Journal of the Australian Ceramic Society Volume 45[1], 2009, 10-12

10

Growth of SiC Whiskers by Carbothermal
Reduction of Mesoporous Silica-Carbon
Composites Infiltrated With SiC Nuclei

Kun Wang
1
, Yi-Bing Cheng
1*
, Huanting Wang
2


1
Department of Materials Engineering, Monash University, Clayton, Victoria 3800, Australia
2
Department of Chemical Engineering, Monash University, Clayton, Victoria 3800, Australia

Email: Yibing.Cheng@eng.monash.edu.au

Available Online at: www.austceram.com/ACS-Journal-2009vol1.asp


Abstract
Mesoporous C-SiO
2
nanocomposite with a low C/SiO
2
molar ratio was infiltrated with polycarbosilane
(PCS) which is a preceramic precursor for silicon carbide. Different silicon carbide nanostructures were
synthesized by carbothermal reduction of mesoporous C-SiO
2
nanocomposites via different heat
treatments. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and
nitrogen adsorption-desorption analysis were used to characterize C-SiO
2
nanocomposites and SiC
products. SiC was not formed in the mesoporous C-SiO
2
nanocomposites without PCS at 1450C.
However, when it was infiltrated with PCS to allow a conversion of PCS into SiC nuclei in the mesopores
during the heat treatment, highly crystalline SiC nanofibers and nanoparticles were produced.

Keywords: mesoporous; carbothermal reduction; preceramic precursor


INTRODUCTION
Silicon carbide is a widely used ceramic material
with attractive properties such as high strength,
stiffness, good wear and corrosion resistance, some
of which are characteristics of a typical covalently
bonded material. SiC materials are commonly
synthesized by chemical deposition (CVD) and
carbothermal reduction reaction using various
starting materials [1-3]. The preparation of high-
quality SiC products requires a set of optimum
synthesis conditions. Firstly, due to the
carbothermal reduction of silica is a heterogeneous
solid-state reaction; the mixing condition of two
reactants greatly influences the properties of SiC
products [4]. Recently, SiC materials with well
defined morphology can be obtained by a C/SiO
2

artefact in a controlled atmosphere [5-6].In our
previews work [7], it was found that SiC
nanoparticles and nanofibers could be successfully
fabricated via carbothermal reduction of
mesoporous carbon-silica nanocomposites.
Meanwhile, a small amount of carbon infiltrated
into the mesopores can significantly change the
partial pressure during the reaction and influence
the microstructures of the SiC products. This paper
presented the formation of SiC nanostructures
obtained from by carbothermal reduction of
mesoporous carbon-silica nanocomposite infiltrated
with and without preceramic precursor. The
objectives here are to understand influences of
seeding in the mesopores on the formation of SiC.
METHODS AND PROCEDURES
Mesoporous silica/carbon composite was prepared
by using our reported method. First, 5 g of H
2
O,
3.28 g of ethanol (anhydrous, Aldrich) and 0.5 g of
1 M HCl (Merck) were mixed in a capped
polypropylene bottle with a magnetic stirrer. To this
solution, 4.1 g of P123 (EO
20
PO
70
EO
20
, MW5800,
Sigma-Aldrich) was added under continuous
agitation to obtain P123 solution. Then 10 g of
tetraethoxysilane (TEOS) (99%, Sigma-Aldrich)
and a given amount (2.35 g) of furfuryl alcohol (FA,
99%, Aldrich) were added into the P123 solution.
The resulting mixture was rigorously stirred at
room temperature for 3 h, followed by aging at
room temperature for 4 days, and drying at 90 C
for 3 days. The black monolith obtained was
carbonized at 550 C for 5 hours with flowing
nitrogen gas, leading to mesoporous C-SiO
2

composites.
To determine the C/SiO
2
ratios of C-SiO
2

composites, thermogravimetric analysis (TGA) was
used to record the mass loss of the samples at a
heating rate of 5 C/min under flowing oxygen. Up
to 700 C all carbon was burned off. The C/SiO
2

ratio was then calculated by taking the total mass
loss as the mass of carbon and the residual mass as
the mass of SiO
2
. The mesoporous C-SiO
2

composites was denoted as 1.01-CS to indicate the
C/SiO
2
molar ratios of 1.01.

