233

Journal of Nuclear Materials 149 (1987) 233-246

North-Holland, Amsterdam

CHEMICAL VAPOR DEPOSITION OF SILICON CARBIDE FOR COATED FUEL PARTICLES

Kazuo MINATO and Kousaku FUKUDA
Department of Fuels and Materials Research, Japan Atomic Energy Research Institute, Tokai-mura, Ibaraki-ken, Japan

Received 18 July 1986; accepted 9 March 1987

Silicon carbide was chemically vapor deposited on the pyrolytic carbon-coated fuel particles in the fluidized bed reactor
using methyl~c~oros~~e, hydrogen, and/or argon. The coating conditions were varied systematically and the deposits were
examined by X-ray diffractometry. The deposits were found to be /?-Sic, B-Sic + Si and /3-Sic + C depending on deposition
conditions. To understand the CVD processes, the thermodynamic analysis was made on the system of the experiment. The
analysis showed that the deposit compositions at thermodynamic equilibrium were @-Sic and B-Sic + C under the experimental conditions. From these results, a model of the CVD process= was presented based on the mass transfer mechanism. This
model explained the experimental results fairly well.

1. Inborn

Silicon carbide (Sic) prepared by chemical vapor

deposition (CVD) has good m&chart&l properties and
good stability for oxidation. These properties make it
interesting both from scientific and engineering points
of view.
Since Pring and Fielding [l] succeeded in CVD of
SiC in 1909, many studies have been reported on CVD
of Sic [2]. Although Pring and Fielding used benzene
(C,H,), tetrachlorosilane (SiCl,) and hydrogen (H,) as
combination
of methyltrichlorosilane
reactants,
(CH,SiC13 or MTS) and hydrogen is the most popular,
partly because methylt~c~oros~~e
wntains the same
number of silicon and carbon atoms. The main purposes for CVD of Sic are coating of base material to
prevent oxidation, infiltration of porous ceramics to
obtain a dense material, and production of structural
elements such as turbine wheels [2].
Chemical vapor deposition of Sic is also applied to
Triso-coated fuel particles for high temperatures gascooled reactors (HTGR). The microspherical fuel is
surrounded by four layers: porous pyrolytic carbon
(PyC), dense PyC, Sic and another dense RyC. The
function of these layers is to retain fission products
within the particle. In particular the Sic layer acts as a
diffusion barrier to metallic fission products and a
miniature pressure vessel of the particle.
The experimental results by Forthmann et al. 131and
Bullock 14) suggested that diffusion behavior of fission

in the Sic layer depend on ~crost~cture

of
the layer. It is, therefore, important toclarify a relationship between deposition parameters, chemical wmposition and microstructure of the deposits.
For wntro~g
chemical composition and morphology of the deposits and determining the optimum
deposition conditions, it is also important to understand
CVD processes. Chemical vapor deposition processes
are quite complex, where gaseous species react to produce condensed phases and gaseous by-products. Understanding of CVD processes requires a knowledge of
the chemistry of the system, the equilibrium thermodynamic yields, possible chemical kinetic rate-limiting
mechanisms and mass transport processes [S]. Thermodynamic analysis of a CVD system provides a fundamental information wncerning the CVD processes. This
analysis elucidates the limiting equilibrium composition
of the gas phase, the identification of the condensed
phases which would be deposited under this limiting
equilibrium state, and their limiting deposition rates.
Several investigators have applied thermodynamic
calculations to CVD systems and demonstrated the
usefulness of the calculation to understand the CVD
processes [6-g]. In the Si-C-H-Cl
system, on the other
hand, some thermodynamic calculations have been reported 19-141 but these were not fully compared with
the results of the deposition experiments and the CVD
processes were not discussed.
In the present study the experiment and the thermodynamic analysis were made on CVD of Sic in order to
products

0022-3115/87/$03.50 0 Elsevier Science Publishers B.V.

(North-Holland Physics Publishing Division)

234

K. Minato, K. Fukuda / Chemical vapor deposition of SIC

Oolrcc!

Hp

Pyrometer

Exhaust

AI

Fig. 1. Schematic diagram of the coating apparatus.

clarify the effect of deposition

conditions
posits and understand
the CVD processes.

on the de.-

2. Experimental
2.1. Procedure
A schematic diagram of a SiC coating apparatus
used in the present experiment is shown in fig. 1. The
fluidized bed reactor for SIC coating was heated by high
frequency induction
coil. The bed tube of 24 mm in
inner diameter was made of graphite with an inlet

nozzle of 3 mm at the base of a 60 cone. Silicon

carbide was deposited on the PyC-coated uranium dioxide (UO,) particles with a diameter of 780 pm and a
density of 6.0 Mg/m3.
Methyltrichlorosilane
was used as a reactant and
hydrogen and/or
argon as a fluidizing gas. Flow rates
of hydrogen
and argon were measured by ffoat-type
flow meters. Liquid methylt~c~orosilane
was pumped
into the gas stream at constant rates. As can be seen in
fig. 1, the gas stream was heated at about 80 o C in order
to vaporize methyltrichlorosilane
completely.
The gas
stream containing
methyltrichlorosilane
vapor flowed
into the fluidized bed of the particles through a water
cooled line. The by-products
and remaining reactant
gases were removed from the off-gas hne by water
scrubbers.
The temperature
of the fluidized bed was measured
with an optical pyrometer by viewing the inner surface
of the graphite tube through a silica glass window at the
top of the furnace. The condition of fluidization of the
particle was also observed through the window and the
deposition was made under the normal spouting [S]: a
stream of the particles rises rapidly in the center as the
spout, having reached a maximum level, falls back onto
the annular space around the spout and travels downward uniformly as a packed bed.
The experimental
variables in the present system are
temperature,
total pressure, flow rates of me~ylt~c~orosilane, hydrogen and argon, and an amount of feed
particles. In the present experiment the total pressure of
the system was fixed at 0.1 MPa and the amount of feed

Fig. 2. Typical ceramograph of the particle after the coating run (HO625).

