TS1NGHDA SCIENCE AND TECHNOLOGY

ISSN 1007 0214 11/19 pp45~49

Volume i , Number i , March 1996
Research on the Silicon Carbide Layer of Coated Fuel Particles *
Xu Shijiang ( # - * ; ) , Yang Bing ( # * ) , Zhu Junguo ( ^ S ) ,
Zhang Bingzhong ( & & ) , Zhao Zhichao ( * . & * ) , Cheng Bihua ( * i j f # 0 ,
Zhang Dongemei ( J 4 ^ ) > Zhang Chun ( & ft)
Institute of Nuclear Energy Technology, Tsinghua University, Beijing 100084
Abstract: The 10MW high temperature gas-cooled test reactor (HTR-10) under construction at INET uses whole
ceramic fuel elements. The main barrier which prevents fission product release is the SiC layer of the coated fuel
particles. Fabrication of high quality SiC layers is one of the key R&D tasks for the HTR-10 fuel element. The SiC
layer was deposited on the fuel particles in a 50 mm conical fluidized bed using the CVD (chemical vapour
deposition) technique. The density, thickness, strength and elastic modulus of the SiC layer were measured. The
microstructure was observed using SEM (scanning electron microscope). Parameters were established for
manufacturing the SiC layer of the coated fuel particles to be used in the HTR-10. It was found that the traditional de-
nsity measurement by the sink-float method is questionable in the low density region and that the SiC layer may be
contaminated by uranium under certain conditions.
Key words: high temperature gas-cooled reactor; fuel element; coated fuel particle; SiC * density; strength; microst-
ructure; uranium contamination
Introduction
The concept of using fuel el ement s fabricated
compl et el y from ceramic mat eri al s was first suggest -
ed in t he earl y 1940's
1
-
1
-
1
. The main idea is t o overcome
t he rest ri ct ed react or operat i ng t emper at ur es caused
by t he l ow mel t i ng point of metallic mat eri al s. The
concept was realized only after t he successful devel-
opment of coat ed fuel part i cl es ( c p ) in t he early
1960' s. The exper i ment al react ors ( Dr agon, Peach
Bot t om and AVR ) under const ruct i on at t hat t i me
i mmedi at el y changed t hei r fuel design phi l osophy t o
adopt cp as t he basic unit for prevent i ng t he release
of fission pr oduct s t o i mprove radiation safety for t he
staff and t he publ i c. The successful operat i on of t hese
r eact or s st i mul at ed great i nt erest of t he devel opment
of HTR ( hi gh t emper at ur e gas-cool ed r eact or ) sys-
t ems . Huge effort has been poured into R&-D of cp.
Thr ough mor e t han 30 years of common effort among
t he i nt ernat i onal HTR fuel communi t y, t he perfor-
Manuscript received: 1995-08-18
* Supported by the National High Technology Develop-
ment Program of China
mance of cp has been great l y i mproved. Two t ypes of
c p , i. e. BISO and TRI SO have been fully developed
and specified as st andar d fuels for HTRs . The operat -
ing experi ence of AVR and i rradi at i on exper i ment s
show t hat cp will perform well at about 1 300 C un-
der normal operat i ng condi t i ons and up t o 1 600 C
under off-normal condi t i ons for several hundred
hour s
C2
'
3
' .
TRI SO cp has a SiC layer i nt ercal at ed bet ween 2
dense pyrolytic carbon l ayers. The ability of SiC t o
rest ri ct release of such fission pr oduct s as Cs , Sr and
Ba is 2 t o 4 orders of magni t ude hi gher t han t hat of
pyrol yt i c carbon
[ 5]
. The i rradi at i on st abi l i t y of SiC is
also much hi gher t han t hat of pyrolytic carbon
[ 6]
.
Ther ef or e TRI SO cp was chosen as t he reference fuel
for all fut ure HTRs , especially when t he HTR fuel
cycle swi t ches from high enri chment urani um t o low
enri chment ur ani um. Based on t hese r eas ons , t he
HTR- 10 ( 10 MW high t emper at ur e gas-cooled reac-
t or ) adopt ed TRI SO cp as its fuel. Research on t he
SiC layer is one of t he key R&D t asks for t he HTR-
10 fuel el ement . The research emphasi s is to mast er
t he t echni que of manufact uri ng a high quality SiC
layer t o meet t he HTR- 10 specifications. Even t hough
t he SiC layer is an ext remel y i mport ant component of
TRI SO c p , quant i t at i ve specifications can be set only
46 Tsinghua Science and Technology, March 1996, 1 ( i ) : 45^49
for its densi t y, t hi ckness and t he st andar d deviation
of t he t hi ckness so far. However , since t he i rradi at i on
behavi our varies even when t hese par amet er s are t he
same or si mi l ar , clarification of t he SiC layer i rradi a-
tion behavi or is also an i mpor t ant research t ask.
