature 


1000 

0 0.2 0.4 0.6 0.8 1 

mass CaF2/(Ca4Si2F2O7+CaF2)


Isopleth section CaSiO 3 –CaF 2 

T. Baak and A. Oelander, Acta Chem. Scand., 9 [8] 1350-1354 (1955). 

Dashed lines after Karandeef. 

B. Karandeeff, Z. Anorg. Chem., 68 [3] 188-197 (1910) 

T(C) 

1600 

1480 

1360 

1240 

1120 

Slag + CaSiO 3(s2) 

CaSiO 3 - CaF 2 

CaF 2 + CaSiO3(s) 

mass CaF 2/(CaSiO 3+CaF 2) 

Slag 


1000 

0 0.2 0.4 0.6 0.8 1


W. H. Gutt and G. J. Osborne, Trans. Br. 

Ceram. Soc., 65 [9] 521-534 (1966). 

Isopleth section Ca 2SiO 4 –CaF 2 

T(C) 

2300 

1840 

1380 

920 

460 

Slag + Ca 2SiO4(s2) 

Ca 2SiO4(s3) + Ca5Si2F2O8 

Ca 5Si2F2O8 + Ca2SiO4(s) 

Slag + Ca 2SiO4(s3) 

Ca 5Si2F2O8 

Ca 2SiO 4 - CaF 2 

Slag 

CaF 2 + Ca2SiO4(s3) 

CaF 2 + Ca5Si2F2O8 

mass CaF 2/(Ca 2SiO 4+CaF 2) 


0 

0 0.2 0.4 0.6 0.8 1


Isopleth section Ca 3SiO 5 –CaF 2 

W. H. Gutt and G. J. Osborne, Trans. Br. Ceram. Soc., 69 [3] 125-129 (1970). 

T(C) 

2300 

Slag + HALITE 

1840 

1380 

920 

460 

0 

Ca 2SiO4 + Ca5Si2F2O8 + HALITE 

Slag + Ca 3SiO5 

Slag + HALITE + Ca3SiO5 Slag + Ca2SiO4(s3) + HALITE 

Ca10Si3F2O15 Ca 5Si2F2O8 

Ca 3SiO 5 - CaF 2 

Slag 

CaF 2 + Ca2SiO4(s3) + HALITE 

CaF 2 + Ca5Si2F2O8 + HALITE 

mass CaF 2/(Ca 3SiO 5+CaF 2) 

[Gutt and Osborne, 1970] 


0 0.2 0.4 0.6 0.8 1


Liquidus surface in CaF 2-CaO-SiO 2 

W. H. Gutt and G. J. Osborne, Trans. Br. Ceram. Soc., 69 [3] 125-129 (1970). 

Ca 3 Si 2 O 7 (s) 

Ca 2 SiO 4 (s2) 

Ca 3SiO5(s) 

CaO 

10 20 30 40 50 60 70 80 90 

CaF 2 - CaO - SiO 2 

Projection (Slag), 1 atm 

CaSiO 3 (s2) 

SiO 2 

Cristobalite 

Ca 4 Si 2 F 2 O 7 

Ca 2 SiO 4 (s3) 

10 20 30 40 50 60 70 80 90 

Slag#2 

Ca 10 Si 3 F 2 O 15 

90 

80 

70 

60 

50 

40 

30 

20 

10 

CaO CaF2 percent by weight 

CaSiO 3 (s) 

CaF 2 (s) 

1 

4300 

4100 

3600 

3100 

2600 

2100 

1600 

13 1100 

T o C


• The Fe-P binary system 

• The Al 2O 3-P 2O 5 system 

• The CaO-P 2O 5 system 

Addition of P 2O 5 

• The Cr 2O 3-P 2O 5 phase diagram in air 

• The Fe 2O 3-P 2O 5 phase diagram in air 

• The FeO–P 2O 5 phase diagram in equilibrium with Fe 

• The MgO-P 2O 5 system 

• The ternary FeO-Fe 2O 3-P 2O 5 system


Addition of P 2O 5 

The associate species containing P were added in order to 

describe the liquid phase in the Al 2O 3-CaO-Cr 2O 3-FeO- 

Fe 2O 3-MgO system containing P 2O 5. 