235

K. Minato, K. Fukuda / Chemical vapor deposition of SC

particles at 8 g. In order to keep the condition of

fluidization at the normal spouting, the variables cannot
be changed independently. For example, when the temperature is decreased, the total gas flow rate has to be
increased. When the fluidizing gas is changed from
hydrogen to argon, the total gas flow rate has to be
decreased. Under these restrictions the experimental
parameters were varied as systematically as possible.
The coating runs in the present experiment could be
classified into three groups according to the composition of the fluidizing gas: pure hydrogen, mixture of

hydrogen and argon, and pure argon. The deposits

prepared in pure hydrogen and mixture of hydrogen
and argon were examined by X-ray diffractometry. The
samples were obtained by crushing the Sic-coated particles and burning off the PyC layers at 800 o C in air.
Since the deposits prepared in pure argon contained
free carbon, the deposits were examined by X-ray diffractometry and electron probe microanalysis (EPMA).
The samples for X-ray diffractometry were the as-deposited particles and those for EPMA the polished
surfaces.

Table 1
Coating conditions and chemical composition of the deposits
Run No.

H1024
HO612
HOP07
HO918
H1022
HO625
HO709
HO703
H1106
HO619
HO710
HO919
H1113
HO626
HO911
HOP12
HO614
HO306
HO321
Ml213
Ml219
Ml221
Ml222
MO311
MO322
Ml227
Ml101
Ml029
Ml223
Ml031
Ml030
A1212
Al224

Deposits

coating conditions
Bed temp.

Flow rate (mi/min)

(C)

Ar

H2

1700
1700
1700
1700
1600
1600
1600
1600
1500
1500
1500
1500
1400
1400
1400
1400
1300
1200
1150
1600
1500
1400
1300
1200
1150
1600
1500
1400
1300
1200
1150
1600
1300

0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1750
1750
1750
1750
1750
1750
2250
2250
2250
2250
2250
2250
2500
2500

7000
7000
7000
7000
7400
7400
7400
1400
8600
7800
7800
8600
8600
7800
7800
8600
8000
9400
9400
1750
1750
1750
1750
1750
1750
750
750
750
750
750
750
0
0

(H 2 + Ar)/MTS

239
357
504
837
304
378
533
885
294
398
562
1028
294
398
562
1028
409
479
419
2.52
252
252
252
252
252
251
251
251
251
251
251
248
248

Free Si

Free C

(WW

ww

Deposition
rate (mg/s)

0
0
0
0
0
0
0
0
6
0
1
0
24
21
13
22
29
58
66
0
0
3
20
49
57
0
0
0
11
42
54
0
0

0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
39
56

0.655
0.389
0.331
0.130
0.519
0.420
0.282
0.185
0.494
0.382
0.227
0.133
0.427
0.306
0.194
0.103
0.328
0.130
0.027
0.245
0.233
0.181
0.186
0.124
0.078
0.226
0.205
0.172
0.167
0.102
0.069
0.100
0.038

236

K. Minato, K. Fukuda / Chemical vapor deposition of SIC

2.2. Results

Thirty three coating runs were carried out under

various conditions, as listed in table 1. Typical ceramograph of the particle after the coating run (H0625) is
shown in fig. 2.
Pure hydrogen was used as the fluidizing gas in the
bed temperature range between 1150 and 1700 o C (1423
and 1973 K), mixture of hydrogen and argon between
1150 and 16OOC (1423 and 1873 K), and pure argon
between 1300 and 1600C (1573 and 1873 K), as can
be seen in table 1. The deposition rate listed in table 1
was defined as the weight gain of the particles divided
by the coating time.
The results of X-ray diffractometry
indicated
that
main phase of the deposits prepared in pure hydrogen
and mixture of hydrogen and argon was B-Sic and that
some deposits contained
free silicon. Typical X-ray
diffraction
patterns of the deposits prepared in pure
hydrogen are presented in fig. 3. The deposits prepared
at 16OOC (H0919) showed sharp and strong peak of
B-Sic alone, whereas peaks of Si as well as P-Sic were
detected in the deposits prepared at 1400C (H0912).
The compositions
of the deposits were observed
to
change from B-Sic to P-Sic + Si around 1400-1500 o C
(1673-1773
K). The contents
of free silicon in the
deposits
were determined
by X-ray diffractometry,
which are shown in table 1. The content of free silicon
increased with decreasing deposition temperature.
The deposits prepared in pure argon were examined
by EPMA and X-ray diffractometry.
The results of
EPMA indicated that the fraction of carbon atoms was
larger than that of silicon atoms in the deposits, mean-

ing that the deposits contained

free carbon. By the
X-ray diffractometry
on the deposits, P-Sic was detected but free silicon was not. Consequently
the deposit composition
was found to be /?-Sic + C.