1 Deposition of the SiC Layer
1. 1 Brief i nt r oduct i on of t he HTR- 10 TRI SO cp
The detailed desi gn of t he HTR- 10 TRI SO cp is
given in Ref. [ 7 ] . The st r uct ur e of t he TRI SO cp is
shown in Fi g. 1. The fuel kernel is a 500 fim di amet er
mi crosphere of U0
2
. Four layers of a porous pyrol yt i c
carbon layer ( buf f er ) , an inner hi gh-densi t y isotropic
pyrol yt i c carbon l ayer , a SiC layer and an out er hi gh-
densi t y i sot ropi c pyrol yt i c carbon layer are succes-
sively deposi t ed on t he ker nel . The t hi ckness of t he
l ayers is 90, 40, 35 and 40 /^m, respect i vel y. The SiC
layer specifications are
:
densi t y > 3 . 1 8 g / c m
3
t hi ckness 35 jjzm
st andar d devi at i on of t hi ckness 4/ ur n
U0
2
kernel
buffer
inner dense pyrolytic carbon
SiC
outer dense pyrolytic carbon
Fig- 1 Structure of the TRISO coated fuel particle
1. 2 Deposi t i on of t he SiC l ayer
The SiC layer was deposi t ed on t he particle in a
<J>50 mm conical fluidized bed usi ng t he CVD t ech-
nique. The schemat i c di agr am of t he coat i ng syst em is
shown in Fi g. 2. The st r uct ur e of fluidized bed is
shown in Fi g. 3. The coat i ng process began by first e-
vacuat i ng t he fluidized bed t o several pas kal s , t hen
back filling wi t h Ar several t i mes to get rid of t he
oxygen to prot ect t he gr aphi t e st r uct ur e from oxida-
t i on. The fluidized bed was heat ed t o t he coat i ng t em-
per at ur e while t he argon cont i nued t o flow. Part i cl es
that had al ready been coat ed wi t h t he buffer and t he
inner dense pyrol yt i c carbon layers were added into
the bed and t he gas flow rat e was adjusted t o opt i -
mize the fluidization st at e. After t he t emper at ur e re-
covered and st abi l i zed, Tri chl osi l ane ( MTS) and hy-
drogen were fed i nt o t he bed and t he flow rat e of Ar
was adjusted accordi ngl y t o mai nt ai n t he optimized
fluidization st at e. As the MTS decomposed, SiC
formed and deposi t ed on t he surface of the particles.
valve mass flowmeter
fluidized bed
9$ <&
m
Ar H
2
MTS evaporator
I i^ 2 Schematic diagram of the coating system
view window
loading vessel
off-gas
water
manometer ^- l
windowll n
vacuum pump
water
pytometer
transformer
Ar
coating gas
Fig. 3 Structure of the fluidized bed
On reaching t he appropri at e t hi ckness, t he MTS
and t he hydrogen were t urned off and t he Ar flow
rat e was increased. The power was swi t ched off and
t he fluidized bed was allowed t o cool down t o t he
t hreshol d of t he graphi t e oxidation t emper at ur e. The
Ar flow was t urned off and t he fluidized bed cont i n-
ued to cool down t o room t emper at ur e. The particles
coated wi t h SiC were unloaded.
The main paramet ers affecting t he propert i es of
t he SiC layer are t he st r uct ur e of t he fluidized bed,
t he loading of t he bed, particle size and wei ght , flow
rat e of fluidizing ga s , concent rat i on and purity of
MTS, r a t i o of Ar and H
2
deposi t i on t emper at ur e, et c.
In t hi s paper , only t he effect of deposi t i on t empera-
t ure on t he propert i es of t he SiC layer is given. The
ot her par amet er s were kept const ant at t he follow-
ing.
-concent rat i on of MTS - l v o i ;
Xu Shijiang ( #- - f r 0 et al
:
Research on the Silicon Carbide Layer 47
t o t a l g a s f l ow r a t e 500 L / h
A r / H
2
1/ 1
l o a d i n g 80 g
T h e t e mp e r a t u r e r a n g e d f r om 1 450 t o 1 650 C *
i n s t e p s of 50 C .
