Fusion Engineering and Design 9899 (2015) 20092014

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Fusion Engineering and Design

journal homepage: www.elsevier.com/locate/fusengdes

Study on fabrication method of lithium alloys with metal grains

Yuu Nakajima a , Masatoshi Kondo b, , Takashi Nozawa c
a
Department of Nuclear Engineering, Tokai University, 4-1-1 Kitakaname, Hiratsuka-shi, Kanagawa 259-1292, Japan
b
Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1 O-okayama, Meguro-ku, Tokyo 152-8550, Japan
c
Japan Atomic Energy Agency, Rokkasyo-mura, Kamikita-gun, Aomori 039-3212, Japan

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Pb-Li and Sn-Li alloys were success- New fabrication methodology of PbLi and SnLi alloys using metal grains.
fully fabricated using small metal
grains of Li, Pb and Sn.
The depletion of Li during the Li alloy
fabrication procedure was due to the
oxidation of Li by the oxides on the
metal grains of Pb or Sn.
The Li concentration in the alloys was
adjusted by the mixture of the liquid
Li alloys having different Li concen-
tration.

a r t i c l e i n f o a b s t r a c t

Article history: Fabrication methods of leadlithium (PbLi) alloys and tinlithium (SnLi) alloys were studied. The alloys
Received 16 September 2014 at various Li concentration were fabricated by the melting and mixing of the small metal grains of Li, Pb
Received in revised form 6 June 2015 and Sn. The concentration of Li in the fabricated alloy was evaluated by two methods, i.e. chemical
Accepted 29 June 2015
analysis by ICP-AES and the evaluation of the melting point of the alloys with the phase diagram. The
Available online 23 July 2015
concentration of Li determined by these two methods agreed well each other. The Li concentration of the
fabricated alloys was lower than that expected from the mass of the Li metal grains used. The depletion
Keywords:
of Li metal was caused by the oxidation of Li with the oxides on the pure Pb or Sn grains in the fabrication
Liquid breeder
Lithium
process. The concentration of Li in the fabricated alloy was successfully adjusted by the addition of the
Lithiumlead alloy Li alloy having different Li concentration.
Lithiumtin alloy 2015 Elsevier B.V. All rights reserved.
Fusion blanket

1. Introduction
Lead lithium (PbLi) alloys and tin lithium (SnLi) alloys are con-
sidered as liquid breeders of fusion liquid blanket. PbLi alloys have
benecial nuclear characteristics, which can have a large tritium
breeding ratio in the fusion blanket. SnLi alloys have preferable
thermo-physical properties such as a low vapor pressure and a high
boiling point [1]. The concentration of Li in these alloys is important
Corresponding author at: Masatoshi KONDO, Tokyo Institute of Technology,
Japan.
E-mail address: kondo.masatoshi@nr.titech.ac.jp (M. Kondo).
parameter since the chemical characteristics of the alloys are deter-
mined by the chemical activity of Li given by its concentration in the
alloys. It is important technology to fabricate the alloys with a target
composition, and to maintain the Li concentration in the alloy dur-
ing a long-term operation of fusion reactors. The concentration of Li
in the alloys can be measured by Inductively Coupled Plasma Mass
Spectroscopy (ICP-MS) [2] or Inductively Coupled Plasma Atomic
Emission Spectroscopy (ICP-AES). In the same time, the composi-
tions can be evaluated by the measurement of their melting point,
since the melting points of the alloys were different depending on
their compositions as summarized in the phase diagram [3,4]. The
former method can indicate the total quantity of Li even if Li is
in the form of oxide such as Li2 O in the alloy. Therefore, its result