3. Thermodynamic

analysis

3.1. Procedure
The computer code SOLGASMIX-PV
[16] was used
in the present study to calculate the equilibrium composition of the system. This procedure is based on the
minimization
of the total free energy of the system,
which was originally developed by White et al. [17] and
extended by Eriksson [l&20] and Besmann [16].
The total Gibbs free energy of a system is given by
the equation
G=

cnig,

= xn,(g,O

+ RT

In a,),

where G is the total Gibbs free energy of a system, R

the ideal gas constant, T the thermodynamic
temperature, n, the moles of chemical species i, g,O the standard chemical potential of species i, and ui the activity
of species i. When ideal conditions are assumed in each
phase, eq. (1) becomes

p=l

r=l

x[(g/RT),,+ln
+

P+ln(n,,/N,)]

i 5 ~p,[(g~/R~)pi+ln(~p~/N,)l
p=2

i=l

q+s+l mp
+

1
p=4+2

1 npr(go/Wplf
r=l

where np, is the moles of species i in phase p, Np the

total moles of species in phase p, mp the number of
species in phase p, and P the total pressure. In eq. (2)
p = 1 corresponds to the gaseous phase, p = 2 - (q + 1)
to the condensed phase solutions, and p = (q + 2) - (q
+ s + 1) to the invariant condensed phases.
The mass of all elements must be conserved:

40

35

30
20

25

ideg)

Fig. 3. Typical results of X-ray diffractometry on the deposits

prepared in hydrogen.

p=l

r=l

c,,,n,i=bj

(_i=l>

2,...,1),

(3)

where cp,, is the number of atoms of element j in

species i in phase p, bj the gram-atoms of element j,
and I the total number of elements.

1% Minato, K. Fukuda / Chemical uupor deposjtion of SC

The
librium
eq. (2)
known

237

set of nPi that minimizes eq. (2) is the equicomposition of the system. To calculate npi in
under the condition of eq. (3), g/RT
must be
and can be expressed by

go/ET=

(l,R)[(G*

- J%),Tj

A,&&RT,
(4)

where (Go - H&)/T

is the free energy function and
A,H&
the heat of formation at 298 K.
To calculate the equilibrium composition for the
CH,SiCl,-H&r
system, 39 gaseous and 4 condensed
species being listed in table 2 were considered. The
necessary values for their free energy function and heat
of formation at 298 K were quoted from JANAF Thermochemical Tables [21] except the values for argon [22].
In the CH,SiCl,-H,-Ar
system, the thermodynamic variables are temperature, total pressure, and
mole ratios of hydrogen to methylt~c~orosilane
(H,/MTS) and argon to hydrogen (ArfH,). The temperature considered here ranged between 1000 and 2200
K. The total pressure was fixed at 0.1 MPa. The ratio of
H,/MTS was varied from 1 to 106.

Hz /

MTS

ratio

4. CVD phase diagram for the H,-MTS

MPa.

system at 0.1

3.2. Results
3.2.1. The CH,SiCI,-H,
system
Variables considered in this system were temperature
and the mole ratio of hydrogen to methyltrichlorosilane
(H,/MTS).
A CVD phase diagram with temperature
and H,/MTS as two ind~endent
variables is shown in
fig. 4. The CVD phase diagram represents specific condensed phases at equilibrium under input conditions.
As can be seen in fig. 4, &Sic would be deposited
under a wide variety of conditions. Carbon would be
codeposited with P-Sic only when H,/MTS value is

2200
2000
1800
1600

(b)

1400
1200
1000
2200

Table 2
Species considered in the calculation

2000
1800

Gas phase
Ar
SiCi,
cc1
CHCl,
CH

SiH
SiCl 4
CCI,
CH,Cl,
CHz

H
SiH,
SiHCI,
ccl,
CH,Cl
CH,

C2H2

c2H.1

Sic

Si

Si,

Cl2

H2

HCI
SiCl
SiH,Cl,
ccl,
C,HCl
CH,
Sic,
Si,

Condensed phase

a-Sic

P-Sic

Si

C (graphite)

Cl
Sic1 2
SiH,Cl
CHCl
CH,SiCl,
C,H
Si,C

1600

Cc)

t400
tzoo
1000

10

lo2

IO3

io4

IO5

i06

Ii, I MIS ratio

5. Efficiency diagrams for the H,-MTS system at 0.1

MPa. (a) Condensed phases; (b) gaseous species containing
Si; (c) gaseous species containing C.

K. Minato, K. Fukuda / Chemical vapar deposition of SC

238

p- SiCt Cls)

1000

10

102

103

/ i
(04

104

106

Ar / MTS rofio

Fig. ft. CVD phase diagram for the &-MIS

molecule of methyltrkhIorosilane
contains an atom of
silicon and an atom of carbon. It was found in the
efficiency diagram that the region where fz-SiC sir&e
phase would be deposited efficiently extended from
1600 to 2000 K in temperature and from 50 to 500 in
H,/MTS. Efficiency diagrams for the gaseous species
containing silicon and carbon are given in figs. 5(b) and
(c)> respectively. The main gaseous species containing
silicon were SiCI,, SiCI,, SiCI,, SiH,CI, SiH,, SiH and
Si. The gaseous species containing carbon was mainly
CH,. The center regions of both of the diagrams where
a small amount of gaseous species exists correspond to
the region where B-Sic would be deposited efficiently.

system at 0.1

MPa,

less than around twenty. Silicon wouId be codeposited

with &Sic at high H-JMTS values.
Isoefficiency fines for the condensed phases are depicted in fig. S(a). The efficiency was defined as m&es
of species i which exist at thermodynamic equilibrium
divided by moles of input methyltrichlorosiIane, since a

2200
1800

I , 1 / I / I , ( , 1 / 1 I 1 I 1j 1
(Hz t Ar)/MTS:
10

2000
(0)

1600

)j-SiCtC(<)

1800

1400

ibl

B-Sic

1600

tl

1200

Ib)

1800

cc;,

4:S;C:;illl

1600-b

sc

B-Sic

i(q

k)
@-SiCtCi;)

t400

i
1200
Ar / MTS

raito

l*ooO

10

20

30

40

Ar/iHzt
Fig. 7. Efficiency diagrams for .the Ar-MTS
system at 0.1
MFa. (a) Deposition of &Sic; (b) gaseous species containing
Si.

