Production of Pb-Li eutectic - The National Fusion Laboratory - Ciemat

Production of Pb-Li eutectic:
cover gases or molten salts
during melting ?
Mª. I. Barrena, J. Mª. Gómez de Salazar, A. Soria,
L. Matesanz
Dpto. Ciencia Materiales e Ing. Metalúrgica. F. CC. Químicas. Universidad
Complutense de Madrid. UCM, Spain
M. Fernández and J. Quiñones
CIEMAT. Avda. Complutense, 22. 28040-Madrid, Spain

Outline
•Rationale of the activity
•Review of current production
techniques
•Design proposals
•Conclusions and future

Rationale -1
• Since early 70´s, Pb-Li eutectic (LLE, Pb15.7Li) represents today the most
consolidate liquid breeder material.
• 6 Li enriched LLE should be manufactured for diverse ITER TBM (EU-
HCLL, US-DCLL, IN-LLCB) according to nuclear material standards.
• Several tones of Pb15.7(2) 6 Li should prospectively to be procure by ITER
parties
• LLE characteristics should be established according to nuclear material QA
requirements
– ISO3131/- 1, /-5, Light Metals and light alloying metal: methods for processing and
treatment
• Li chemical activity determine LLE activity: title has large impact on NFT.
• 3 H solubility in LLE would largely depends on Li-disproportioning by bad
mixing or local aggregation.
– Other properties less modified
• 2 at% Li deviations are unacceptable from QA of LLE as Nuclear Material

Uncertainty in the eutectic composition ( T-soly)
- overestimation depending on the
experimental protocole for production
and for its determination
- W-T data for a total of 52 points {0 < x Li
(at%)

Rationale -2
Key QA aspects:
1. Material certified application database according with the
material design functionalities [see., E. Mas de les Valls et al.,
JNM ]
2. Certified characterization techniques supporting database
3. QA demands to (LLE) characteristics: constitutive and
compositional
- QA constitutive specifications: & Li aggregation
- Compositional specifications apply for Li title
certification & impurity levels
Production and material testing routes should be fixed
according to QA standards
In the EU, TBM Consortium of Associates (CIEMAT) is
generating a procurement plan for 6 LLE according to
nuclear standards

Roadmap for Pb - Li eutectic QA procurement
• Revision of set of ISO norms
– ISO3131/- 1, /-5, Light Metals and light alloying metal: methods for
processing and treatment, in force for Nuclear Materials and IAEA
Regulations.
• Fixing Material specification in terms of:
– maximum allowable impurity contents
– Li contents global deviations (ex. < ± 0.2 Li at%)
– Homogeneity criteria (ex. maximum size and distribution of Li and other
Li-Pb phases aggregates
• Establishment of a production route (with specification of endorsing
ISOs) according to previous material QA criteria.
• Establishment of set of certification tests for Material QA (fine
calorimetry at eutectic, x-ray phase study, Atomic Absorptions
Technique, …)
Lack of database reproducibility for key FT properties can
not even more potentially be justified in terms of material
uncertainties

Programme goals
• In parallel to EU ITER/DA F4E activities
(GRT-030) Spanish TECNO_FUS
2009/2012 Programme (CIEMAT, UCM) is
facing production of 6 LLE according to
ITER QA standards
6 LLE FUNCTIONAL (REPRODUCIBLE)
DATABASE
CERTIFIED CHARACTERISATION
6 LLE PRODUCTION ROUTES

Certified characterization
Present EU Pb –Li alloy specs.
INGOTS A 15.8-16.1±0.2%at Li
Institute of Physics of the
University of Latvia (IPUL)
INGOTS B 18.8±4.1–19.4±3.5%at Li
"Jost-Hinrich Stachov Metahandel",
Germany
MICROSTRUCTURE NEARLY EUTECTIC
MICROSTRUCTURE HYPEREUTECTIC

Pb-Li binary diagram
Y Ref. at.% Li Alloy origin T-control Analysis Uncertainties
88 [5] 16.98 CEA, Li(99.5) and
Pb(99.994)
-- -- --
Figure 1: Phase diagram of Pb-Li system
[Tegze and Hafner, 1989]
91 [6] 16.55 Alloyed at home Poor detail N.S.
91 [3] 16.98 laboratory, Li(99.4) from
Metallgesellschaft with
0.5 Na, 0.01 K, 0.03 Ca,