http://dx.doi.org/10.1016/j.fusengdes.2015.06.184
0920-3796/ 2015 Elsevier B.V. All rights reserved.
2010 Y. Nakajima et al. / Fusion Engineering and Design 9899 (2015) 20092014
Fig. 1. Results of oxygen mapping analysis by EPMA on surface cross sections of Pb
grains, (a) type A Pb grains and (b) type B Pb grains.
cannot directly give the alloy composition. The latter method may
indicate the alloys composition, when the correlation between Li
concentration and the melting point of the alloy has high accuracy
in the phase diagram.
The Li alloys could be fabricated with melted Li and Pb or Sn
[5, 6]. When the alloys are fabricated by the mixture of these liquid
metals at high temperature, the segregation of the composition may
be caused since Li concentration become locally higher than the
target composition in the melt due to the large difference of the
densities. In the same time, the high temperature condition can
cause selective evaporation of Li due to its high vapor pressure and
the selective oxidation of Li even in the glove box lled with high
purity Argon (Ar).
The purpose of the present study is to investigate the adequate
fabrication methodology of the Li alloys and the method of the
adjustment of Li concentration in the alloys. The experimental stud-
ies on the fabrication of Li alloy were performed with small metal
grains of Pb, Sn and Li. The chemical reactions, which caused the
depletion of Li from the alloys in the fabrication process, were inves-
tigated. The adjustment of Li concentration in the fabricated alloy
was performed by the mixture of the Li alloys having different Li
concentration.
2. Experimental conditions
The raw materials for fabricating the alloys are the metal grains
of Li, Pb and Sn. Two types of lead grains with different purities were
prepared. The diameter of these grains was approximately 2.5 mm.
The Pb grains of high purity 99.999% were supplied from Furuuchi
Chemical Co., and these were called type-A Pb grains in the cur-
rent work. The Pb grains of low purity 99.9% were supplied from
KOJUNDO CHEMICAL LABORATORY CO., LTD, and these were called
type-B Pb grains. The grains of Li were supplied from Chemetall
GmbH, and the purity was 99%. The Sn grains were supplied from
KOJUNDO CHEMICAL LABORATORY CO., LTD, and the purity was
99.9%. The surface of the type- B Pb grains had black color, though
the surfaces of the type-A Pb grains had metallic cluster. The results
of Electron Probe Micro Analyzer (EPMA) analysis on the surface
cross sections of these Pb grains were shown in Fig. 1(a) and (b).
It was found that the surface of the type-B Pb grains was oxidized,
and the depth of the oxygen rich layer was approximately 10 m.
Such oxides were not detected on the surface of type-A Pb grains.
The results of EPMA surface analysis on the Sn grain were shown
in Fig. 2. The results indicated that the surface of the Sn grain was
partially oxidized.
Fig. 3 shows the schematic diagram of experimental apparatus.
The alloy fabrication was performed in the glove box lled with Ar
gas having purity of 99.999%. The grains of Li and Pb or Sn were
placed in the crucible made of 316 type austenitic steel, which
has the chemical compositions of Fe-18Cr-12Ni-2Mo. The condi-
tions of the fabrication tests were summarized in Table 1. The test
Fig. 2. Results of oxygen mapping analysis by EPMA on surface of Sn grain.
temperature was slightly higher than the melting points of Pb and
Li. Then, the alloy was fabricated by stirring and mixing the melt-
ing grains. In some cases, this procedure was performed at higher
temperature since the melting points of the alloys was expected to
be higher. The temperature of the outer crucible was controlled by
a sheathed heater and a thermocouple placed on an outside of the
outer crucible. The outer crucible was wound by the heat insula-
tion. The power of the heater was kept at constant when the melting
grains wereixed by the stirrer.
The metal grains were heated by the heater and mixed by the
stirring rod. The temperature of the alloy during the fabrication
process was monitored by the thermocouple directly inserted into
the alloy. The thermocouple was calibrated by the melting point
of pure metals of Pb and Sn. The stirring rod made of Mo wire or
musher type stirrer was used to mixing the grains or the melts.
The time for stirring and mixing of the melted grains was approx-
imately 10 min in all the tests. It was quite important to mix the
metals vertically, since the densities of Pb and Li were signicantly
different. Therefore, the musher type stirrer (Fig. 3), which can mix
the metals and/or the alloys well only by the vertical motion, was
developed in the current work. Furthermore, the mixing procedure
with the musher type stirrer must be performed by automation
machine.
The segregation of Li and the formation of Li rich alloy in the mix-
ing procedure led to failure of the alloy fabrication. Then, the effect
of the initial layout of the grains on the fabrication was investigated
by changing the initial layout of the metal grains in the crucible
before the heating and the mixing. The initial layouts were illus-
trated in Fig. 4. In the layout (a), the Li grains were randomly mixed
into Pb or Sn grains. In the layout (b), Li grains were arranged in
a form of layer structure. In the layout (c), the Li grains were just
placed on the top part of Pb or Sn grains.
Fig. 3. Schematic diagram of experimental apparatus.
 Y. Nakajima et al. / Fusion Engineering and Design 9899 (2015) 20092014 2011

Table 1
Fabrication condition of lithium alloys and results of alloy fabrication.

