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Kinetics of synthesis of silicon carbide by

carbothermal reduction of silicon dioxide


C. Y. Chen, C. I. Lin, and S. H. Chen

carbide1 have been previously reported. In continuation of


Carbothermal reduction of silicon dioxide in a flowing the previous published research, the eects of the follow-
stream of inert gas was investigated by weight loss ing factors on the reaction rate, namely inert gas flow rate,
measurements, X-ray diVraction, and scanning electron sample size, reaction temperature, SiO /C molar ratio, grain
2
microscopy. T he results obtained indicate that the size of SiO or C, and initial bulk density are reported
2
reaction rate can be increased by increasing either the in the present study. Furthermore, rate equations for the
sample size or reaction temperature. Furthermore, consumption of SiO and C and the production of SiC
2
the reaction rate was found to increase on decreasing were determined. In order to clarify the eect of Fe O on
2 3
the inert gas flow rate, Si/C molar ratio, grain size of the reaction, the eects of the amount and size of Fe O
2 3
silicon dioxide or carbon, or the initial bulk density. particles on the yield of silicon carbide were also studied.
Empirical equations for the consumption rates of SiO
2
and C, as well as the production rate of SiC, were also EXPERIMENTAL PROCEDURES
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determined. T he results also indicate that Fe O acts Helium (Tung-Hsin) with minimum 99% purity was used
2 3
as a catalyst on the reaction and that both the amount for the general reaction work and 9999% argon in the case
and the Fe O particle size may change the degree of of the catalytic study. Reagent grade quartz, obtained from
2 3
influence on the reaction. BCT /365 Strem Co., with a purity of 998% served as the silicon
dioxide source except for the catalytic study where 995%
T he authors are in the Department of Chemical quartz from Johnson Matthey was used. Reagent grade
Engineering, National T aiwan University of Science carbon black, obtained from Strem Co., with a purity of
and T echnology, T aipei, T aiwan 106. Manuscript 995% was used as the general carbon source and 999%
received 19 December 1998; in final form 12 April 1999. graphite from Merck in the catalytic study. Reagent grade
Fe O obtained from Kobayashi, was employed as additive
2000 IoM Communications L td. 2 3
in the catalytic study.
Quartz and carbon powders were initially dried in a
nitrogen stream at 50C and then screened separately.
INTRODUCTION Grains of quartz and carbon within the range 325/350 mesh
Synthesis of silicon carbide by carbothermal reduction (4143 mm) were used. Silicon dioxide and carbon powders,
with known molar ratios, were mixed in a beaker for 12 h
SiO (s)+3C(s)=SiC(s)+2CO(g) . . . . . . (1) (6 h in the catalytic study), using ethanol as the dispersing
2
has been extensively studied. The following three reaction medium. These mixed samples were then dried in a nitrogen
stages were observed to be the most reasonable mechanism stream at 50C, and transferred to an alumina crucible
for the overall reaction.1 24 mm dia. The weights of the solid samples were in the
Initial stage range 15 g.
The crucible containing the solid sample was then placed
SiO (s)+C(s)SiO(g)+CO(g) . . . . . . . (2) in the centre of a horizontal reaction tube. The tube
2
Propagation stage was heated from room temperature to 500C at a rate of
0167 K s1 and from 500C to the desired temperature at
C(s)+SiO(g)SiC(s)+CO(g) . . . . . . . (3)
025 K s1. The temperature was then held constant during
SiO (s)+CO(g)SiO(g)+CO (g) . . . . . . (4) the entire reaction process. Inert gas was passed during the
2 2
C(s)+CO (g)2CO(g) . . . . . . . . . . (5) heat up and reaction stages. The pressure in the alumina
2 tube was maintained at 1 to 3 cm H O higher than atmos-
Termination stage 2
pheric. Finally, the reaction system was shut down once
When either carbon or silicon dioxide is completely the reaction time was reached.
consumed, the entire reaction stops After measuring their weights, the samples were further
calcined in air at 700C for 4 h, and the weights remeasured.
There are some reports on the morphology and size of the The amount of residual carbon present after reaction could
silicon carbide thus produced.14 Reports on the kinetics of then be calculated from the weight loss of the sample. The
the reaction are also numerous.217 The eect of temperature samples were then subjected to X-ray diractometry to
on the reaction rate is the primary focus of many of these determine the silicon carbide content. The weight of residual
reports.5,6,9,11,13,1618 The eects of the following factors silicon dioxide could be calculated from the weight of the
on the reduction rate have, however, been rarely studied: calcined sample and the amount of silicon carbide produced
reaction time,16 inert gas flow rate,13 SiO /C molar by reaction.
2
ratio,16,19 and grain size of SiO or C (Refs. 10, 15). Scanning electron micrographs of the reacted solid
2
There are two reports on the catalytic eect of Fe O on samples were also taken.
2 3
the carbothermal reduction.7,20 Shimoo and Kobayashi20
found that Fe O might promote the reaction while Viscomi
2 3 RESULTS AND DISCUSSION
and Himmel7 found the opposite eect.
Phase transformations of solid samples during reaction,21 The operating variables covered are given in Table 1. The
as well as the eect of contact area on the yield of silicon bold values represent the standard operating variables. This

