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CERAMICS
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Ceramics International 40 (2014) 1261312616
www.elsevier.com/locate/ceramint

Short communication

Synthesis and characterization of nanostructured silicon carbide crystal

whiskers by solgel process and carbothermal reduction
Bin Lin, Yong-Cai Song, Chang-Rui Zhang, Jin-Shan Yu
State Key Laboratory of Advanced Ceramic Fibers & Composites, College of Aerospace Science & Engineering, National University of Defense Technology,
Changsha 410073, PR China
Received 17 February 2014; received in revised form 6 April 2014; accepted 16 April 2014
Available online 26 April 2014

Abstract

Silicon carbide whisker is a promising reinforcement material for metal and ceramic matrix composites. In this paper, nanostructured -SiC
whiskers were synthesized from an organicinorganic hybrid precursor via a carbothermal reduction of silica by carbonized phenolic resin. The
organicinorganic hybrid precursor for the carbothermal reduction was synthesized by gelating the mixture of water soluble phenolic resin and
silica sol. The products after the carbothermal reduction were characterized by X-ray Diffraction, Fourier transform infrared spectroscopy,
scanning electron microscopy, and transmission electron microscopy. The results show that the products synthesized at 15001700 1C are highly
ordered and pure -SiC crystal whiskers with diameters of 30150 nm. The microstructure of whiskers changes with the variation of the reaction
temperature. Interestingly, threaded rod shaped SiC whiskers were obtained at 1600 1C. The growth of SiC crystal whiskers at different
temperatures is controlled by different reaction kinetics. The solidsolid reaction is the dominat kinetics in the carbothermal reduction, with
solidgas reaction and gasgas reaction as the additional reaction kinetics.
& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: A. Powders: solid state reaction; A. Solgel processes; B. Whiskers; D. SiC

1. Introduction the synthesis of SiC whiskers such as carbothermal reduction,

Silicon carbide (SiC) is one of the most important non-oxide
ceramics due to its unique characteristics such as high melting
point, excellent oxidation resistance, high chemical inertness, high
thermal conductivity, good microwave absorbing ability, wide
energy band gap, and high mechanical strength. It is considered as
a promising material in many elds including aerospace structures,
biomaterials, high temperature semi-conducting devices, membrane
supports, and catalysis in harsh environments [16].
Among the different forms of SiC, whiskers have unique
technical importance. They have been widely used as the
reinforcement material for the fabrication of metal and ceramic
matrix composites. Compared to bers, SiC whiskers offer
composite materials an easy processing, isotropic mechanical
properties, better resistance to high temperature environments and
greater effect of fracture. Different methods have been used for
chemical vapor deposition, combustion of agro-wastes like
coconut shells and rice husks. Research on the synthesis of SiC
whiskers by novel technologies is still increasing in terms of
quality, dimension, purity and cost [713].
In this paper, a convenient and low cost method, with the
potential to be developed for mass production, was studied to
fabricate nanostructured SiC whiskers including a solgel
process of water soluble phenolic resin and silica sol, and
the carbothermal reduction between phenolic resin and silica.
The products were nanosized SiC whiskers; excitingly,
threaded rod shaped SiC crystal whiskers were obtained
through the carbothermal reduction at 1600 1C.
2. Experimental
2.1. Synthesis of SiC whiskers

n
Corresponding author. Tel.: 86 731 84576433. Water soluble phenolic resin was synthesized in a three-
E-mail address: nudt_libin@163.com (B. Li). necked ask using phenol and formaldehyde as the starting

http://dx.doi.org/10.1016/j.ceramint.2014.04.099
0272-8842/& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
12614 B. Li et al. / Ceramics International 40 (2014) 1261312616

materials. A small quantity of NaOH ( o 0.5 wt%) was added

into the ask as the catalyst and then washed away by water
after the solgel process. The three-necked ask was heated to
95100 1C, and kept for 1 h.
The organicinorganic hybrid precursor was synthesized by
adding silica sol into the as-received water soluble phenolic
resin with an optimized atomic ratio of Si/C=1/3 in order to
get relatively pure SiC. The mixture was heated at 95100 1C
till it becomes gelated. After that, the gelated organic
inorganic hybrid precursor was milled to powders and sieved
through a 180 mesh screen. Then the powders were preheat
treated to make sure the dehydration of silica gel and the
carbonization of water soluble phenolic resin at 1000 1C in N2
for 30 min and underwent the carbothermal reduction at
different high temperatures (1500, 1600 and 1700 1C) in Ar
for 60 min.