System Associate species Description 

MeOx : P2O5 Al2O3‐P2O5 AlPO4(SGPS)‐ Berlinite 

Cr 2O 3 –P 2O 5 

Fe 2O 3 –P 2O 5 

CaO ‐ P 2O 5 

FeO ‐ P 2O 5 

MgO ‐ P 2O 5 

CrPO 4 

FePO 4(SGPS) 

Ca 3P 2O 8, Ca 2P 2O 7, CaP 2O 8 [Serena 2011] 

Fe 3P 2O 8, Fe 2P 2O 7, FeP 2O 6, 

Mg 3P 2O 8 (SGPS), Mg 2P 2O 7, MgP 2O 8 

1:1 

3:1, 2:1, 1:1


Modelling of binary P-containing phases 

System Phase Description Used data 

Fe-P fcc-A1 

bcc-A2 

FeP 

Fe2P 

Fe3P 

Al 2O 3-P 2O 5 

CaO-P 2O 5 

3Al 2O 3 . P2O 5 

AlPO 4(s3) Berlinite 

AlPO 4(s2) 

AlPO 4(s1) 

Al 2O 3 . 3P2O 5 

CaO . 2P 2O 5 

2CaO . 3P 2O 5 

CaO . P 2O 5 

2CaO . P 2O 5(s1,s2,s3) 

3CaO . P 2O 5(s1,s2,s3) 

4CaO . P 2O 5 

(Fe, O, P) 1 (Va) 1 

(Fe, O, P) 1 (Va) 3 

stoichiometric 














[99Lee] 

[99Lee] 

[99Lee] 

[99Lee] 

[99Lee] 

- 

SGPS 

SGPS 

SGPS 

- 

[Serena 2011] 

[Serena 2011] 

[Serena 2011] 

[Serena 2011] revised (T tr) 

[Serena 2011] revised (T tr) 

[Serena 2011]

Modelling of binary P-containing phases 



Cr 2O 3-P 2O 5 

FeO-P 2O 5 

Fe 2O 3-P 2O 5 

MgO-P 2O 5 

CrPO4 5Cr . 

2O3 P2O5 3Cr . 

2O3 P2O5 FeO . P2O5 2FeO . P2O5 3FeO . P2O5 Fe . 

2O3 3P2O5 2Fe . 

2O3 3P2O5 Fe . 

2O3 P2O5 3Fe . 

2O3 P2O5 MgO . P 2O 5 

2MgO . P 2O 5 

3MgO . P 2O 5 














- 

- 

- 

- 

- 

SGPS changed 

- 

- 

S f, H fus [Oetting, 1963] 

SGPS changed

Modelling of ternary P-containing phases 



FeO-Fe 2O 3-P 2O 5 

Fe 7P 6O 24 

Fe 18P 2O 24 

Fe 10P 6O 26 

Fe 4P 2O 10 

3FeO . 2Fe 2O 3 . 3P2O 5 (stoichiometric) 

16FeO . Fe 2O 3 . P2O 5 (stoichiometric) 

8FeO . Fe 2O 3 . 3P2O 5 (stoichiometric) 

2FeO . Fe 2O 3 . P2O 5 (stoichiometric) 

- 

- 

- 

-


T(C) 

1500 

1300 

FCC_A1 

1100 

900 BCC_A2 

700 

500 

300 

100 

Binary Fe-P phase diagram [99Lee] 

Fe 3 P(s2) 

Fe 2 P(s) 

Fe - P 

1 atm 

FeP(s) 

P/(Fe+P) (mol/mol) 

Slag 

FeP(s) + P(s2) 

Slag + P(s2) 

0 0.2 0.4 0.6 0.8 1


T(C) 

Binary Al 2O 3-P 2O 5 phase diagram 

Berlinite (AlPO 4) - It was first described in 1868 for 

an occurrence in the Västana iron mine, Scania, 

Sweden and named for Nils Johan Berlin (1812–1891) 

of Lund University. 