ISSN 09679782 British Ceramic Transactions 2000 Vol. 99 No. 2 57


58 Chen et al. Kinetics of synthesis of silicon carbide

CONVERSION OF SiO2, XSiO , %


2
YIELD OF SiC, YSiC, %

SOAKING TIME, h
SOAKING TIME, h
1 SiC yield versus soaking time for various helium flow
2 SiO consumption versus soaking time for various helium
rates; reaction temperature 1500?C 2
flow rates; reaction temperature 1500?C
means that whenever the eect of any particular variable is
not studied, then its value is maintained at the bold value
in that series of experiments. Most of the results from the
experiments are presented by plotting the consumptions of

CONVERSION OF C, X C, %
SiO and C, X and X , as well as the yield of SiC, Y
2 SiO C SiC
as a function of 2 time. The consumptions and yield are
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defined as follows
moles of SiO consumed
X 2 . . . . . (6)
SiO2 moles of SiO before reaction
2
moles of C consumed
X . . . . . . . (7)
C moles of C before reaction
moles of SiC produced
Y . . . . . (8)
SiC
moles of SiO before reaction
2
The percentage of Fe O added to the sample is defined by SOAKING TIME, h
2 3
equation (9)
weight of Fe O 100 3 C consumption versus soaking time for various helium
% Fe O added= 2 3 (9) flow rates; reaction temperature 1500?C
2 3 weight of SiO , C, and Fe O
2 2 3
The experimental error was usually less than 5%.
the yield of SiC. According to the aforementioned mechan-
Eect of helium flow rate ism, namely reactions (2)(5), an intermediate gas product
SiO is formed prior to production of SiC, most of which
The eects of helium flow rate on the yield as well as
eventually converts to SiC. However, a small amount of
consumption rates are shown in Figs. 13. It may be
SiO diuses from the solid matrix to the surface and is
observed that, the faster the gas flow, the slower the
carried away by the helium stream. This loss of SiO, though
reaction. The reason for this is that when the flow rate of
small, makes the yield of SiC lower than the consumption
helium is increased, mass transfer through a thinner gas
of SiO . It should be mentioned here that when the soaking
film increases.22 Thus, the product gases SiO(g), CO(g), 2
time was zero, some formation of SiC and conversion of
and CO (g) (equations (2)(5)) are easily removed away
2 SiO and C was observed (Figs. 13). This is due to reaction
from the solid matrix and, consequently, the overall reaction 2
during heat-up period.
rate is reduced. Van Dijen and Metselaar13 reported
opposite results and gave no explanation of this.
If all the consumed SiO is all converted to SiC, then the Eect of sample height
2 The eect of sample height on the yield of SiC is depicted
consumption of SiO , X , should be equal to the yield of
2 SiO2 in Fig. 4. A clear trend was observed: the higher the sample
SiC, Y . However, according to Figs. 1 and 2, the fraction
SiC height, the higher the yield of SiC. When the sample height
of SiO consumed was, under all conditions, higher than
2 is high, the gases SiO and CO cannot easily diuse out,
Table 1 Values of operating variables thereby increasing the concentrations of SiO and CO
in the solid sample and, consequently, reactions (3) and
Variable Value* (4) are accelerated. However, there are no reports in the
literature with which these results of the eect of sample
Helium flow rate, 105 m3 s1 1, 2, 3, 5 height can be compared.
Sample height, mm 7, 10, 16, 20
Reaction temperature, C 1300, 1400, 1500, 1550
SiO /C molar ratio 1/5, 1/4, 1/3, 1/1
Eect of reaction temperature
2 Experiments were conducted at four dierent temperatures,
Grain diameter of SiO , mm 42, 68, 113
2 in the range 1300 to 1500C, and the results are shown in
Grain diameter of C, mm 51, 90, 134
Initial bulk density, kg m3 3395, 4074, 4753, 5772 Fig. 5. It can be seen that increase in reaction temperature
accelerates the reaction. When the reaction temperature
* Bold values are standard operating variables. was <1300C, the yield of SiC was very low. Most investi-