2 Properties of the SiC Layer
2. 1 De ns i t y , t hi c kne s s and t he s t andard devi at i on of
t he t hi c kne s s
U p t o n o w , d e n s i t y , t h i c k n e s s a nd t h e s t a n d a r d
d e v i a t i o n of t h e t h i c k n e s s a r e t he onl y p a r a me t e r s
n o r ma l l y s peci f i ed f or t h e Si C l a ye r of T R I S O c p us e d
i n H T R , e v e n t h o u g h t h e y do n o t e xc l us i ve l y speci f y
t h e i r r a d i a t i o n b e h a v i o u r of t h e T R I S O c p . T h e d e n s i -
t y wa s d e t e r mi n e d by t i t r a t i on us i ng t h e l i qui ds di o-
d i n e me t h a n e a nd b r o mf o r m. T h e c oa t e d pa r t i c l e s
we r e c r u s h e d , t h e k e r n e l s we r e r e mo v e d , a n d t h e n t h e
f r a g me n t s of t h e c oa t i ng we r e h e a t e d in ai r at a b o u t
8 0 0 "C t o b u r n off t h e pyr ol yt i c c a r b o n , t h e Si C pi eces
we r e c ol l e c t e d a n d ul t r a s oni c a l l y wa s h e d a n d dr i e d.
T i t r a t i o n wa s c a r r i e d o u t at r o o m t e mp e r a t u r e . T h e
d e n s i t y of t h e t i t r a t i on me di a wa s c or r e c t e d f or t e m-
p e r a t u r e . T h e t h i c k n e s s wa s me a s u r e d us i ng t h e me t -
a l l o g r a p h i c me t h o d . T h e d e n s i t y , t h e a ve r a ge t hi c k-
n e s s a n d t h e s t a n d a r d de vi a t i on of t he t h i c k n e s s a r e
g i v e n i n T a b l e 1.
Table 1 Density* thickness and standard deviation of
the thickness
deposition
t emper at ur e/ C
1 450 1 500 1 550 1 600 1 650
dens i t y/ g- cm-
3
3-21 3.19 3.21 3.18 3.16
thickness/jum 35-3 28.3 30.0 35.2 36-7
st andard deviation//mm 2.3 1-6 2-2 2-5 3-1
2- 2 Mi c r o s t r u c t u r e of t he Si C l a ye r
T h e s ur f a c e mo r p h o l o g y a nd t h e f r a c t ur e s t r u c -
t u r e of t h e Si C l a ye r s we r e o b s e r v e d wi t h S E M. T h e
r e s u l t s of t h e o b s e r v a t i o n s a r e gi ve n in det ai l in Ref.
[ 8 ] , t he c o n c l u s i o n s ar e r e p r o d u c e d h e r e .
De pos i t i on t e mp e r a t u r e h a s a ver y s t r o n g effect
b o t h on t h e s ur f a c e mo r p h o l o g y a nd t he f r a c t ur e
s t r u c t u r e . As t he de pos i t i on t e mp e r a t u r e i n c r e a s e s ,
t h e s ur f a c e mo r p h o l o g y g o e s f r om a c a ul i f l owe r
s t r u c t u r e wi t h a r o u g h s ur f a c e t o a c a ul i f l owe r s t r u c -
t u r e wi t h a s mo o t h s ur f a c e a n d , finally-, t o a g r a n u l a r
s t r u c t u r e . T h e f r a c t ur e s t r u c t u r e c h a n g e s f r om a fi ne
p o r o u s s t r u c t u r e wi t h i n t e r g r a n u l a r f r a c t ur e s t o a
d e n s e h o mo g e n e o u s s t r u c t u r e wi t h t r a n s g r a n u l a r
f r a c t ur e s a nd* t h e n , t o a c oa r s e p o r o u s s t r u c t u r e wi t h
t r a n s g r a n u l a r f r a c t u r e s .
2- 3 St r e n g t h and e l a s t i c mo d u l u s
T h e me c ha ni c a l i nt e gr i t y a nd s t a bi l i t y of T R I S O
cp d e p e n d s on t h e Si C l a y e r s , t h e r e f o r e , t h e me a s u r e -
me n t of t h e s t r e n g t h a nd el as t i c mo d u l u s of t he Si C
l a ye r i s ve r y i mp o r t a n t t o t h e cp d e s i g n , t o pr e di c t i on
of t h e p e r f o r ma n c e of t h e T R I S O cp a nd t o e va l ua t i on
of t h e Si C f a br i c a t i on p r o c e s s . T h e br i t t l e r i ng test
1
-
9
-
1
wa s us e d t o me a s u r e t h e me c ha ni c a l p r o p e r t i e s . T h e
de t a i l s of t he me a s u r e me n t wa s a l s o gi ve n in t he l i t -
erature
1
-
8
-
1
wi t h t he ma i n r e s u l t s ci t ed in Ta b l e 2.