50
Ar)

60

70

80

90

KKJ

(%I

Fig. 8. CVD phase diagrams for the H,-Ar-MTS

0.1 MPa.

system at

K. Minato, K. Fukuda / Chemical vapor deposition of Sic

3.2.2. The CH,SiCl,-Ar system

Variables considered in this system were temperature
and the mole ratio of argon to methylt~c~oros~ane
(Ar/MTS). A CVD phase diagram is shown in fig. 6.
The region where @-Sic single phase would be deposited did not exist. Carbon would be always codeposited with fl-Sic. Carbon single phase would be deposited at high temperatures and high Ar/MTS values.
An efficiency diagram for the deposition of P-Sic is
presented in fig. 7(a). Since almost all the carbon atoms
would be deposited as C or Sic, this diagram represents
the content of &Sic in the deposite. The content of
B-Sic depends on temperature as well as Ar/MTS as
indicated in fig. 7(a). An efficiency diagram for the
gaseous species cont~~g
silicon is shown in fig. 7(b).
The main gaseous species were SiCI,, SiCI,, SiCl, and
Si.
3.2.3. The CH$iCl,-H,-Ar
system
Variables considerd in this system were temperature,
the mole ratio of hydrogen plus argon to methyltrichlorosilane ((Hz + Ar)/MTS), and that of argon to hydrogen plus argon (Ar/(H, + Ar)). Fig. 8 shows CVD
phase diagrams with temperature and Ar/(H, + Ar) as
two independent variables. These diagrams indicate an
important role of hydrogen in the CVD processes. When
Ar/(H, + Ar) value becomes large or concentration of
hydrogen becomes low, compositions of the deposits
will change from &Sic to B-Sic + C or from B-Sic + Si
to B-Sic depending on temperature and (H, + Ar)/MTS
value.

4. Modeling of CVD prmxsses

4.1. General concept
Although CVD processes are very complicated, Jones
and Shaw [23] and Jones [24] have described the
processes occur through a series of sequential steps: (1)
transport of the reactive species to the deposition regions, (2) transfer of the species from the main gas
stream to the deposition surface, (3) adsorption of one
or more reactants, and possibly of non-reactive species,
(4) chemical reaction either between adsorbed species
or adsorbed and gaseous species, (5) desorption of reaction products, (6) transfer of the products to the main
gas stream and (7) transport of the products away from
the deposition region.
Steps (l), (2), (6) and (7) are mass transport processes
in the vapor, whereas steps (3), (4) and (5) are surface
kinetic processes. Among these steps, the slowest step

239

limits the deposition rate. When chemical kinetic steps

are rapid, mass transfer is a possible rate-limiting step
and thermodynamic equilibrium is achieved on the substrate surface. On the contrary, when mass transfer step
is rapid, chemical kinetics is a possible rate limiting
step.
4,2. Mass transfer rate-limiting step
It is assumed that gaseous species are transferred
from bulk gas stream to the substrate through the
laminar boundary layer [25] and that the deposition rate
is proportional to the diffusion flux of the species:
r= FJ,

(5)

where r is the deposition rate, F the proportionality

constant, and J the diffusion flux through the boundary
layer.
For gaseous species i in fluidking gas j, the diffusion flux is given by Ficks law
Ji = Djj dC,/dx,

(6)

where J;: is the flux of species i through the boundary

layer, Dij the binary diffusion coefficient for the species,
and dC,/dx the concentration gradient of species i.
The binary diffusion coefficient can be given by the
expression [26]

where A is the proportionality constant, P the total

pressure, T the thermodynamic temperature, and M,
and Mj the molecular weights of species i and j,
respectively.
When a uniform concentration gradient is assumed
across the boundary layer and the concentration is
converted to partial pressure through the ideal gas law,
the concentration gradient of species i is expressed by
dCi/dx=

(tit -8 Pi)/RTL,

(8)

where bpi is the partial pressure of species i in the bulk

gas, spi the partial pressure of species i at the deposition surface, R the ideal gas constant, and L the
thickness of the boundary layer. When chemical kinetic
step is rapid and the diffusion of gaseous species through
the boundary layer is rate-limiting step, the partial
pressures of species i in the bulk gas and at the deposition surface are considered to be those in the input gas
and at thermodynamic equilibrium, respectively.
The thickness of the boundary layer can be given by

K. Minato, K. Fukuda / Chemical vapor deposition of Sic

240
the equation

Substitution

[27]

of eqs. (6)-(12)

into eq. (5) leads to

~~l/2~0.75-m,'2
I.=

where B is the proportionality

constant, p the viscosity,
d the diameter of the particle, p the density of the fluid,
and u the linear velocity of the fluid.
The viscosity of fluid j is dependent on the temperature and can be evaluated approximately
by the expression [23]
/.L,= GjT,

where Z is the proportionality

constant.
When mass
transfer is the rate-limiting
step, the deposition rate is
considered to be expressed by eq. (13).

(10)

where G, is the proportionality

constant and m the
empirical constant which varies between 0.6 and 1.0.
When the ideal gas law is assumed, density of the
fluid is proportional
to the total pressure and inversely
proportional
to the temperature:

p=--

PM,

5. Discussion
5.1. Comparison
namic analysis

Linear velocity is proportional

to the volumetric flow
rate and temperature
and inversely proportional
to the
total pressure:

(12)
where E is the proportionality
input volumetric flow rate.

constant

and

1200
t

L
1

p-SIC+

Q the

.
.

