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NP- 18955
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MOLTEN-LT
BREEDER REACTOR CONCEPT
Q u a r t e r l y Report f o r t h e Period Ending A p r i l 30, 1 9 7 1
nformation Extension, Oak Ridge, Tennessee \
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NP- is955
MQUTti SAUCI&BEUFi EUACTOR CONCEEC r QUiETmY IiitPOKT FOR TIiE PERIOD~EMIINC APRIL 30, i971.
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Chemical investigations on th6 feasibility of a plutonium stesf;' up Moltsn Salt'.Reactor have been in progress in.the Radiochemistry Ditisicm. at Trombay for over two years. The-work programm6'andthd pro&ress cf work have been reported in a series of semi-annual and quarterly progress. reports (1-63.. oUri& the per-i&under report a seoond experimfnt.,has been qarried &t on ths solubility of P"F5 in LiF-136F2-ThF4(71d3i. $5yd5,,f3.s m/O)'in the temperature range of. 510'. to'787'Ci. Th6 s,olubility'of PuF3 in th6 salt mixtur6 of the. above composition was found to ba between 0.7 m/o at the lowest temperatur-6 and around 4 m/c at th6 highest temperature.. Analysis of the salt scmp~fs withdrawn from'equilibrated melts using 10 micron and 15 m/iFron (OHNLsupplied) porosity filter frits '. at the sam6'temp6rature agreed within 5s thereby indicating that the measured.solubility values’ are -e’tie 'within ths limits of sxperimental 'errors. 2T
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DISCUSSIONS
The MSBRCommittee met on several ti’oas%ons 6& w$Qi the assistarM of the workinS group ?n l&%R finalised a working paper,. outlining the various devslopm6ntal effort required t0 be put i+ In this 0Ontext:tha committee also pr6pared a pap6r cm th6 development vjprk that , oould be aarrisd out within the neti four yea&i A stat8m6ntof the propoasd four year proe;ramm8with the personnel and stores' szid 6quipm6nt requireDSntt3 have been prspared and submitted to the DiI%?ot'O~,-CT’ The main feature of ,the paper on the four year development programmeis that it is oonfin6d to the presently acO8pt6d and mOS+feEtSib conoept naely,a Sin&s fluid two-r6&ion'reaotor system.
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3.
E""TAL
3.t
Labarptow SP ace
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FACILITIES -*
Four old glove boxes i n t h e RadiOChemi6try Division have been decontaminated and handed over t p
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not be reused because of corrosion and d e t e r i o r a t i o n of perspex p-18.
h t h e addition of two new glove boxes and two fumehoods in t h e apace
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b
cleared it i s a n t i c i p a t e d that the devslapment work on reprocessing could be i n i t i a t e d .
3.2
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Process Chemht-T Apparatus
It has been reporte
by
3-
cmLt h a t
r€duative extr=tion
of
P l u t d u m , uranium and protactinium i n t o l i q u i d bismuth could be c a r r i e d out e i t h e r in low carbon s t e e l o r melybdenum apparatus. 'The use of de&
.
containers f o r holding s a l t and bismuth i s . , p r e f e m d as mild
is m o s -suceptible t o corrosion by fused salt. I n view of t h i s .a molybdenum crucible has been fabricated using 20 mil molybdemun sheet by eleotron bean welding.
A s p e c i a l graphite former has been f a b r i c a t
t o hold the p l a t e i n the form of crucible and ease of welding i n t h e e l e c t r o n beam welding u n i t a v a i l a b l e with Atonic Fuels Mvision. The e x t r a c t i o n s t u d i e s would be i n i t i a t e d as soon as lithium and bismuth becom available. 2.
3.3
Servicss Most of t h e high temp&atm equipment used f o r t h e E B R
development work and reprocessing s t u d i e s reguj re continuous water c o o l i w while the experiments are i n progress f o r days together.
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In
order t o ensure continuous supply of cooling water i n t h e event of 1
s h o r t supply of water from the.municipa1 mains as overhead tank of 1000 gallons capacity i s being erected and the necessary piping work t o the
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experimental assemblies are i n progress.
It is a n t i c i p a t e d t h a t this would c a t e r t o the need sf a l l water cooling systems f3r a period Cf 8 t o 10 hours i n the event of water supply f a i l u r e . I
. t
& .- I
temperature.
Ths Least square l i n e drawn i n fig. 1 f i t s the equation 1
log s
(do)
= 2.677
- 2.201
where S(m/o) i s t h e s o l u b i l i t y of ArF
1 0 3 ~
(1)
0 . ; .
i n mole percent. The apparent heat m f solution of PuF has bsen calculated t o be I O kcal from the
3
3
r e l a t i on s2
-
&(T~-T,)
log s1
2.303 T,T2
Ilecently ORNL group ham reported the s o l u b i l i t y of PuF i n
3
LiF-BeF2-W (72-16-12 m/o) i n the temperature range of 54OoC to
4
690째C.