British Ceramic Transactions 2000 Vol. 99 No. 2


Chen et al. Kinetics of synthesis of silicon carbide 59

YIELD OF SiC, YSiC, %


YIELD OF SiC, YSiC, %

SOAKING TIME, h SOAKING TIME, h

4 SiC yield versus soaking time for various sample heights; 7 SiC yield versus soaking time for various grain sizes of
reaction temperature 1500?C silicon dioxide; reaction temperature 1500?C
YIELD OF SiC, YSiC, %

YIELD OF SiC, YSiC, %


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SOAKING TIME, h SOAKING TIME, h

5 SiC yield versus soaking time for various reaction 8 SiC yield versus soaking time for various grain sizes of
temperatures carbon; reaction temperature 1500?C

Eect of grain size


Two series of experiments were performed. In one series,
the mean grain size of the carbon was kept at 51 mm while
YIELD OF SiC, YSiC, %

the grain size of the silicon dioxide was varied as 42, 68,
and 113 mm. In the other series, the grain size of the silicon
dioxide size was kept at 68 mm while the grain size of the
carbon was varied as 51, 90, and 134 mm. The corresponding
results are shown in Figs. 7 and 8, which indicate that the
smaller the grain size of either silicon dioxide or carbon,
the faster is the reaction. However, this eect was very weak
when the grain size was smaller than 68 mm. Shimoo et al.9
and Weimer et al.15 have also reported similar results.

Eect of initial bulk density


SOAKING TIME, h In this series of experiments, four experimental runs with
dierent initial bulk densities of 3395, 4074, 4753, and
6 SiC yield versus soaking time for various SiO /C molar 5772 kg m3 were carried out. The results, shown in Fig. 9,
2
ratios; reaction temperature 1500?C indicate that when the initial bulk density is increased, the
rate of reaction decreases. This is because when the initial
bulk density is increased, the contact areas between SiO (s)
gators have also observed that higher temperature produces 2
and C(s), SiO (s) and SiO (s), or C(s) and C(s) increase
more SiC (Refs. 5, 6, 9, 10, 13, 1618). 2 2
while the areas of SiO (s) and C(s) available for reactions
2
(4) and (3) or (5) respectively decrease. Although the
Eect of SiO /C molar ratio increase in contact area between SiO (s) and C(s) is likely
2 2
The eect of the SiO /C molar ratio on the yield of SiC is to increase the rate of reaction (2) in the initial stage, the
2
depicted in Fig. 6 showing that the lower the molar ratio decrease in areas of SiO (s) and C(s) reduces the rate of
2
the faster the reaction. Furthermore, the eect on reaction reactions (3)(5) in the propagation stage. Since the initial
rate was strong for the ratio 1/1 compared with 1/3 but stage is very short and the propagation stage prevails over
much less so for ratios <1/3. A similar trend has been almost the entire reaction time, the net result is that the
reported by some investigators.9,16 overall rate reduces as the initial bulk density is increased.