C(s)

~
B

G+
&

B-Sic

data with thermody-

The experimental
results of the present study together with the calculated CVD phase diagram for the
CH,SiCl,-H,
system are shown in fig. 9, where the
experimental
results quoted from the literature [28-41)
are also plotted. The total pressure of the system was
0.1 MPa in this presentation.
The results by fluidized
bed reactors [33-411 were distinguished
from those by
fixed bed reactors [28-321 in fig. 9. Among the fixed
bed reactors, one [32] was hot wall arrangement
and the
rest [28-311 cold wall arrangement.
Horizontal bars in
fig. 9 indicate estimated ranges of H,/MTS
values.
The deposit compositions
of the present experimen-

(11)

RT .

of experimental

/
L________________J
r-Si t C(s)
__
PP-Sic
_
&-Sic+ Sits)
lo2

10
H2 /MTS

This work

fluidized
fixed bed
bed reocta rector
.
.
0
0
___._
q
@
.

I&

lo3

ratio

Fig. 9. Comparison of the experimental results including those quoted from the literature 128-411 with the calculated CVD phase
diagram for the H,-MTS system at 0.1 MPa.

241

K. Minato, K. Fukuda / Chemical vapor deposition of Sic

tal results were @-Sic + Si and B-Sic depending on the

bed temperature as seen in fig. 9. On the other hand, the
calculated CVD phase diagram indicated that the deposit composition at thermodynamic equilibrium was
P-Sic under the present experimental conditions. The
experimental results above 1500 C (1773 K) agreed
with the thermodynamic
analysis but those below
1500 C (1773 K) did not.
The deposit compositions of the experimental results
from the literature [28-411 were P-Sic + C, B-Sic + Si
and j&Sic as shown in fig. 9. Under the conditions
where thermodynamic equilibrium composition was BSic + C, the deposits of P-Sic + C and /i-Sic were
obtained experimentally. The former experimental composition agreed with the thermodynamic analysis. The
latter result conflicted with the analysis, but the deposit
composition might be P-Sic + C since under these conditions the calculated content of free carbon was less
than 5%, as revealed in fig. 5(a), which is near the
detectable limits by X-ray diffraction technique. Under
the conditions where the equilibrium composition was
/3-Sic, B-Sic + C was deposited at higher than 2000 K,
P-Sic between 2000 and 1700 K, and p-Sic + Si at
lower than 1700 K. The same tendency was also observed in other experiments [42-471, but these results
could not be plotted in fig. 9 due to the lack of
H,/MTS values in these reports.
The experimental results of the present study together with the calculated CVD phase diagram for the
CHsSiCl,-H,-Ar
system are given in fig. 10. When the
fluidizing gas was pure argon, the deposit composition
in the experiment was /I-Sic + C, which was consistent
with the thermodynamic analysis. When the mixture of
hydrogen and argon was used as the fluidizing gas, the

2coo-

deposits of &Sic and B-Sic + Si were obtained experimentally though the equilibrium composition was /I-Sic.
This is the same tendency as that seen in fig. 9. The
experimental results above 1400 C (1673 K) agreed
with the thermodynamic
analysis but those below
1400 C (1673 K) did not.
The experimental results from the literature [33,34,48]
together with the calculated CVD phase diagrams are
shown in figs. 11(a) and (b). When the fluidizing gas
was pure argon in figs. 11(a) and (b), the deposit
composition of the experimental results was P-Sic + C,
which agreed with the thermodynamic analysis. When
the fluidizing gas composition (Ar/(H, + Ar) was 50%
in fig. 11(a), the deposit composition of the experimental results was B-Sic though the equilibrium composition was B-Sic + C. This disagreement may be attributed to the small content of free carbon. When Ar/(H,
+ Ar) was 25% in fig. 11(b), the experimental results
were consistent with the analysis. When Ar/(H, + Ar)
was 75%, the experimental results agreed with the analysis except one result. This disagreement was considered
to be caused by the small content of free carbon.
As described above, the experimental results were in
agreement with the present thermodynamic analysis ex-

(H2tAr)/MTS.250

OoOo10

20

30

40

50

Ar/(HZ+Arl

60

70

80

90

100

1%)

Fig. 10. Comparison of the present experimental results with

the calculated CVD phase diagram for the H,-Ar-MTS
system at 0.1 MPa.

Ar /(l+tArl

1%)

Fig. 11. Comparison of the experimental results quoted from

the literature [33,34,48] with the calculated CVD phase diagrams for the H,-Ar-MTS
system at 0.1 MPa.

242

K. Minato, K. Fukuda / Chemical vapor deposition oj SC

cept two points: (1) free carbon was codeposited with

@-Sic at higher than 2000 K though the equilibrium
com~sition
was &Sic
and (2) free silicon was
codeposited with &Sic at lower than 1700 K though
the equilibrium composition was P-Sic. These conflicting points are of importance to consider the deposition
processes.

eq. (15). These reactions result in a decrease in Sic

deposition efficiency. Silicon is codeposited with SiC
depending on temperature at high concentration of
hydrogen. If the concentration of hydrogen is too high,
no condensed phase is obtained.