Their data was found t o f i t t h e equation 2 log S (m/o)
=
3.01
- 2.41
x 103D
-.-.
with an apparent heat of s o l u t i o n of 11,008f?37 cal/mole
(2 1
Using the
above equation t h e s o l u b i l i t y values f o r three temperatures have been calculatcd and plotted i n f i g . 1. The 0iW-L group have determined the s o l u b i l i t y values only i n
a temperaturs range of 150째C whereas the prssent experiment covers a range of 280OC. The conposition of the base s d t used by these workers i s d s o d i f f e r e n t from t h a t of the present work. If t h e analozy of s o l u b i l i t y behaviour
qf
CeF ( 8 ) i s applicable i n t h e case of FuF
.3
3
both i n binary LiF - B F
and ternary LiF-BeF -ThF mixtures, then 2 2 4 s o l u b i l i t y should be prsdominently governed by t h e empirical paraneter
u =
1ThF4J
b =
[Li.F-2BEF23ThF4
[ThEi
+
i c h is the 'free' LiF contsnt, basis the s o l u b i l i t y of PuF3
determined by O l W workers should l i e very close t o FuF s o l u b i l i t y o b t d n e d by us in t h e pressnt experiment.
However, the
a r e higher than t h e present experiment by about 25"b.
3
values
It may be
because of considerable s c a t t e r i n t h e analytical d a t a of ORNL emup
respectively a n d t h a t
9f
the OFINL composition is 0.43
3
4.
m L z im m lT A L Details of the experimental determinatim of s o l u b i l i t y i f
h F have been described i n the previous qu&erly
rep&.
the present experiment a total of eleven samples have been withdrawn i n t h e
3
temperature
of 510" t o 787°C both i n the cooling and heating cycle.
Out of these eleven samples eight hEve been withdrawn us-
10 micron
Porosity f i l t e r f r i t s , one using' 15' micron porosity f i l t e r frit while two were duplicate samples a t temperatures of 570" and 787°C takcn with
i
15 micron porosity.
e
The composition of LiF-BeF24hF 4 used i n t h e present experiment was 71.3-15.5-13.2m/~on the basis of chemical analysis f o r
Li,
5.
€!e m d Th
from samples withdrawn f r o m the equilibrated melts.
RJ~S-UUCSA" DISCUSSIONS
The r e s u l t s of the s o l u b i l i t y of PuF3 i n LiF-&F2-ThF4
(71.3,
15.5, 11.2 m/o) i n the t e m p e r a t u r e ' r w e of 510" t r 7C7"C obtained by chemical analysis and alpha cofinting are given i n Table I.
The r e s u l t s show t h a t t h e r e i s good agreement between two s e t s of r e s u l t s . The duplicate samplss withdrawn at 570°C and 787°C using 15 micron f i l t e r
frits sh?w Yh higher and 6.3% lower thcn the -.,orresponding s o l u b i l i t y values obtained using 10 micron porosity f i l t e r frits. This trend i n i
the a n a l y t i c a l values supgests t'nat the experimentally detemined s d u b i 1 i t y T a l u e s a r e true r a t h e r than due t o p a r t i c l e s entering i n t o t h e f i l t e r
f r i t s while sampling.
The s c a t t e r i n the data may be due t o t h e small
varictions tbt may be occurring i n thc porosity of the frits duke Welding.
If t h i s were the case, it i s very d i f f i c u l t t o estimate the
v a r i a t i o n i n porosity of the frit d u m fabrication. Hpwever, it may be mentioned t h a t such f i l t e r frit was individually checked by s t a t i c pressure t e s t bsfors using end those showing the maximum uniformity were only selected f o r sampling
t
The d a t a obtained from measurements on samples taken during
cooling and heating cycles together with those of the duplicate samples
are plotted i n Fig.1 i n terms *f m/o of FuF3 vs the reciprocal absolute 4
w
w
and a l s o t h e temperature range covered being narrower. I n any case t h e i r r e s u l t s show t h he PuF s o l u b i l i t ues as higher comparsd
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t o our r e s u l t s which i s q u i t e s a t i s f a c t o r y from the point of view of
BBR(Pu) f e a s i b i l i t y .