2. 4 Ur ani um c ont ami nat i on of t he Si C l ayer
Ur a n i u m c o n t a mi n a t i o n wo u l d c e r t a i nl y c on-
t r i b u t e t o t h e r e l e a s e of f i ssi on p r o d u c t s f r om t he Si C
l a ye r u p o n i r r a d i a t i o n , b e c a u s e f i ssi on r e a c t i o n s wo u h
oc c ur i ns i de t h e Si C l a ye r d u r i n g r e a c t o r o p e r a t i o n
a n d wo u l d c a us e s e r i ous d a ma g e t o i t s s t r u c t u r e a nd
p r o p e r t i e s . Na u mi d i s et al
[ 1 0 ]
d e t e r mi n a t e d t h e ur a ni -
u m t r a n s p o r t t h r o u g h t he c o a t i n g l a ye r s of BI SO c p.
Table 2 ' Effect of temperature on the mechanical properties
deposition t emper at ur e/ C
st rengt h a
average val ue/ MPa
median val ue/ MPa
standard deviation s/ MPa
(s/tfo) X100
Weibull par amet er / m
<Vo.oooi/MPa
elastic modulus E
average val ue/ GPa
standard deviation s/GPa
s/E/%
1450 1500 1 550 1 600 1 650
670
659
146
22
5.4
31
392
188
48
1 285
1 282
233
17
6.4
124
455
107
24
1 447
1 412
269
19
6.6
153
422
111
26
783
780
153
21
5.8
63
330
172
52
693
680
214
31
4.1
19
330
118
36
* the allowable strength of the SiC layer at fracture ratio of 10
48
They found t hat at t emper at ur es as hi gh as 2 000 ' C
ur ani um cont ami nat i on of t he out er dense pyrol yt i c
carbon layer was negligible
1
-
10
-
1
. Since t he SiC layer is
normal l y coated at much l ower t emper at ur es. 1 500 to
1 600 C. diffusion of ur ani um t hr ough t he i nner py-
rolytic carbon layer shoul d be very low, t herefore.
t here is no* much concern about t he pr obl em of ura-
ni um cont ami nat i on of t he SiC l ayer. Duri ng t he
pr epar at i on of t he cp sampl es for t he i rradi at i on ex-
peri ment . ur ani um cont ami nat i on was moni t ored layer
by layer wi t h low backgr ound a- spect r omet er . The
measur ed dat a show t hat t he SiC layer could be con-
t ami nat ed. For exampl e, one bat ch of cp had t he fol-
lowing a-activity dat a: 8.24 X 10
_ 5
Bq/ ( mi n- pa r t i c l e )
for t he buffer layer, bel ow t he det ect i on limit of t he
i nst r ument for t he i nner dense pyrol yt i c carbon lay-
er, 2. 4 X1 0 V (min part i cl e) for t he SiC layer, be-
low t he det ect i on limit of t he i nst r ument for ihe out er
dense pyrol yt i c car bon. The dat a shows t hat t he SiC
layer is seri ousl y cont ami nat ed. The reason for t he u-
rani um cont ami nat i on at such low t emper at ur es is not
clearly known yet. for t he densi t y and t he st r uct ur e of
t he i nner dense pyrol yt i c car bon have met t he TRI SO
cp specifications, per haps t her e is a pr obl em wi t h t he
pur i t y of MTS .
3 Conclusions and Discussion
DI t can be seen from Tabl e 1 t hat t he TRISO cp
wi t h t he specified pr oper t i es can be manufact ured un-
der t he given process par amet er s. The measured re-
sul t s show t hat deposi t i on t emper at ur e has a signifi-
cant effect on t he pr oper t i es of t he SiC layer. The de-
position t emper at ur e shoul d be st ri ct l y controlled at
about 1 500 t o 1 550 C.