5.2. Chemistry of the system

Es. (13) in section 4.2 was modified to be applied to

the observed deposition rates. Due to the definition of
the observed deposition rate, the diameter of the particles was assumed to be constant though it actually
grew from 780 pm to about 860 pm. The assumption
yields an error of less than 5%. The total pressure of the
system was 0.1 MPa in all the coating runs and the
empirical constant m was found to be 0.64 both for
pure hydrogen and for a mixture of hydrogen and argon
(see Appendix). Finally eq. (13) is reduced to

Based on
analysis, the
ered.
Although
CHsSiCl, is
CH,SiCl,(g)

the results of the present thermodynamic

following chemical processes were considthe overall equation to produce Sic from
expressed by
-+ Sic(s)

+ 3HCl(g),

(14)

sufficient hydrogen is necessary to obtain the deposit of

pure SIC. From inspecting the results of the thermodynamic calculation, the reaction processes are considered
to be divided into three steps. In the first step, molecules of CH,SiCl, are thermally decomposed into intermediate gaseous species of hydrocarbon and silicon
chloride. In the second step, hydrocarbon is thermally
decomposed into elemental carbon and hydrogen:
CH,-+C+2H,,

(15)

and silicon chloride is reduced by hydrogen to produce

elemental silicon and hydrogen chloride:
SiCl, + H, -+ Si + 2HC1,
SiCl, + $H, -+ Si + 3HC1,
and
SiCl, + 2H, --, Si + 4HCl.

(16)

In the final step, carbon and silicon atoms combine to

form Sic.
If the concentration of hydrogen is low, the reaction
of eq. (15) exceeds the reactions of eq. (16), and consequently carbon is codeposited with Sic. That is the case
at low H,/MTS values in the CH,SiCl,-Ha
system
and in the CH,SiCl,-Ar
system. If the concentration of
hydrogen is adequate, pure Sic is deposited efficiently.
If the concentration of hydrogen is high, elemental
silicon is further reduced by hydrogen:
Si + $H, + SiH,
Si + 2H, + SiH,,
and
Si + HCl+ H, + SiH,Cl.
(17)
The high concentration of hydrogen also prevents the
formation of elemental carbon through the reaction of

5.3. Application of the model to the experimental data

r=Kf

(18)

and

f = Q12Z-0.43(gSi -s psi)
%Ei*,

(19)

where r is the deposition rate, K the proportionality

constant, b~si the partial pressure of CH,SiCl,
in the
input stream, *psi the sum of the equilibrium partial
pressure of Si containing species, Msi the molecular
weight of SiCl,, MH,_Ar the apparent molecular weight
of the fluidking gas, and GH2_AI the constant of the
fluidizing gas. The equilibrium partial pressure were
calculated in section 3.2 and the constant GH2_Ar were
evaluated in the Appendix.
The observed deposition rates are plotted as a function of f in fig. 12. According to the model, thermodynamic equilibrium is achieved at the deposition surface
when mass transfer is the rate-limiting step, and the
the~~yna~~
analysis indicated that the deposit wmposition was B-Sic at equilibrium under these experimental conditions. This means that eq. (18) can be
applied only to the coating runs which yielded P-Sic.
The straight line was fitted to the data of those coating
runs by the least squares method and the slope K was
found to be 2.54. In the coating runs which yielded
@-Sic + Si, the deposition rates were considered to be
controlled by chemical kinetics and the thermodynamic
equilibrium was not achieved at the deposition surface.
It can be seen in fig. 12 that the proposed model
explained the experimental results fairly well.
The details of the model will be verified in the

K. Minato, K. Fukuda / Chemical vapor deposition of SC

1.0r-I

0.8 11
2

0.6

0.6.

.-z

c6
0
[3

0.4

z
::
a0 0.2

0.2

ov

0
Funciion

, .
0.1
f

0.2

,
/ .
/ H2 : 7000 ml /min

0.3

MTS/(HptMTS)

.$/I
$y
.A /

3 I #
,/ l
1 8

aJ
0
mo.4

n
.g

17OOC (197310
/

-Irl
F

0.8.

F
2

243

( a31

Fig. 14. Comparison of the experimental results with the mass

transfer rate-limiting model as a function of partial pressure of
MTS in the input stream.

( Mm. kg.5. K0.75/~2)

Fig. 12. Comparison of the experimental results with the mass

transfer rate-limiting model.

deposited only in the presence of the thermodynamic

limitation: (equilibrium limit) = (mass flow rate of
MTS) x (molecular weight of SiC/molecular weight of
MTS) x (the efficiency of deposition of B-Sic defined
in section 3.2). In these figures the observed deposition
rates are smaller than the thermodynamic equilibrium
limits, meaning that other mechanisms limited the deposition rates. The observed deposition rates were more
dependent on temperature at the lower temperatures
than those at the higher temperatures. This indicates
that two mechanisms controlled the deposition rates: at
the higher temperatures the observed deposition rates
were controlled by mass transfer and chemical kinetics

following. When the temperature is the only variable

and the other parameters are held constant in eq. (19),
the deposition rate is expressed by
r=K,T0.43(#Si-sPsi),

(20)

where K, is the proportionality constant. Eq. (20) is

compared with the observed deposition rates in fig. 13,
where the limit of deposition rate by the thermodynamic equilibrium is also presented. The limit of deposition rate by the thermodynamic equilibrium was
defined as the deposition rate at which Sic would be

Temperature

0.5 - ------

0,
z

(Kl

eg_ilibrium
_-__---_--_

mass transfer
9 .
. .

0.05 - H2 : 7000-9400
Hz/MTS:357-479

E
c3

0.02 -

0.1 :

E
.6

mass transfer
l
.

.
.

ml/min
.

H2 : 1750 ml/min
Ar : 1750 ml/min
(H2tAr)/MTS:252

1 /T

H2 : 750 ml/min
Ar : 2250 ml/min
(H2tArVMTS:25i

( l0-4/K)

Fig. 13. Comparison of the experimental results with the mass transfer rate-limiting model as a function of temperature.