I n the naxt experiment, it i s proposed to determine the s o l u b i l i t y of PuF i n the base salt composition of
t
3
m/o). This should make it possible t o m a k s d i r e c t Comparison between CMNJJ values and values obtained hy us f o r LiF-&F2-ThF4(72-16-12
the same salt composition.
about
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The lithium and bismuth ordered a r e expected t o a r r i v e i n month's t i m . supply position of nickel, inconel e t c . a l s o
appear t o have improved m d order f o r these materials a r e being placed f o r e a r l i e s t delivery of materials.
7.
AN.ALYSIS
The s d t sanplss were analysed by alpha counting and by potentionetric methods f o r plutonium , a f t e r dissolution 70b perchloric a q i d . The base salt wcs Estimated f o r L i , Ik and Th a f t e r removal of plutonium by an anion cxchmge method i n corc. EC1 medium.
Details
of the procedur;. f o r a a l y s i s have been given i n prscseding quarterly
reports. 8.
SXJNImY The s o l u b i l i t y of PuF3 i n LiF-BeF2-ThF 4 mixture of com-
position I
71.3, 15.5, 13.2 m/o has been determined i n t h e temperature
of 510" t o 7 8 7 O C m d t h e values have been found t o vary between at 510째C and 4 m 787째C. The duplicate s o l u b i l i t y values deternined using 15 micron f i l t e r frits a t 570 and 787째C confirms t h a t the s o l u b i l i t y values m e t r u e within t h e experimental e r r o r s . The limited s c a t t e r of the d a t a obtained using d i f f e r e n t f i l t e r f r i t s 5
I
he samples by the
s of experiment c o n f i r m the preliminaqr
hese values a r e corns o l u b i l i t y required t o j u s t l f y a
t i a l of ~ E ~ ( P U concept ),
.
T
at i s required XIS s t o r e s requiresubmitted a f t u r year work programme with personnel ment. '
1. 20
3.
Progress %port on molten salt breeder reactor project f o r
half yea: endire July 31, 1969, E i R C i n t s r n a l communication. Progress eport on nolten s a l t breeder reactor project for half y e w sndiig January 31, 1970, hBC i n t e r n a l communication. t no1tr.n salt breeder reactor f c r t h e period Progress * ~ g o r on
4.
ending Ap;<l 30, 1970, BAC i n t e r n a l cornmication. Progress :-;port on n d t e r ? salt breedsr r e a c t w f o r t h e period endJu:y 31, 1970, BARC i n t e x a l comunication.
5.
Progress iepo;.t on mclten sal: breeder r e a c t o r tnc: period ending October 3.0, 1970, E A C i n t e r n a l comnunicatlon.
6.
Progress i*spc.rt on moltcn salt breeder r s a o t o r fqr t h e period endin5 Jan~cry31, 1971, BLRC i n t a r n d compicat~-o;l.
7
Holten Salt Reactnr Program-Semi-annual pGogress report f o r t h e 2Eriod ending ilugust 31, 7970 - OWL 4622 pp 91-92.
8.
Barton, .':JI Eredig, L.O. Inorg. Chcm. 9, 307 (1970). C.J.
Gtlpatraick and J.L.
6
FredricksGn,
LJ
Solubility of PuF3 i n LiF-â&#x201A;ŹkF,-!PhF4(71.3,
15.5, 13.2 m/o)
~
c
S.No.
Temp.
OC
l/P OK
w/o
w/n
Ii 1
0.70
0.73
4.277
0.99
0.99
5.020 4 834 7 0480
1 018
1.17
1.12
1.?3
1.75
1.'8
8 076
1.88
1.93
70.43
24 6
2.55
12.40
13e28
0,970
13 *53
13-385
0.943
14 64
14-74
0.943
73-44
73.89
3 -08 3e39 3 e37 3 031
3 032 3 94: 34 9 3w q 3
1a277
545
1.221
"570
1.186
570
1.186
62 5
1.113 1.076
7
656 677
1.052
10.09
8
72 8
0.999
9
"757 Y87 787
6
10 11
Q/O
Chemical
3 177
3 .@7 4249 5 e048 4.786 7.345 7 0857
510
4 5
m/0
Chemical Fbdiochsmical
counting
.
f
7
CHEMICAL is ‘4 0 Q - - ----
f+?EI 6995
ANALYSIS HEATING COOLING - COUNTING HEATING COOLING
LEAST .SBUARE LINES ORNL LEAST SQUARE UNI
I . SOLUBILITY OF PuF3 IN LIF-BsF2 t-( Pl*3, IS*!5 ,I302 m/o) , H-(68*2,. 20.3;, q*3 mm , l-045
Ia95
. .
I.145
103/ 1 (‘It)
8
I.195
-ThF4 I I *24S
I*295