British Ceramic Transactions 2000 Vol. 99 No. 2


60 Chen et al. Kinetics of synthesis of silicon carbide

YIELD OF SiC, YSiC, %

SOAKING TIME, h
a
9 SiC yield versus soaking time for various initial bulk
densities; reaction temperature 1500?C

Reaction rate equations


Based on the data obtained, the following equations for the
rates of consumption of SiO and C and the production of
2
SiC were obtained using the regression method
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dC
r = C =76104 exp(412 132/RT )
C dt
d0742 d0549 C0308 C0316 C0046
SiO2 C SiO2 C SiC
r0218 f 0311h0460, mol m3 s1
0
. . . . . . . . (10)
dC b
r = SiO =12104 exp(401 513/RT )
SiO2 dt 2
10 Scanning electron micrographs of reacted solid sample;
d0801 d0392 C0476 C0283 C0077 reaction temperature 1500?C; reaction time 4 h; a no
SiO2 C SiO2 C SiC
r0241 f 0304h0412, mol m3 s1 additive; b with 5 wt%Fe O
0 2 3
. . . . . . . . (11)
to the flow rate are presented by the positive and negative
dC
r = SiC =25104 exp(436 012/RT ) exponents of h and f respectively. When the value of initial
SiC dt bulk density is changed, not only the value of r but
0
d0474 d0315 C0407 C0328 C0013 also the values of C and C are changed. Therefore, the
SiO2 C SiO2 C SiC SiO2 C
eect of initial bulk density cannot be represented by the
r0234 f 0352h0414, mol m3 s1 exponents of r alone.
0 0
. . . . . . . . (12) The rates of consumption of SiO and C and the yield
2
of SiC, as calculated by integrating equations (10)(12), are
where
plotted as solid lines in Figs. 19. Good agreement exists
C =molar concentration of carbon, kg mol m3 between the calculated and the experimental results. These
C
C =molar concentration of silicon dioxide, equations are therefore believed to be helpful for designing
SiO2
kg mol m3 a reactor for this reacting system.
C =molar concentration of silicon carbide,
SiC
kg mol m3 Eect of iron oxide
d =diameter of the carbon grain, m
C Scanning electron micrographs of reacted samples without
d =diameter of the silicon dioxide grain, m
SiO2 Fe O and with 5%Fe O are shown in Fig. 10a and b
f =helium flow rate, m3 s1 2 3 2 3
respectively. It may be observed that the surface of the
h=height of solid sample, m
grains in Fig. 10b is rougher than those in Fig. 10a. Thus,
R=gas constant 8314, kJ kg mol1
more surface area has been generated by the reaction which
T =reaction temperature, K
is consequently promoted further. This observation sup-
t=reaction time, s
ports the mechanism proposed by Shimoo and Kobayashi.20
r =initial bulk density of the solid sample, kg m3
0 Another interesting finding from Fig. 10 is that whiskers
It should be noted here that the rate equations (10)(12) were found in the reacted sample without Fe O addi-
2 3
incorporate in them the rates of chemical reaction, pore gas tion while none were observed in the sample with Fe O
2 3
diusion, and film mass transfer. addition.
It may also be noted that the fact that the reaction rate The eect of addition of dierent amounts of Fe O was
2 3
increases with increase in reaction temperature is fully also investigated by varying the fraction of added Fe O as
2 3
represented by the exponential terms, while the fact that 29, 48, 91, and 167 wt-%, while the size of Fe O grains
2 3
the reaction proceeds faster for smaller grain sizes of silicon was between 200 and 230 mesh (average grain diameter
dioxide or carbon is represented by the negative exponents 67 mm). The reaction temperature was maintained at 900C
of d and d in the rate equations. Other reaction whereas the reaction time was 3 h. The yield of silicon
SiO2 C
characteristics such as the rate of reaction being directly carbide obtained in each run is shown in Table 2. It can be
proportional to the sample size and inversely proportional seen that as the amount of added Fe O was increased, the
2 3