Test ID Target Li Quantity of alloy Layout of grains Temp. [ C] Analysis subject Li concentration [mol%]
composition [cm3 ] (Fig. 4) (Maximum
 [mol%] temperature) by by  by
M.P. ICP-AES Eq. (5)

PbLi
Type B Pb
1 17 2 a 350-(400) Alloy 10

Alloy 12 11 12.1
2 17 30 a 350-(417)
Depositions adhered 34
to stirring rod

3 17 30 a 367-(486) Alloy 12 11 12.1

4 17 30 b 350-(372) Segregation 40

5 17 2 c 327-(420) Segregation 43

6 22 30 a 357-(587) Alloy 20 19 19.4

Alloy 26 25 25.0
7 29 30 a 347-(480)
Depositions adhered 47
to stirring rod

Type A Pb
8 17 (Musher type 30 a 350-(523) Alloy matrix 17 15
stirrer)

9 30 30 a 400-(477) Alloy 28 28

Sn-Li
10 20 2 a 350-(495) Alloy 20

11 20 30 a 350-(366) Alloy 16 15

12 20 30 b 350-(352) Alloy 20

13 20 2 c 232-(388) Segregation 43

14 25 30 a 350-(562) Alloy 23 22

15 30 30 a 400-(548) Alloy 30 29

The fabrication quantities of the Li alloy were 2cc and 30cc.
The necessary quantities of the raw materials were estimated with
the target Li concentration. The target Li concentration Li (molar
concentration) was determined by equation of,
mLi /MLi
xLi =
mPb or Sn /MPb or Sn + mLi /MLi
where m and M are the mass of raw materials used and the atomic
weight of Li and Pb (or Sn), respectively.
After the fabrication of the alloy, the heater was stopped and the
alloy was naturally cooled in the glove box. The temperature- time
cooling curve was obtained by the thermocouple inserted in the
alloy. The line change in the curve indicated the melting point due to
the formation of primary crystals in the curve. The Li compositions
of these alloys were determined by the melting point on their phase
diagram.
Some pellets of the alloys were made by the solidifying the alloy
spilled on the pallet (Fig. 3). The tips of the pellet were taking out
Fig. 4. Initial layout of metal grains in crucible for the alloy fabrication.
by a drilling of the pellet. Then, the chemical analysis by ICP-AES
was performed with the solution, in which the tips dissolved in a
nitric acid. There was no residue in a nitric acid solution used for
the ICP-AES analysis.
The adjustment of the Li concentration in the fabricated alloys
(1) was performed by the mixture of the alloys having different Li con-
centration. The test conditions are summarized in Table 2. After the
alloy was melted in the crucible, the alloy was charged into the
alloy . Then, the alloys were stirred and mixed for approximately
10 min by the stirring rod.
3. Results and discussion
3.1. Layout of the metal grains for the fabrication
Fig. 5(a) and (b) shows the temperature-time cooling curves
obtained from the fabricated alloys. The line changes in the
curves due to the formation of primary crystals in the alloys
were detected as indicated by broken circles in Fig. 5. The line
change could not appear when the alloys were eutectic alloys.
The temperature at these points was used to determine the Li
concentration of the alloys based on the correlation between the
temperature and the composition in the phase diagram. Then,
the evaluated Li concentration was summarized in Table 1. The
results indicated that the concentration of Li was lower than that
expected from the mass of Li metal in all the tests except for the
tests 8 and 9, in which the type-A Pb grains were used as raw
materials.
The test results indicated that PbLi and SnLi alloys were
homogeneously fabricated without the occurrence of segregation
when the grains of Li and Pb or Sn were uniformly mixed as the
2012 Y. Nakajima et al. / Fusion Engineering and Design 9899 (2015) 20092014

Table 2
Test results for adjustment of Li concentration in alloys.

Test ID Target Li content. Alloy (mass [g]) Alloy (mass [g]) Li content by m.p. [mol%]

16 Pb25Li (142) Pb (type B, 87.0) 5

17 Pb-17Li Pb19Li (100) Pb5Li (15.0) 17
18 Pb25Li (99.7) Pb5Li (94.3) 17

19 Sn22Li (83.5) Sn15Li (25.4) 20

Sn-20Li
20 Sn15Li (38.8) Sn22Li (61.8) 21

Table 3
Metal impurities of PbLi alloys by ICP-MS.

