Journalof NuclearMaterials103&104(1981)585~$90 585

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IRRADIATION STUDY OF LITHIUM COMPOUND SAMPLES FOR TRITIUM BREEDING APPLICATION*

L. Yang, R. Medico, W. Baugh and K. Schultz

General Atomic Company
P.O. Box 81608
San Diego, California 92138

Fifty-four Inconel-600 clad LiA102, Li20, Li4SiO4 and Li7Pb2 samples were prepared and
irradiated in the Oak Ridge Reactor at 600o - 1OOOoC for a period of about six months
to a fast neutron fluence (SO.18 MeV) of 1.1 - 2.7 x 1025 n/m2. This paper describes
the fabrication techniques for these samples and the post-irradiationexamination
results of the microstructures of these compounds and their compatibilitywith the
cladding material.

1. INTRODUCTION Li20, Li4SiO4, and LiA102 powders were prepared

In the development of lithium compounds for
tritium breeding in a fusion reactor blanket,
information on the irradiation behavior of can-
didate materials is needed for establishing the
feasibility and the operating conditions. Fifty-
four Inconel-600 clad Li20, LiA102, Li4SiO4 and
Li7Pb2 samples were prepared and irradiated in
Oak Ridge Reactor (ORB) to evaluate the effect
of high temperature irradiation on the micro-
structures, compatibilitywith cladding, and
tritium release behaviors of these potential
solid breeding compounds. This paper describes
the fabrication of the test samples and the post-
irradiation examination results on the micro-
structures and compatibilityof the test samples.
2. SAMPLE FABRICATION
The capsule (designatedas (X-5) in which these
samples were irradiated represents one of a
series of capsules for irradiating graphite sam-
ples in ORR under the high-temperature-gas-cooled
reactor Base Program at General Atomic. Test
holes of 3.429 rmndiameter were provided for
this test free of neutron charge. To facilitate
tritium release, the lithium compound test sam-
ples are mostly low density ones (60-80% dense)
and have a diameter of about 1.5 mm and a height
of 2-3 mm. Since the thermal neutron flux in ORR
is orders of magnitude higher than that in the
fusion reactor blanket, 6Li-depleted (6Li enrich-
ment = 0.05%) samples were prepared for this
experiment so that the rates of tritium and
helium generation during irradiation are real-
istic. Li-metal containing 0.01% of 6Li was
procured from Oak Ridge National Laboratory.
Natural Li-metal of 99.99% purity (6~i enrich-
ment = 4.94%) was obtained from Research Organic/
Inorganic Chemical Corporation. LiOH was pre-
pared from each of these Li-metals by reacting
with deionized water. Calculated amounts of
6Li-depletedLiOH and natural LiOH were mixed to
attain LiOH of 0.05% 6~i enrichment, Li2CO3 was
then precipitated from the LiOH obtained with
co2. The precipitated Li2CO3 was recovered by
filtration and the precipitate was then dried in
an oven at 100C overnight.
from the Li2CO3 powder obtained by heating in
vacuum with the appropriate additives and the
test samples were fabricated from these powders
by the cold-pressingand sintering technique.
Table 1 describes how these powders were pre-
pared and Table 2 shows the cold-pressingand
sintering conditions. All operations involving
handling of the powders (mixing, grinding, and
pressing) were carried out in a dry box of
moisture content less than 2 ppm.
6Li-depletedLi7Pb2 was prepared by melting
calculated amounts of 7Li metal containing
0.01% 6Li, natural Li metal, and high purity
(99.99% pure) lead in a covered iron crucible
under argon gas. To insure thorough mixing,
the melt was maintained at 8200C for one hour.
After cooling, the content in the crucible was
broken into pieces of about 0.5 to f mm sizes.
Since fully dense Li7Pb2 granules of such sizes
released tritium readily at 55OoC, therefore
no attempt was made to prepare porous Li7Pb2
pellets. Instead Li7Pb2 pieces of such sizes
were used for the present experiment.
The lithium compound test samples were con-
tained in Inconel-600 thimbles of 3.175 mm
O.D. and 0.635 mm wall thickness. All thim-
bles were outgassed in vacuum at 1OOOoC for one
hour. After the test samples were loaded into
the thimbles, the thimbles were welded shut in
a helium atmosphere. In general, the length of
the thimble is such that less than half of the
volume inside the thimble was occupied by the
test sample. Therefore there is ample room for
accommodating any swelling of the test sample
during the irradiation.
Table 3 shows the sample dispositions in the
capsule and the testing conditions. The total
irradiation time is about six months.
3. HOT CELL EXAMINATION RESULTS
Hot cell examinations of the microstructures
and compatibilitybetween the lithium compound
test samples and the Inconel-600 cladding have
been completed. The highlights are given below.

%Work supported by Department of Energy, Contract DS-ATO3-7bET51011.