11

Kun Wang , Yi-Bing Cheng and Huanting Wang
The mesoporous C-SiO
2
composite was infiltrated
with polycarbomethylsilane (PCS) (MW 800,
Electronic grade, Sigma-Aldrich). 0.5 g PCS was
dissolved in 9.5 g xylene. Then 1 g mesoporous C-
SiO
2
composite was immersed in the solution for 2-
3 hours under stirring, followed by washing with
deionized water and centrifugation, puting into an
oven under 90 C overnight for a drying process.
The sample was labelled as 1.01-CS-PCS to
indicate the 1.01-CS mesoporous host.
The C-SiO
2
composites with and without PCS were
then transferred into a sealed tube furnace equipped
with a vacuum pump. Before heating, the furnace
was vacuumed to evacuate air. To produce SiC, the
C-SiO
2
composites were heated under argon
atmosphere with a flowing rate of 250 ml/min and
at a heating rate of 2 C/min up to 1450 C, and
kept at this temperature for 5 hours. Then be cooled
down to room temperature at a cooling rate of 2
C/min. To investigate the effects of mesopores on
the structure of SiC products, some samples were
preheated at 1200 C for different holding time
before the final temperature.
Thermogravimetric analysis (TGA) (Perkin-Elmer,
Pyris 1 thermogravimetric analyzer) was conducted
at a heating rate of 5 C /min to 700 C. X-ray
diffraction (XRD) patterns were recorded on a
Philips PW 1140/90 diffractometer with Cu K
radiation at a scan rate of 2 /min and a step size of
0.02. Scanning electron microscopy (SEM) images
were taken with a JSM-6300F microscope (JEOL).
Transmission electron microscopy (TEM) images
and selected-area electron diffraction (SEAD) were
taken with a Philips CM20 microscope. The
samples were degassed at 250 C for 5 hours prior
to the measurement. Nitrogen adsorption-
desorption experiments were performed at 77 K by
a Micromeritics ASAP 2020MC. The pore volume
was estimated from the desorption branch of the
isotherm at P/P
0
= 0.98 assuming complete pore
saturation. The pore size distribution was calculated
from the desorption branch of the isotherm by using
Barrett-Joyner-Halenda (BJH) method.

RESULTS AND DISCUSSION
Fig. 1 shows the nitrogen adsorption-desorption
isotherms and pore size distributions of samples
with a carbon/silica ratio of 1.01 infiltrated with
and with out PCS under different heating
procedures. The BET surface area and pore volume
of these samples are summarized in Table 1. When
the mesoporous C/SiO
2
was infiltrated with PCS,
the BET surface area decreased from 530.2750 to
454.2307 m
2
/g, and the peak pore size slightly
varies from 4.3 to 3.9 nm. It indicates a minor
difference in their pore structures. After heat
treatment at 1200 C for 2 hours, the BET surfaces
and pore volume decline dramatically, but the
sample is still mesoporous.
The TEM images of samples with a carbon/silica
ratio of 1.01 infiltrated with PCS before and after
heating procedure are shown in Fig.1. Sample 1.01-
CS-PCS (Fig. 2 a) shows a typical wormhole pore
structure as its precursor [7]. After being heated at
1200 C for 2 hours, the mesoporous structures
have been rearranged.


