Test ID Na Bi Fe Cr Ni W Mn Mo Ta Hg Ti

8 (Pb15Li) 48 6.8 7.8 <0.1 0.3 <0.1 <0.1 <0.1 <0.1 0.4
9 (Pb28Li) 110 6.0 22 0.8 1.6 0.3 <0.1 <0.1 <0.1 0.4

layout (a) (Fig. 4). The concentrations of Li in the alloy analyzed by
ICP-AES analysis were summarized in Table 1. The Li concentration
agreed with that determined by the measurement of the melting
point. The Li concentration of the depositions adhered to the sur-
face of the stirring rod in tests 2 and 7 was analyzed by ICP-AES,
and the results were presented in Table 1. The Li concentration of
the depositions was much higher than that of the alloy matrix. The
metal impurity in the PbLi alloys fabricated in tests 8 and 9 was
analyzed by ICP-MS (Table 3).
In the tests performed with the layouts (b) and (c), some insol-
uble residues were formed during the mixing procedure. The
insoluble residues formed in tests 4 and 5 had black color. The
concentration of Li in the residues was approximately 40 wt%.
The insoluble residues must be formed by the segregation of Li dur-
ing the fabrication procedure. The results indicated that well mixing
Case 6
640 Case 9 Case 1
of Li and Pb (or Sn) grains before the heating and the melting led to
the alloy fabrication without the segregation.
3.2. Heat for alloy formation and chemical reaction during alloy
fabrication procedure
The temperature of the melting grains and/or the alloys in the
crucible rapidly increased after a start of stirring. The trend of the
temperature increase of the alloys could be different in some tests
due to the different reaction rate and the different temperature
distribution in the alloys by the manual stirring. Then, the heat
release from the alloys is also different in these tests. Small re was
observed during the mixing procedure in the test performed with
type B Pb grains and Sn grains as shown in Fig. 6. The re was not
observed in the test with type-A Pb grains. The highest tempera-
ture during the test was summarized in Table 1. The temperature
increase, T, is due to the heat for formation, Q, of Li alloys and/or
Li oxides as
Case 7

Q
620 Pb-28Li T = ,
Temperature[K]

(2)
mcp
600 Pb-26Li
Case 3
580 Case 2 where m and cp are the mass and the heat capacity of the
560 Pb-10Li alloy, respectively. For example, the temperature increase in tests
Pb-12Li 2 and 3 were evaluated by the heat for formation. The heat
540 or for the formation of Pb-11Li alloy was estimated to 6.19 kJ/mol
520 Pb-20Li (exothermic reaction) by the extrapolation of the literature value
Case 8 near of 5.83 kJ/mol at 800 K [7,8] according to the Kirchhoffs law.
500
eutec The temperature increase by the heat for the alloy formation
0 200 400 600 800 1000
point
Time[sec] was theoretically estimated to 179 K. The temperature increase in
the tests 2 and 3 was smaller than that theoretically estimated
(a) Pb-Li alloy possibly due to the heat release from the alloys in the mixing
690 Case 14 procedure.
Case 15
The other reason for the temperature increase is the heat gen-
670
Temperature[K]