244

K. Minato, K. Fukuda

/ Chemical oapor deposition of Sic

possibly controlled the deposition rates at the lower

temperatures.
When the partial pressure of the reactant is the only
variable in eq. (19) the deposition rate is given by the
equation
=Kp(bPSi-sPSi)~

(21)

where K, is the proportionality constant. The observed

deposition rates are shown in fig. 14 as a function of the
mole ratio of MTS/(H, + MTS) or the partial pressure
of MTS in the input stream. The equilibrium partial
pressure spsi is negligible in this case as revealed in fig.
5. It can be seen in fig. 14 that the observed rates agreed
with the mass transfer rate-limiting model.
According to eq. (19X the dependence of deposition
rate on composition of the fluidking gas is expressed by

r=Kc

-L

MSi

+ &)lz(

z)l*,

(22)

where K, is the pro~rtiona~ty

constant. The observed
rates at 1600C (1873 K) are plotted in fig. 1.5 as a
function of the mole ratio of Ar/(H, + Ar) or composition of the fluidking gas. It can be seen again in fig. 15
that the observed deposition rates agreed with the proposed mass transfer rate-limiting model.

0.2
1;

(H2tAr)/M~~~

6. Conclusions
Silicon carbide was chemically vapor deposited on
the PyC-coated fuel particles in the fluidized bed reactor using methyltrichlorosilane, hydrogen, and/or argon.
The coating conditions were varied systematically and
the deposits were examined by X-ray diffractometry. To
understand the CVD processes, the thermodyna~c
analysis was made on the system of the experiment and
the model of the CVD processes was proposed. From
the experiment and the analysis, the following was
concluded:
(1) When the fluidizing gas was pure hydrogen and the
ratio of H,/MTS ranged from 239 to 1028, /?-SIC
single phase was deposited between 1500 and
1700C (1773 and 1973 K) and free Si was
codeposited with &Sic between 1150 and 1500 C
(1423 and 1773 K). The former result agreed with
the thermodynamic analysis but the latter did not.
(2) When the fluidking gas was mixture of hydrogen
and argon and the ratio of (Hz + Ar)/MTS was
around 250, j&Sic single phase was deposited between 1400 and 16OOC (1673 and 1873 K) and
free Si was codeposited with P-Sic between 1150
and 1400 o C (1423 and 1673 K). The former result
agreed with the thermodynamic analysis but the
latter did not.
(3) When the fluidking gas was pure argon and the
ratio of Ar/MTS was 248, free C was codeposited
with P-Sic at 1300C (1573 K) and 16OOC (1873
K). This result agreed with the thermodynamic
analysis.
(4) The proposed model of the CVD processes, which
was based on the mass transfer mechanism, explained the experimental results fairly well.

Appendix

0.6

Viscosities of pure hydrogen and argon were calculated by the equation 1491

(H2tArl/MTS:251

0.6

(A.1)

Ar /

( H, t Ar 1

Fig. 15. Comparison of the experimental results with the mass

transfer rate-limiting model as a function of composition of the
fluidking gas at 1600 C (1873 K).

where (1 is the viscosity (FPa . s), r. the characteristic

diameter of the molecule (A}, h4 the molecular weight
of the gas (g), e the characteristic energy of interaction
between the molecules (J), k the Boltzmann constant
(J/K), T the thermodynamic temperature (K), and f a
function of kT/e. The necessary values to calculate the
viscosities were tabulated in ref. 1491.

245

K. Minato, K. Fukuda / Chemical vapor deposition of SC

Viscosities of mixture of hydrogen and argon were

calculated by the equation [49]
P2

Pl

(A.21
pm

1+

(X2/XJcp12

1-e

temperatures. The viscosities of the fluidizing

therefore, can be expressed by

gases,

/.+, = 0.236 x To.a

(pPa.s),

(A.51

pAr = 0.645 x To.64

(@a.~),

(A4

~O.SH,+O.SAr

(pPa.s),

(A.7)

(PPaes).

(A.81

(x,/x2)92,.

where p,,, is the viscosity of the mixture, p, and p2 the

viscosities of pure components 1 and 2, respectively, Xi
and X2 the mole fractions of components 1 and 2,
respectively, and +i2 and cp2i the functions of molecular weights and viscosities of the pure components
which are given by

0.602

To.@

and
~0.25H2+0.75Ar

oh33

To.64

Acknowledgments

and

(A4
The results of the calculation are shown in fig. 16.
This figure indicates that the empirical constant m for
the fluidizing gases was about 0.64 around the discussed

The authors wish to express their thanks to Dr. K.

Iwamoto and Dr. T. Kondo, former and present Director of Department of Fuels and Materials Research of
Japan Atomic Energy Research Institute, for their interest and encouragement. Thanks are also due to Dr. K.
Ikawa, former General Manager of Fuel Irradiation and
Analysis Laboratory, and Dr. T. Ogawa, Research
Engineer of the Laboratory, for their advice on the
experiment and analysis.

References
100

PI J.N. Pring and W. Fielding, J. Chem. Sot. 95 (1909) 1497.

PI J. Schhchting, Powder MetaII. Int. 12 (1980) 141,196.

90
80
70
60

50

a
=G
40
A
c
::
u
.z
>
30

20

Temperoture (K)
Fig. 16. Evaluated viscosities of the fhtidizing gas as a function
of temperature.