Table 1. Nitrogen adsorption-desorption results
samples
BET surface
(m
2
g
-1
)
Peak pore
size (nm)
Pore volume
(cm
3
g
-1
)
1.01-CS 530.2750 4.30 0.568223
1.01-CS-PCS 454.2307 3.80 0.439833
1.01-CS-PCS-
1200/2h
76.8172 3.73 0.075155
















XRD patterns shown in Fig. 3 reveal that both 1.01-
CS heated at 1450 C for 5 hours and 1.01-CS-PCS
heated at 1200 C for 2 hours remain amorphous,
whereas 1.01-CS-PCS-1450/5h, 1.01-CS-PCS-
1200/2h+1450/5h exhibit crystalline structures of
silicon carbide as the diffraction peaks are indexed.
Infiltration of PCS conduces the information of -
SiC phase.
0.0 0.2 0.4 0.6 0.8 1.0
0
50
100
150
200
250
300
350
400


V
o
l
u
m
e

a
d
s
o
r
b
e
d

(
c
m
3
g
-
1
)
P/P
0
1.01-CS
1.01-CS-PCS
1.01-CS-PCS1200/2h
(a) N
2
adsorption-desorption isotherms
(b) Pore size distributions
Fig.1 Samples with a carbon-silica ratio of 1.01
0 2 4 6 8 10 12 14 16 18 20


1.01-CS
1.01-CS-PCS
1.01-CS-PCS-1200/2h
P
o
r
e
-
s
i
z
e

D
i
s
t
r
i
b
u
t
i
o
n
Pore Size (nm)
100 nm
(a) 1.01-CS-PCS (b) 1.01-CS-PCS-1200/2h
Fig. 2 TEM images of 1.01-CS-PCS (a) before and
(b) after heat treatment at 1200 C for 2h
200 nm

12

Journal of the Australian Ceramic Society Volume 45[1], 2009, 10-12
The broad peak centered at about 23, which results
from the residue amorphous carbon and silica,
became weaker when the sample was heated at
1200 C for 2 hours before up to the final
temperature.

















Fig. 4 shows the SEM images of SiC nanoparticles
and nanofibers obtained by precursors infiltrated
with PCS finally heated at 1450 C with and
without preheating. Preheating at 1200 C, which
cause the formation of SiC nuclei by the pyrolysis
of PCS, conduce the formation of SiC nanofibers.
Therefore, there are more SiC fibers in the sample
with a preheating at 1200 C (Fig.4(b)).






























The TEM images of the nanofibers and
nanoparticles are shown in Fig. 5. The SiC
nanofibers possess a high density of planar defects,
stacking faults, which is consistent with the
reported results. The nanoparticles exhibit irregular
shapes with 20-60 nm in size. Selected area
electron diffraction (SAED) patterns in Fig. 5
(insert) confirm that both nanofibers and
nanoparticles are highly crystalline.

CONCLUSION
The use of ordered mesoporous carbon-silica
nanocomposites infiltrated with polycarbosilane
appears to be a promising route to produce highly
crystalline SiC even if the mesoporous precursor
has a very low C/SiO
2
ratio. The pore volume and
pore connectivity of the carbon-silica hosts allow a
good diffusion of the gaseous species during the
carbothermal reduction reaction. Conversion of
polycarbosilane into SiC nuclei induces the
formation of SiC fibers, due to the reaction between
SiC and SiO
2
at lower temperature to generate more
SiO gas.

ACKNOWLEDGEMENT
Thanks the Australian Research Council and Monash
University for the support.

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4 m
(a) 1.01-CS-PCS-1450/5h
4 m
(b) 1.01-CS-PCS-1200/2h+1450/5h
Fig.4 SEM images of samples with a C/SiO
2
ratio of 1.01
infiltrated with PCS under different heating procedures
10 20 30 40 50 60 70 80
SiC SiC
SiC
SiC
1.01-CS-1450/5h
1.01-CS-PCS-1450/5h
1.01-CS-PCS-1200/2h
1.01-CS-PCS-1200/2h+1450/5h
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
2 (Degree)

Fig. 3 XRD patterns of the products obtained from
mesoporous C-SiO
2
composites infiltrated
with/without PCS
a b
Fig. 5 TEM images and SAED patterns (insert) of 1.01-CS-
PCS-1200/2h+1450/5h, (a) nanoparticles and (b) nanofibers