0022-3115/81/0000-0000/$02.75
0 1981North-Holland
586 L. Yang et al. / Lithium compound samples for tritium breeding application

TABLE 1. PREPARATION OF Li20, Li4SiO4, AND LiAlO2 POWOERS

Vacuum Furnace Heating

Temperature Time Grinding
Starting Materials (?I (hrl Operation Final Product

Li2CO3 powder 900 15 Sapphire

mortar

LiCO3 powder 1260 Agate Li4Si04 powder

+ SiO2 powder f<lOO R mortar K43 /.I)

LiCO3 powder 1050 4 Sapphire LiAl02 powder

mortar
+ Al203 powder (<O.l pl K43 /.I)

TABLE 2. PRESSING AN0 SINTERING OF TEST SAMPLE PELLETS

L-
Cold-Pressing Vacuum Sintaring Sintaring Oenrity of
Pressure Temperature Time Sintered Pellets
Test Sample (MPa) (C) (hr) 1%)

Liz0 55 .207 1050 4 60 - 70

Li4Si04 55.207 900 16 70-90

1050 4 90 - 100

LiAlO 2 55 .207 1050 4 60 - 70

TABLE 3. SAMPLE DISPOSITIONS AN0 TESTING CONDITIONS

Neutron Fluence x 1O-25

(nlm2) Number of Test Samples
Temperature
Fast
fC) Thermal Li20 Li4Si04* LiAlO 2 Li7Pb2
f> 0.16 YeVl

1000 1.6 2.7 4 4 4 0

950 1.7 2.9 6 6 6 0
860 1.1 2.0 4 4 4 0
750 0.6 1.6 4 4 0 0
600 0.6 1.1 1 1 0 2
*Half ara low density samples; the other half are high density samples.

LiAlO2. High temperature irradiation sample irradiated at 750C but not into the
(850 - 1000C)
did not change the micro- pores of the samples irradiated at 850C and
structures of LiA102 test samples (compare 1ooooc. This difference in pore structures
Figs. 1 and 2) but the irradiated samples will probably affect the tritium release
had poor mechanical integrity, the edge and behaviors of irradiated Li20 and should be
corners of which tended to crumble during borne in mind in selecting the surface tem-
polishing. No interaction between LiA102 perature, power density, and diameter of the
and the Inconel-600 cladding was observed breeding element. Grain boundary attack of
(see Fig. 3). the cladding was observed for all the Li20
test samples. The maximum penetration was
Li20. Irradiated Li20 showed considerable about 150 pm at 1000C and about 75 um at
sintering and pore structure redistribution 75ooc. A typical example is shown in Fig. 8.
(compare Figs. 4, 5, 6 and 7). It appears
that the pores became closed in samples 3. LiqSiO4. For the low density samples, no
irradiated at temperatures above 85OoC, but significant grain growth occurred at 750C,
remained mostly open in the sample irradiated although some pore consolidation happened
at 75OOC. This conclusion is based on the (compare Figs. 9 and 10). At higher tem-
observation that the epoxy resin used to peratures, the grains grew into large size
impregnate the sample prior to metallographic and the structural integrity of the sample
polishing penetrated into the pores of the irradiated at 1OOOoC was lost because of
 L. Yang et al. /Lithium compound samples for tritium breeding application 581

Fig. 1. Microstructuresof 70% dense Fig. 4. Pore structures of 68% dense

LiAlO2 after irradiation at 950C. Li20 after irradiation at 75OOC.

Fig. 2. Microstructures of 70% dense Fig. 5. Pore structures of 68% dense

LiA102 before irradiation. Li20 after irradiation at 8500C.

Fig. 3. Interface between 70% dense Fig. 6. Pore structures of 68% dense
LiA102 and Inconel-600 cladding after ~i20 after irradiation at 1000C.
irradiation at 950C, showing no reactiOIl..
 L. Yang et al / Lithium compound
Fig. 7. Pore structures of 70% dense
Li20 before irradiation.
Fig. 8. Interface between 68% dense Li20
and Inconel-600 cladding after irradiation
at 8500C.
grain boundary separation (see Fig. 11). For
the high density samples, no significant
grain growth occurred at 750C, 850C and
9500C (compare Figs. 12 and 13). Grain
boundary separation was apparent at 9500C and
became serious at 1000C (Fig. 14). It is
interesting to note that spherical voids are
present in some grains and at some grain
boundaries (see Figs. 11 and 14) of samples
irradiated at lOOoOC, although the origin of
these voids Is not clear. Grain boundary
attack of the cladding occurred in all sam-
ples. The maximum penetration varies from
about 125 um at 1OOOoC to about 50 urnat
75ooc. A typical example is shown in Fig. 15.
4. Li7Pb2. There was no significant change in
the microstructuresof the Li7Pb2 granules
after irradiation at 6000C. The maximum
samples for tritium breeding application
Fig. 9. Microstructuresof 72% dense
Li4SiO4 after irradiation at 7500C
Fig. 10. Microstructuresof 70% dense
Li4SiO4 before irradiation.
grain boundary penetration of the cladding
observed was about 50 urn. A typical example
is shown in Fig. 16.
Measurements of the tritium content in the
Inconel-600,thimblesand the residual tritium
content in the lithium compound test samples
are under planning. The results should indi-
cate how the above-describedchanges in micro-
structures upon high temperature irradiation
affect the tritium release behaviors of these
lithium compounds.
ACKNOWLEDGMENT
We wish to thank Dr. Theodore C. Reuther of the
Materials and Radiation Effects Branch, Division
of Development and Technology, Office of Fusion
Energy, for his interest and support.
 L. Yang et al. / Lithium compound samples for tritium breeding application 589

Fig. 11. Microstructuresof 72% dense Fig. 14. Microstructure6of 95% dense
Li4SiO4 after irradiation at 1OOOoC. Li4SiO4 after irradiation at 1OOOoC.

Fig. 12. Microstructuresof 95% dense Fig. 15. Interface between 72% dense
Li4SiO4 after irradiation at 85OOC. Li4SiO4 and Inconel-600 cladding after
irradiation at 1OOOoC.

Fig. 16. Interface between 100% dense

Fig. 13. Microstructures of 95% dense Li7Pb2 and Inconel-600 cladding after
Li4Si04 before irradiation. irradiation at 6000C.