2) The measur ed densi t y of t he SiC layer deposi t -
ed at 1 450 C is hi gher t han t he one deposited at 1
500 C. appr oachi ng t he t heoret i cal val ue. However.
mi cr ost r uct ur e obser vat i on revealed t hat t he SiC de-
posi t ed at 1 450 C has a porous st r uct ur e. The mea-
sured s t r engt h and elastic modul us dat a also show
t hat t he SiC layer deposi t ed at 1 450 C is inferior t o
t he one deposi t ed at 1 500 C. Therefore, t he densi t y
measur ement must be in er r or . One expl anat i on could
be t hat t he SiC layer deposi t ed at 1 450 C possesses a
highly developed open pore st r uct ur e so t hat t he
t i t rat i on liquid penet r at es into t he pores and t he mea-
sured densi t y is t he t r ue densi t y i nst ead of an appar -
ent densi t y. Therefore, SiC layers having t he same
measured densi t y may act ual l y have different densi -
ties and specification of t he t hr ee par amet er s: densi -
Tsinghua Science and Technology, March 1996, 1 U) - 4549
ty, t hi ckness, and st andar d deviation of t he t hi ckness,
can not exclusively det ermi ne t he performance of t he
SiC layer under service. As one of t he main quality
cont rol par amet er s, t he measured value of density
must be carefully eval uat ed and should be cross-
checked wi t h ot her charact eri zat i on met hods, such as
mi cr ost r uct ur e observat i on.
3) The surface morphol ogy and t he fracture
st r uct ur e of t he SiC layer are functions of t he deposi-
tion t emper at ur e. The st r engt h and elastic modul us of
t he SiC layer are closely related t o t he surface mor-
phol ogy and t he fracture st r uct ur e. If t he surface
mor phol ogy is smoot her, and t he fracture st r uct ur e is
more homogeneous, t hen t he strength and the elastic
modul us are hi gher.
4) SiC layer may be cont ami nat ed during fabrica-
t i on. The reason is not clear yet . Fission of uranium
in t he SiC layer will seriously damage the structure
i mpai ri ng t he performance under service.
The contamination and subsequent damage may
be anot her reason that specification of the three stan-
dard parameters can not exclusively specify the per-
formance of the SiC layer when irradiated. In manu-
facturing TRISO cp for the HTR-10. uranium con-
tamination should be carefully monitored and efforts
should be made to keep it as low as possible.
Acknowledgement
As guest professor of Tsinghua University, ex-
director of the Institute of Material of Energy Tech-
nology, KFA Juelich, Germany, Prof. Nickel is sin-
cerely acknowl edged for his help in presenting the
50 mm (diameter) fluidized bed and t he uranium ker-
nels for t hi s research. The aut hor s are very grateful
to t he Int ernat i onal At omi c Energy Agency for fi-
nancing t he st udy. The aut hors also owe t hanks t o
t hei r colleagues of t he new materials division and t he
radi at i on safety division of I NET, who helped in mea-
suri ng t he propert i es for t hi s wor k.
References
1 Scott J L. History of coated particles. ANS Transactions,
1975. 170 171
2 Nickel H. Irradiation behaviour of advanced fuel element
for the helium-cooled high temperature reactor ( HTR) .
Juel-spez-565. May 1990
3 Schenk W. Gontard R. Nabielek H. Performance of HTR
fuel samples under high-irradiation and accident simulation
conditions with emphasis on test capsules HFR-P4 and Sl-
Pl . Juel . - 2992. Nov. 1994
4 Gontard R. Nabielek H. Performance evaluation of modern
HTR TRISO fuels. HTA-IB-05/ 90. July 1990, 259-280
Xu Shijiang ( # - f r c ) , et al
:
Research on the Silicon Carbide Layer 49
5 Nickel H. Long-t erm test of HTR fuel elements in the Fed-
eral Republic of Germany. Juel . -spez-383. 1986, 16
6 Voice E. The formation and st ruct ure of silicon carbide py-
rolytically deposited in a fluidized bed of microspheres.
OECD Dragon High Temperat ure Reactor Project, Dorch-
est er, England 1970, 38
7 &mtL, mm*. & m.&mmm#7tft&i+.*^i
56. 1993, 13 ( 4) ; 37-44
Xu Shijiang. Cheng Bihua, Jin Lei. Design of HTR fuel ele-
ment . Chinese Journal of Nuclear Science and Technology.
1993. 13 ( 4) : 37-44
8 Xu S J, Zhu J G, Yang B. Effect of deposition temperature
on the properties of pyrolytic SiC. J Nucl Mater 1995, 224-
12 16
9 Bongartz K. Gyarmati E. Schuster H. et al. The brittle ring
t est : a method for measuring st rengt h and Young' s modu-
lus on coating of HTR fuel particles. J. Nucl. Mater 1979.
62:123 137
10 Gruemeir H B. Wallura E. Beitraege der Roentgen-
mikroanalyse zum Problem des Urant ransport es in
beschichteten Kernbrennstoffeilchen. Beitr. Elektornen-
mikroskop Direktabb. Oberf. 5 (1972) 215 263