2.2. Characterization of SiC whiskers

The phase composition and crystallinity of the materials

were characterized by powder X-ray diffraction (XRD) on a
Bruker ADVANCED D8 diffractometer (Bruker, Germany) at
a wavelength of 1.5418 (Cu K radiation).
The investigation of chemical bonds was performed via a
Fourier transform infrared (FT-IR) spectrometer (Avatar 360,
Nicolet Instrument Corp., Wisconsin, USA) on discs pressed
from composites powders mixed with KBr.
Microstructures of the products were observed on a JSM-
5600LV Scanning Electron Microscope (SEM), and an FEI Fig. 1. XRD patterns of SiC crystal whiskers synthesized at different
temperatures.
Tecnai G2F20 Field Emission Transmission Electron Micro-
scope (FE-TEM) with a resolution of 0.2 nm at an accelerating
voltage of 200 kV.

3. Results and discussion

XRD patterns of the as-received products after the car-

bothermal reduction at different temperatures are shown in
Fig. 1. Comparing XRD patterns shows that the crystalline
phases of the products synthesized at 15001700 1C are quite
similar, and the crystallinity of the products increases slightly
with increasing reaction temperature. From the XRD patterns,
it can be easily observed that there are four sharp diffraction
peaks located at 35.81 (111), 41.41 (200), 60.01 (220) and
71.81 (311), all of which are attributed to -SiC. No other
obvious diffraction peak is found. Therefore, it can be
concluded that the products synthesized at 15001700 1C are
Fig. 2. FT-IR spectrum of SiC crystal whiskers synthesized at 1600 1C.
relatively pure -SiC.
To analyze the chemical bonds of the products, FT-IR
spectroscopy is employed and the spectrum of the products carbothermal reduction in this study. Meanwhile, the silica sol
synthesized at 1600 1C is shown in Fig. 2. The only one strong is dried to silica at high temperatures, which supplies the
absorption peak centered at 830 cm  1 is attributed to the silicon source in the reaction. The product -SiC grows during
stretching vibration of SiC, also suggesting the existence and this redox reaction.
high purity of SiC. The microstructures of the products synthesized at different
When heated at high temperatures, the phenolic resin in the temperatures are shown in Fig. 3. Apparently, the products
organicinorganic hybrid precursor pyrolyzed and carbonized obtained at 1500, 1600, 1700 1C are SiC crystal whiskers.
to carbon. It is well known that the carbon residual of phenolic However, the morphologies of these are quite different. The
resin is very high, which can supply the carbon source for the whiskers synthesized at 1500 1C are like tree branches, with
 B. Li et al. / Ceramics International 40 (2014) 1261312616
Fig. 3. SEM photographs of SiC crystal whiskers synthesized at 1500 (a),
1600 (b) and 1700 1C (c).
many speckles on the surface, which are like the barks of a tree
(Fig. 3(a)). The diameter of the whiskers is about 30100 nm.
It can be seen that the speckles, or attachments, are quite
different from the backbone of the whiskers. As analyzed
above, -SiC crystals grow from the carbothermal reduction
between carbon and silica. The reduction of silica by carbon
takes place through the following reaction:
SiO2(s) 3C(s)-SiC(s) 2CO(g)
However, reaction (1) is generally slow because it is a solid
solid haptoreaction, and solid phase nucleation has a relatively
slow diffusion rate [1]. Therefore, it gives opportunity to some
derived phases to form, including CO and SiO at the same
time. CO and SiO join the reactions, and another kind of
formation of SiC occurs [8,11]. The SiC generated in
the solidgas reaction (5) and gasgas reaction (6) deposits
12615
on the surface of the whiskers, which form the outer part of the
whiskers. These additional reactions to form SiC are as
follows:
SiO2(s) C(s)-SiO(g) CO(g) (2)
SiO2(s) CO(g)-SiO(g) CO2(g) (3)
CO2(g) C(s)-2CO(g) (4)
SiO(g) 2C(s)-SiC(s) CO(g) (5)
SiO(g) 3CO(g)-SiC(s) 2CO2(g) (6)
As shown in Fig. 3, with increasing reaction temperature,
the microstructures of the whiskers change. In Fig. 3(b), more
attachments on the backbones can be seen, and threaded rod
shaped SiC crystal whiskers are obtained. Compared to Fig. 3
(a), the whiskers synthesized at 1600 1C are a little thicker,
with a diameter of 50150 nm, and the outer screw threads
are quite clear. It is probably because reactions (5) and (6) are
much easier to take place at higher temperatures.
The microstructures of the whiskers synthesized at 1700 1C
change again. It is impossible to distinguish the outer part or