2600 

2100 

1600 

1100 

600 

100 

Al2O3(s) + P2Al6O14(s) 

Slag 

P2Al6O14(s) 

Al 2 O 3 - P 2 O 5 

AlO4P(s2) 

AlO4P(s) 

P 2O 5/(Al 2O 3+P 2O 5) (g/g) 

[Stone, Egan, 1956] 

[Tananaev, Maksimchuk, 1978] 

AlO4P(s3) P6Al2O18(s) 

P6Al2O18(s) + P2O5(s2) 

0 0.2 0.4 0.6 0.8 1 

P.E. Stone, E.P. Egan, J.R. Lehr, J. Am, 

Ceram. Soc., 39 [3], (1956), pp.89-98. 

I.V. Tananaev, E.V. Maksimchuk,Y. G. 

Bushuev, S.A. Shestov, Izv. Akad. Nauk SSSR, 

Neorg. Mater., 14 [4], (1978), pp.719-722.


T(C) 

2600 

2100 

1600 

1100 

600 

100 

CaP4O11(s) 

O5P2(s2) + CaP4O11(s) 

CaO-P 2O 5 phase diagram 

Ca2P6O17(s) 

Slag 

Ca(PO3)2(s) 

CaO - P 2 O 5 

Ca2O7P2(s3) 

Ca2O7P2(s2) 

Ca2P2O7(s) 

1 atm 

Ca3(PO4)2(s) 

[Hill, 1944] 

Ca3(PO4)2(s3) 

Ca3(PO4)2(s2) 

CaO/(CaO+P 2O 5) (g/g) 

[Trömmel, 1961, DTA] 

[Trömmel, 1961, hot stage microscope] 

Ca4(PO4)2O(s) 

MeO + Slag 

MeO + Ca4(PO4)2O(s) 

0 0.2 0.4 0.6 0.8 1


T(C) 

2500 

2300 

CORUNDUM + Slag 

2100 

1900 

1700 

1500 

1300 

1100 

900 

700 

500 

300 

Cr10P2O20(s) 

Cr 2O 3-P 2O 5 phase diagram in air 

Cr6P2O14(s) 

Cr 2 O 3 - P 2 O 5 - O 2 

p(O 2 ) = 0.21 atm, 1 atm 

Slag 

CrPO4(s) 

P 2O 5/(Cr 2O 3+P 2O 5) (mol/mol) 

[J.V. Tananaev, E.V. Maksumchuk, 1978] 

CrPO4(s) + P2O5(s2) 

Slag + P2O5(s2) 

0 0.2 0.4 0.6 0.8 1 

I.V. Tananaev, E.V. Maksimchuk,Y. G. 

Bushuev, S.A. Shestov, Izv. Akad. Nauk 

SSSR, Neorg. Mater., 14 [4], (1978), 

pp.719-722.

FeO-P 2O 5 phase diagram in equilibrium with Fe 


T(C) 

1500 

1300 

MeO + Slag + Fe(s2) 

1100 

900 

700 

500 

300 

100 

Fe 18 P 2 O 24 

SPINEL + Fe(s) + Fe 3 P 2 O 8 

Fe 3 P 2 O 8 

Fe 2 P 2 O 7 

FeO - P 2O 5 - Fe 

Fe/(FeO+P 2 O 5 ) (mol/mol) = 0.0001, 1 atm 

Slag + Fe(s) 

Slag + Slag#2 

FeP 2 O 6 

P 2O 5/(FeO+P 2O 5) (mol/mol) 

Slag + Fe(s2) 

Slag + Fe(s) + FeP 2 O 6 

[L.Chang, 2010] 

Slag + Fe(s) 

O 5 P 2 (s2) + Fe(s) + FeP 2 O 6 

0 0.2 0.4 0.6 0.8 1


T(C) 

1700 

1500 

1300 

1100 

900 

700 

500 

300 

100 

P 2 O 5 (s2) + Fe 2 P 6 O 18 

Fe 2O 3–P 2O 5 phase diagram in air 

Fe 2 P 6 O 18 

Slag 

Fe 2O 3 - P 2O 5 - O 2 

p(O 2 ) = 0.21 bar 

Fe 4 P 6 O 21 

FePO 4 

Fe 2O 3/(Fe 2O 3+P 2O 5) (mol/mol) 

[L.Zhang,M.Schlesinger,R.Brow,2011] 

Slag + Fe 2 O 3 

Fe 6 P 2 O 14 

Slag + SPINEL 

0 0.2 0.4 0.6 0.8 1 

L. Zhang, M. E. Schlesinger, R. K. 

Brow, (J. Am. Ceram. Society, 

Vol.94, Issue 5, (2011), pp.1605- 

1610. 