British Ceramic Transactions 2000 Vol. 99 No. 2


Chen et al. Kinetics of synthesis of silicon carbide 61

Table 3 Yield of SiC for dierent sizes of Fe O grains


No addition 2 3
added; reaction temperature 1500?C, reaction
b-SiC
time 3 h
Graphite Average size of
SiO2 (cristobalite) Fe O grain, Yield of SiC, Percentage increases in
2 3
Si-Fe alloy mm Y ,% Y ,%
SiC SiC
None 646 ...
115 872 +350
2.9wt% Fe2O3 added 67 912 +413
42 916 +418
39 916 +419

to produce the siliconiron alloy (Fig. 11), thus reducing


4.8wt% Fe2O3 added the yield of silicon carbide.
In the other series of experiments, the size of Fe O grains
2 3
was varied as 120/140 mesh (average grain diameter
115 mm), 200/300 mesh (average grain diameter 67 mm),
325/350 mesh (average grain diameter 42 mm), and 350/400
mesh (average grain diameter 39 mm), while the amount of
9.1wt% Fe2O3 added added Fe O was kept constant at 48 wt-%, reaction
2 3
temperature at 1500C, and reaction time at 3 h. The results
are presented in Table 3. It can be seen that as the size of
added Fe O was reduced from 115 to 67 mm the yield of
2 3
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silicon carbide increased. However, further reduction to


16.7wt% Fe2O3 added 39 mm showed no additional increase. No literature on this
topic was found. Hence comparison is not possible.

CONCLUSIONS
The rate of carbothermic reduction of silicon dioxide can
be increased by increasing the sample size and reaction
20 25 30 35 40 45 50 temperature. It can also be increased by decreasing the
2h helium flow rate, SiO /C molar ratio, grain size of silicon
2
dioxide or carbon, and initial bulk density.
11 X-ray diraction patterns of partially reacted solid
Based on the experimental data obtained, equations for
samples with various amounts of added Fe O
2 3 the rates of consumptions of SiO and C and the production
2
of SiC have been derived.
yield of silicon carbide also increased initially, reached a Fe O was found to increase the yield of silicon carbide.
2 3
maximum, and then reduced. The optimum amount of The amount and size of Fe O particles were also observed
2 3
Fe O added is thus about 48 wt-%. This diers somewhat to vary the degree of influence.
2 3
from the results of Shimoo and Kobayashi20 who observed
that the rate of reaction increased monotonically with REFERENCES
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2 3 2. . and . : in Proc. Br. Ceram. Soc., (ed.
As has been argued previously, Fe O oxidises carbon
2 3 D. Taylor), 115; 1983, Stoke-on-Trent, British Ceramic
and subsequently provides more surface area (Fig. 10b) for
the reaction, thus accelerating the reaction and increasing Society.
the yield of silicon carbide. However, a reaction between 3. . . , . , and . : J. Mater. Sci.,
1992, 27, 27052712.
Fe O , SiO , and C may produce a SiFe alloy, as shown 4. . , . . , and . . : J. Am. Ceram.
2 3 2
in Fig. 11, which would consume some amount of SiO Soc., 1996, 49, 269375.
2
and reduce the yield of silicon carbide. These two mechan- 5. . . and . . : J. Am. Ceram. Soc., 1972, 55,
isms compete with each other as the factor controlling (8), 414417.
enhancement in the yield of silicon carbide. When the 6. .-. and . . : Ceram. Bull., 1975, 54, (2), 195198.
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2 3
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Fe O addition, Yield of SiC Percentage increases in 14. . . : J. Am. Ceram. Soc., 1992, 75, (1), 170174.
2 3
wt-% Y ,% Y ,% 15. . . , . . , . . , and . . :
SiC SiC
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None 646 ... 16. . , . , . , and . : J. W uhan Univ. T echnol., 1994,
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British Ceramic Transactions 2000 Vol. 99 No. 2


62 Chen et al. Kinetics of synthesis of silicon carbide

19. . , . , . , and . : J. Jpn Inst. 21. . . and . . : J. Mater. Sci. L ett., 1998, 17, 657
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