backbone from a single whisker, and the whiskers look quite
homogeneous with a diameter of 50100 nm. It is presumed
that the diffusion rate becomes very high at 1700 1C, and most
of SiC whiskers are generated from the solidsolid reaction.
Even if there are some parts of SiC whiskers generated from
the solidgas reaction and gasgas reaction, the deposited SiC
will easily epitaxially grow along with the lattice orientation of
the backbone crystals; therefore, homogeneous SiC whiskers
are obtained.
High-resolution transmission electron microscopy (HRTEM)
was performed to analyze the atomic structures of the whiskers.
As shown in Fig. 4, the whisker synthesized at 1700 1C displays a
very high order degree. The (111) planes are perpendicular to the
axial direction of the whisker. The interplanar spacing of (111)
planes is about 2.5 , which is very close to the theoretical value
(JCPDS Card no. 73-1665), indicating a fairly high degree of
crystallinity of -SiC. As shown in Fig. 4, the preferred growth
direction of crystal whiskers is along with the crystal direction of
[111] in the lattice structure of -SiC.
(1)
Fig. 4. HRTEM photograph of SiC crystal whiskers synthesized at 1700 1C.
12616 B. Li et al. / Ceramics International 40 (2014) 1261312616
4. Conclusions
In the present studies, we have studied a method to fabricate
nanostructured SiC whiskers by a solgel process and a
carbothermal reduction using an organicinorganic hybrid
precursor comprising water soluble phenolic resin and silica
sol. The products obtained from the carbothermal reduction at
15001700 1C are highly ordered -SiC whiskers with dia-
meters of 30150 nm. Different microstructures of whiskers
are formed at different reaction temperatures, which is caused
by different reaction kinetics. Threaded rod shaped crystal
whiskers form at 1600 1C. The solidsolid reaction is the
dominat kinetics in carbothermal reduction, with different
amounts of solidgas reaction and gasgas reaction at different
temperatures, which is the additional reaction kinetics to form
different surface morphologies of the whiskers.
Acknowledgment
The authors wish to thank the National Natural Science
Foundation of China (50902150), National High-tech R&D
Program (2012AA7024034) and National Key Laboratory
Foundation (9140C820304120C82288) for the nancial sup-
ports of this work.
References
[1] A. Naja, F. Golestani-Fard, H.R. Rezaie, N. Ehsani, A study on solgel
synthesis and characterization of SiC nano powder, J. Sol-Gel Sci.
Technol. 59 (2011) 205214.
[2] V.G. Lutsenko, Silicon carbide whiskers with superlattice structure: a
precursor for a new type of nanoreactor, Acta Mater. 56 (2008)
24502455.
[3] H.P. Martin, R. Ecke, E. Mller, Synthesis of nanocrystalline silicon
carbide powder by carbothermal reduction, J. Eur. Ceram. Soc. 18 (1998)
l737l742.
[4] B. Li, C.R. Zhang, H.F. Hu, Y.B. Cao, G.J. Qi, R.J. Liu, Preparation of
silicon carbide coatings from liquid carbosilanes by chemical vapor
deposition, J. Mater. Eng. Perform. 16 (2007) 775778.
[5] P.V. Prabhakaran, K.J. Sreejith, B. Swaminathan, S. Packirisamy,
K.N. Ninan, Silicon carbide wires of nano to sub-micron size from
phenolfurfuraldehyde resin, J. Mater. Sci. 44 (2009) 528533.
[6] A. Naja, F. Golestani-Fard, H.R. Rezaie, N. Ehsani, Synthesis and
characterization of SiC nano powder with low residual carbon processed
by solgel method, Powder Technol. 219 (2012) 202210.
[7] G.Y. Yang, R.B. Wu, J.J. Chen, F.F. Song, Y. Pan, Growth of silicon
carbide whiskers in FexSiy ux, Mater. Chem. Phys. 106 (2007) 236239.
[8] X.T. Li, X.H. Chen, H.H. Song, Synthesis of -SiC nanostructures via the
carbothermal reduction of resorcinolformaldehyde/SiO2 hybrid aerogels,
J. Mater. Sci. 44 (2009) 46614667.
[9] Z.Y. Ryu, J.T. Zheng, M.Z. Wang, B.J. Zhang, Synthesis and character-
ization of silicon carbide whiskers, Carbon 39 (2001) 19291941.
[10] X.K. Li, L. Liu, Y.X. Zhang, S.D. Shen, S. Ge, L.C. Ling, Synthesis of
nanometre silicon carbide whiskers from binary carbonaceous silica
aerogels, Carbon 39 (2001) 159165.
[11] T. Belmonte, L. Bonnetain, J.L. Ginoux, Gas ow nature inuence on
silicon carbide whiskers synthesis in xed bed, Vacuum 47 (1996)
291295.
[12] I.C. Leu, Y.M. Lu, M.H. Hon, Factors determing the diameter of silicon
carbide whiskers prepared by chemical vapor deposition, Mater. Chem.
Phys. 56 (1998) 256261.
[13] R. Koc, G. Glatzmaier, J. Sibold, -SiC production by reacting silica gel
with hydrocarbon gas, J. Mater. Sci. 36 (2001) 995999.