Slag Atlas, 2nd Ed., Verlag Stahl- 

Eisen, Düsseldorf, 1995., p.68.


T(C) 

3000 

2500 

2000 

1500 

1000 

500 

0 

MeO + Slag 

MeO + Mg3O8P2(s) 

MgO-P 2O 5 phase diagram 

Slag 

MgO - P 2 O 5 

Mg3O8P2(s) 

P 2O 5/(MgO+P 2O 5) (g/g) 

[J. Berak, 1958] 

P2Mg2O7(s) P2MgO6(s) 

Slag + P2MgO6(s) 

P2MgO6(s) + P2O5(s2) 

0 0.2 0.4 0.6 0.8 1 

J. Berak, Rocz. Chem., 32 [1], 

(1958), pp.17-22.

Isothermal section in FeO-Fe 2O 3-P 2O 5 at 900 o C 


Fe 2 P 2 O 7 

FeP 2 O 6 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

P 2 O 5 

Slag 

Fe3P2O8 Fe4P2O Fe 10 

10P6O26 Fe 18 P 2 O 24 

Fe 2 O 3 - P 2 O 5 - FeO 

900 o 

C 

Fe 7 P 6 O 24 

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 

0.9 

0.8 

0.7 

0.6 

0.5 

0.4 

0.3 

0.2 

0.1 

FeO Fe 2 O 3 

mole fraction 

Fe 2 P 6 O 18 

Fe 4 P 6 O 21 

FeO 4 P 

Fe 6 P 2 O 14 

SPINEL + Fe 2 O 3 + Fe 6 P 2 O 14 

Slag Atlas, 2nd Ed., Verlag Stahl- 

Eisen, Düsseldorf, 1995., p.68. 

A. Modaressi, J.C. Kaell, 

B.Malaman, R. Gerardi, C. Gleitze, 

Mat. Res. Bull. 18 (1983), No. 1, 

pp.101-109.


Conclusions 

• All systems were assessed using experimental phase diagram information. 

Other experimental information, eg. enthalpies and activities, is scarce. 

• The liquid phase in all subsystems was evaluated using associate species 

model (two cations per species). 

• CaF 2 has so far been integrated into the reduced core system CaO-MgO- 

Al 2O 3-FeO-Fe 2O 3-SiO 2. All binary and 5 ternary systems were described. 

• The stoichiometric phases 3CaO . 3Al 2O 3 . CaF2, 11CaO . 7Al 2O 3 . CaF2, 

4CaO . 2SiO 2 . CaF2, 3CaO . 2SiO 2 . CaF2(Cuspidine), and 9CaO . 3SiO 2 . CaF2 were 

incorporated. 

• The Al 2O 3-CaF 2-CaO system is critically evaluated according to the 

experimentally determined miscibility gap in the liquid phase. 

• In the thermodynamic assessments of the binary systems Al 2O 3-P 2O 5, CaO- 

P 2O 5, Cr 2O 3-P 2O 5, FeO-P 2O 5, Fe 2O 3-P 2O 5, MgO-P 2O 5 as well as the ternary 

FeO-Fe 2O 3-P 2O 5 system 28 stoichiometric solid phases containing P were 

incorporated.


Fe 2O 3 

FeO 

Future developments 

Cr 2O 3 

SiO 2 

Al 2O 3 

P 2O 5 

K 2O 

CaO 

Na 2O 

MgO 

+ ternaries


Fe 2O 3 

FeO 

Future developments 

Cr 2O 3 

SiO 2 

Al 2O 3 


K 2O 

CaO 

Na 2O 

MgO 

+ ternaries?


Happy Birthday, Gunnar! 

Best wishes!

CaF 2 - RWTH Aachen University

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