Case 12 eration by the chemical reaction for the formation of Li oxides. The
650

630

610

590

570 Case 10
Case 11
550
0 200 400 600 800 1000
Time[sec]
(b) Sn-Li alloy
Fig. 5. Temperature-time cooling curve (a) PbLi alloy and (b) SnLi alloy. Fig. 6. Small re in the mixing procedure of the alloy fabrication.
 Y. Nakajima et al. / Fusion Engineering and Design 9899 (2015) 20092014
35
Li concentration of alloys
30
measured by ICP-AES
25
[mol%]
T
Test 14
20
Test 6
15 Test 11
Tests 2 and 3
10
10 15 20 25
Target Li concentration of alloys
Fig. 7. Relation between target Li concentration and that in alloy evaluated by ICP-
AES.
Fig. 8. Model of Li alloy formation and chemical reaction for Li oxide formation in
fabrication procedure.
heat for the oxide formation by possible chemical reactions at 523 K
was calculated by thermodynamic database MALT 2 code [9] as,
PbO2 + 4Li 2Li2 O + Pb + 934.074 kJ,
SnO2 + 4Li 2Li2 O + Sn + 628.644 kJ,
The heat generation by Eqs. (3) and (4) is large. These reactions
locally caused on the Pb or Sn grains surface, and may contribute
to the small re generation during the mixing procedure.
The temperature increase in test 8 was large, though the type
A grains without oxides were used. This was because the melted
grains were rapidly mixed by the musher type stirrer. Then, the
heat for dissolution was generated within a short period and the
heat was not escaped from the crucible.
3.3. Loss of Li during the alloy fabrication
The concentration of Li in the fabricated alloys was lower than
that expected from the mass balance of the raw materials in all
the tests except for the tests 8 and 9, in which type A Pb grains
were used. Fig. 7 shows the relation between the Li concentration
expected from the ratio of the raw materials (target Li concen-
tration in Table 1) and that in the fabricated alloys measured by
ICP-AES. The difference between the target Li concentration and
the experimental results became smaller with the lower concen-
tration of metal Pb or Sn in the alloy. This relation indicated that
the depletion of Li was caused by the oxidation of Li with the oxides
adhered and dissolved in Pb and Sn metals. Then, the depletion of
Li due to its oxidation by the oxide of Pb or Sn (Figs. 1 and 2) was
modeled as shown in Fig. 8. In the fabrication of SnLi alloy, the
quantity of the oxides on the Sn grain surface was smaller than that
on type B Pb grains (Figs. 1 and 2). However, the oxygen poten-
tial in the Sn metal is much higher than that in the Li metal as
Gf,SnO2 = 227 KJ/atomO Gf,Li2 O = 497 KJ/atomO at 600 K, if
2013
the equilibrium oxygen potentials for their saturation conditions
were assumed. Therefore, the high oxygen potential of Sn metal
could be also the reason of the oxidation of Li in the fabrication
Test 15
5
process of the SnLi alloy.
Then, the quantity of Li reacted with the Pb oxide on the type
Test 7
B Pb grain surface was evaluated according to the formation of Li
oxides. The total quantity of the Pb oxide on the grains was esti-
mated from the results of EPMA analysis shown in Fig. 1(b). The
Li concentration  (molar concentration) after the consideration
of Li depletion and the reduction of the oxides due to the Li oxide
formation was expressed as
30 35
mLi mLi
MLi
 = 100, (5)
mLi MLi mPb +mPb
MLi
+ MPb
where mLi and mPb(or Sn) are the quantity of Li and Pb used in the
tests, respectively. mPb (or Sn) and mLi are gain or loss of the
quantity of Pb and Li respectively. The Li oxides formed during the
fabrication procedure could be removed by the stirrer during the
mixing procedure as the depositions (Table 1). The concentration
of Li in the PbLi alloys by Eq. (5) was summarized as  in Table 1.
It was found that the concentration of Li was well agreed with that
by ICP-AES. In the tests 8 and 9, the concentration of Li in the fab-
ricated alloy was agreed with that expected from the mass of the
raw materials, since the quantity of the Pb oxides, which can react
as Eq. (3), was small.
3.4. Adjustment of Li concentration in alloy
The adjustment of Li concentration in the fabricated alloy
was performed by the mixture of the alloys having different Li
concentration. The results are summarized in Table 2. When the
type-B Pb grains were charged to Pb-25Li alloy, the Li concentra-
(3)
tion in the alloy became lower than that expected from the mass
(4) balance possibly since the Li in the alloys reacted with the Pb oxides
on the Pb grains surface, and depleted from the alloy. In the other
case, the Li concentration was successfully adjusted by the current
method.
4. Conclusion
The experimental studies on the fabrication of Li alloy were per-
formed with small metal grains of Pb, Sn and Li. Major conclusions
are follows;
(1) The PbLi alloys and the SnLi alloys with various Li concentra-
tion were fabricated with the small metal grains of Li, Pb and Sn.
The Li content of the fabricated alloy was determined by two
methods, i.e. the chemical analysis of ICP-AES and the measure-
ment of melting point. The concentration of Li determined by
these two methods agreed well each other.
(2) Small metal grains of Li and Pb or Sn should be well mixed
before the heating and the melting to prevent the formation of
Li rich alloy by the segregation of Li.
(3) It was found that Li was partially depleted from the raw mate-
rials in the fabrication procedure of Li alloys. It was made clear
that the Li depletion was due to the oxidation of Li with the
oxides on the Pb and Sn grains used as the raw materials for the
alloys fabrication.
(4) The adjustment of Li concentration in the fabricated alloy was
performed by the mixture of the liquid Li alloys having different
Li concentration.
2014 Y. Nakajima et al. / Fusion Engineering and Design 9899 (2015) 20092014

Acknowledgment [3] R.E. Buxbaum, J. Less-Common Met. 97 (1984) 2737.

[4] R.N. Lyon, Liquid Metals Handbook, The Atomic Energy Commission, 1952,
June.
This work was partially supported by the Japan Atomic Energy [5] D.H. Jansen, E.E. Hoffman, J. Nucl. Mater. 3 (1959) 249258.
Agency under the Joint Work contract 26K306, as a part of Broader [6] K. Natesan, W.E. Ruther, J. Nucl. Mater. 307311 (2002) 743748.
Approach activities. [7] W. Gasior, Z. Moser, J. Nucl. Mater. 294 (2001) 7783.
[8] A. Neubert, J. Chem. Thermodyn. 11 (1979) 971.
[9] H. Yokogawa, Netsu Bussei 7 (1993) 6365.
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