131 R. Forthmann, E. Gyarmati, J. Linke and E. WaIlura,

High Temp.-High Press. 14 (1982) 477.
141 R.E. Bullock, J. Nucl. Mater. 125 (1984) 304.
151 K.E. Spear, in: Chemical Vapor Deposition 1979, Eds.
T.O. Sedgwick et al. (The Electrochemical Society, Princeton, 1979) p. 1.
161 T.M. Besmann and K.E. Spear, J. Electrochem. Sot. 124
(1977) 786.
171 M. Ducarroir and C. Bernard, J. Ehxtrochem. Sot. 123
(1976) 136.
PI P.E. Freund and K.E. Spear, J. Less Common Mater. 60
(1978) 185.
[91 S. Minagawa and H.C. Gatos, Japanese J. Appl. Phys. 19
(1971) 844.
[lOI M. Turpin and A. Robert, Proc. British Cer. Sot. 22
(1973) 337.
1111 F. Christin, R. Nastain and C. Bernard, in: Chemical
Vapor Deposition 1979, Eds. T.O. Sedgwick et al. (The
EIectrochemicaI Society, Princeton, 1979) p. 499.
WI A.I. Kingon, L.J. Lutz, P. Liaw and R.F. Davis, J. Am.
Ceram. Sot. 66 (1983) 558.
[I31 G.S. Fischman and W.T. Petuskey, J. Am. Ceram. Sot. 68
(1985) 185.
1141 D. Selbmann, E. Wolf, M. Schonherr and A. Leonhardt,
Krist. Tech. 13 (1978) 395.

246

K. Minato, K. Fukuda / Chemical vapor deposition of Sic

[IS] C.F. Wallroth, Xl-669-RW

(1970).
1161 T.M. Besmann, ORNL/TM-5775 (1977).

[17] W.D. White, SM. Johnson and G.B. Dar&zig, J. Chem.

Phys. 28 (1958) 751.
[18] G. Eriksson, Acta Chem. Stand. 25 (1971) 2651.
[19] G. Eriksson and E. Rosen, Chemica Scripta 4 (1973) 193.
[20] G. Eriksson, Chemica Scripta 8 (1975) 100.
[21] D.R. Stull and H. Prophet, JANAF Thermochemical
Tables, Second Edition (1971), 1974 Supplement (1974),
1975 Supplement (1975), and 1976 Supplement (1976).
1221 R. Hultgren, P.D. Desai, D.T. Hawkins, M. Gleiser, K.K.
Kelley and D.D. Wagman, Selected Values of the Thermodynamic Properties of the Elements (American Society
for Metals, Metals Park, 1973).
(231 ME. Jones and D.W. Shaw, in: Treatise on Solid State
Chemistry, Vol. 5, Ed. N.B. Hannay (Plenum Press, New
York, 1975) p. 283.
[24] D.W. Shaw, in: Crystal Growth - Theory and Techniques, Vol. 1, Ed. C.H.L. Goodman (Plenum Press, New
York, 1974) p. 1.
[25] T.M. Besmann and K.E. Spear, J. Electrochem. Sot. 124
(1977) 790.
1261 E.N. Fuller, P.D. Schettler and J.C. Giddings, Ind. Eng.
Chem. 58 (1966) 19.
[27] R.B. Bid, W.E. Stewart and E.N. Lightfoot, Transport
Phenomena (John Wiley & Sons, New York, 1960).
1281 W. von Mbnch and E. Pettenpaul, J. Electrochem. Sot.
125 (1978) 294.
[29] A.C.W. van Kemenade and C.F. Stemfoort, J. Crystal
Growth 12 (1972) 13.
[30] N. Setaka and Z. Inoue, J. Am. Ceram. Sot. 52 (1969) 624.
1311 M. Bomrke and E. Fitzer, Ber. Dtsch. Keram. Ges. 43
(1966) 180.

1321 F. Kobayashi, K. Ikawa and K. Iwamoto, J. Crystal

Growth 28 (1975) 395.
[33] A. Naoumidis, R. Benz and J. Rottmann, High
Temp.-High Press. 14 (1982) 53.
[34] E. Gyarmati and H. Nickel, Jlil-900-RW (1972).
[35] R.J. Lauf and D.N. Broski, ORNL/TM-7209 (1980).
[36] R.J. Lauf and D.N. Broski, ORNL/TM-7571 (1981).
137) E. Erben and H. Hausner, EUR-4946e (1973).
[38] L.H. Ford, D.E. Walker and F. Furguson, in: Special
Ceramics 5, Eds. P. Popper et al. (The British Ceramic
Research Association, 1972) p. 49.
[39] M. Akita, T. Iseki and H. Suzuki, Bull. Tokyo Inst.
Technol. 127 (1975) 83.
[40] E.H. Voice and V.C. Scott, in: Special Ceramics 5, Eds. P.
Popper et al. (The British Ceramic Research Association,
1972) p. 1.
[41] L.H. Ford, N.S. Hibbert, B.E. Ingeby and D.E.Y. Walker,
TRG-R 1544(s) (1967).
[42] P. Krautwasser, G.M. Begun and P. Angelini, J. Am.
Ceram. Sot. 66 (1983) 424.
[43] T.D. Gulden, J. Am. Ceram. See. 52 (1968) 424.
[44] R.J. Weiss and R.J. Dienfendorf, in: Silicon Carbide 1973,
Eds. R.C. Marshall et al. (U~ver~ty of South Carolina
Press, Columbia, 1974) p. 80.
[45] F. Holub, SGAE EBR, No. 2195 (1973).
[46] J.I. Feder, Thin Solid films 40 (1977) 89.
[47] M.J. Chappel and R.S. Millman, J. Mater. Sci. 9 (1974)
1933.
1481 R. Forthmann and E. Gyarmati, J. Nucl. Mater. 58 (1975)
189.
[49] L.A. Bromley and C.R. W&e, Ind. Eng. Chem. 43 (1951)
1641.