Experimental Procedure
• Material
– Ingot A
– Ingot B

Previos work – Temperature distribution
• Ingot A
– Homogeneous distribution
• Wall solidification
• Ingot B
– T f >> del ingot A
• High temperature areas
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Ingot B

conc. Li / % at
conc. Li / % at
Previous work – Chemical analysis
Ingot A
Ingot B
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50
Lingote A
ThermoX ELAN
Lingote B
ThermoX ELAN
6
Li
6
Li
40
7
Li
[Li] A
= 18.31 ± 0.50 % at
40
7
Li
[Li] A
= 24.04 ± 1.38 % at
Composición nominal fabricante
Composición eutéctico Pb - Li
Composición nominal fabricante
Composición eutéctico Pb - Li
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0 2 4 6 8 10
muestra
0 2 4 6 8 10
muestra

Y
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Y
Previos work –Li elemental analysis
• %at Li
(distribution)
– A < B
– >> first solidification
areas
– >> eutectic
– >> nominal
composition
– Dependence with
position
– Similar behaviour
than T
2.0
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Temperatura / 0 C
Temperatura / 0 C
Previous Work
320 ASM (up dated 1993)
Hubberstey et al.;
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Este trabajo
Lingote A
Czochralski & Rassow;
; Lingote B
Grube & Klaiber
Pogodin & Schtilineshkii
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ASM (up dated 1993)
Hubberstey et al.; Grube & Klaiber
Czochralski & Rassow; Pogodin & Schtilineshkii
Este trabajo
Lingote A: Tf c
= ; Tf e
= ; Lingote B: Tf c
= ; Tf e
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Li / % at
0 5 10 15 20 25 30
Measurement T eut(M) ≈237 °C y T eut(S) ≈231 ° C
– Ingot A shows the highest homogeneity
220

Basic scheme of our melting system
A: Induction Furnace (8 kW)
B: Reactor (Cr-Ni Alloy)
C: Gases battery

Equipment designed
Vacuum
Thermocouple
Gas Innlet
Windows
SiC crucible & Pb-Li ingots

Experimental description
• Material
– Pb(s) ultrapure
– Li(s) ultrapure
• Experimental condition
– Atmosphere
• N 2 , Ar, molten salt,...
– Temperature
• 350 – 800 °C
– Time?
– Crucible
• C, CSi, SiO 2

Crucible material selection - Reactivity of the LLE

Experimental setup
Group Ingot Temp (°C) time (min) Gas Crucible
I
PbLi 0 450
PbLi 1 550 15 N 2 (T)
C
PbLi 2 650 SiC
PbLi 4 600 15
SiC
II
Ar
PbLi 3 650 30 SiO 2
III PbLi 5 700 - 800 5-15 Ar (BIP) SiC
IV
PbLi 10 350 8
PbLi 8 400 15
PbLi 7 450 15
PbLi 6 700 5
V PbLi 9 400 3
VI PbLi 11 350 8
Ar (BIP)
+ eutectic LiCl/KCl
Air + eutectic
LiCl/KCl
Ar (BIP) + eutectic
LiCl/KCl
C
SiC
SiC
SiC

Results - Chemical characterization by ICP-MS
Group Ingot %at Li
PbLi 0 16.6
I
PbLi 1 17.5
PbLi 2 16.4
II
PbLi 4 17
PbLi 3 15.8
III PbLi 5 17.3
PbLi 10 15.5
IV
PbLi 8 16.6
PbLi 7 13.5
PbLi 6 13.7
V PbLi 9 15.2
VI PbLi 11 31.55

Q (mW/mg)
Results - Microstructure & DSC characterization
0,5
0,4
0,3
0,2
Eutectic
Eutectic Pb-Li ingots
0,1
0,0
-0,1
-0,2
-0,3
-0,4
-0,5
-0,6
-0,7
-0,8
-0,9
Eutectic
0 100 200 300 400 500
T (ºC)

Q (mW/mg)
Results - Microstructure & DSC characterization
0,4
0,3
0,2
0,1
Eutectic
Solidification
Hipoeutectic Pb-Li ingots
0,0
-0,1
-0,2
Melt
-0,3
-0,4
-0,5
-0,6
-0,7
Eutectic
0 100 200 300 400 500
T (ºC)

Q (mW/mg)
Results - Microstructure & DSC characterization
0,3
0,2
Eutectic
Solidification
Hipereutectic Pb-Li ingots
0,1
0,0
-0,1
-0,2
-0,3
oxidation
Melt
-0,4
-0,5
Eutectic
0 100 200 300 400 500
T (ºC)
Intermetallic Pb-Li

XRD pattern of the oxidized phases
Li3N and PbO

Results – Melting points

Ongoing efforts
• Impurity control
• Optimization of the melting process
– Impurity control
– Design of the thermal treatment
– Reduce of oxidation process
• Li