Materials Science and Engineering, A168 (1993) 183-187 183
Microstructure of chemically vapour codeposited SiC-TiC-C
nanocomposites
R. Hillel and M. Maline
IMP-CNRS, UniversitOde Perpignan, 66860, Perpignan Cedex (France)
F. Gourbilleau and G. Nouet
LE RMA T, URA-CNRS 1317, ISMRA, 14050 Caen (France)
R. Carles and A. Mlayah
URA-CNRS 74, Universit~ Toulouse III, 31062 Toulouse Cedex (France)
Abstract
SiC-TiC-C nanocomposites were chemically vapour codeposited onto a graphite substrate under atmospheric pressure,
in the temperature range 950-1150 °C, using the TiCI4-C4H 10-SiH2CI2-H2 gas system. SiC, TiC and excess carbon molar
compositions were calculated using determination by electron probe microanalysis-wavelength-dispersive spectroscopy
of the atomic percentages of Si, Ti and C after having identified SiC and TiC by Auger electron spectroscopy. The (220)
preferential orientation corresponding to r-SiC + cubic TiC, revealed by X-ray diffraction, decreased with deposition
temperature and almost no texture remained at 1050 °C. The apparent crystallite size along the (220) direction was about
10-20 nm. Micro-Raman spectra showed that the Raman size of the excess carbon did not exceed a few nanometres and
that TiC and SiC were structurally disordered. Using transmission and high resolution electron microscopies, codeposits
were found to consist of needles of SiC + TiC embedded in a poorly crystallized SiC matrix. They were stacking faulted
and 10-15 nm broad. The needles were predominantly (220) oriented perpendicular to the substrate, whereas secondary
needles were growing in { 111 }planes with (112) average direction.
1. Introduction
Combining two or more different ceramics through
dispersed composites offers the promise of tailoring
properties. Combinations such as SiC-TiC are
examples providing enhancement of mechanical
properties or protection against oxidation. However,
most of these mixtures, fabricated by high-temperature
and high-pressure sintering, are found to consist of
grains of several micrometres which limits their appli-
cations under extreme conditions (stress and tempera-
ture). So recently, increasing interest has focused on
structures with nano-sized particles, because these
materials are expected to provide improved properties
compared with composites presenting coarser struc-
tures [1, 2]. Among the available techniques for the
preparation of nanocomposites [3] chemical vapour
deposition (CVD) is a very attractive method for
codepositing ceramics which are very intimately
dispersed under near equilibrium conditions [4].
Taking into account previous works concerning CVD
codeposition in the ternary system Ti-Si-C [5-8], we
have prepared SiC-TiC-C nanocomposites. Owing to
the drastic reduction in grain size and the strong
imbrication of the phases, characterization of these
materials required cross-checking of different data
from complementary microanalytical techniques.
2. Experimental procedure
Deposits were prepared by conventional thermal
CVD, under atmospheric pressure [9]. The reactor
chamber consisted of a vertical silica tube (~b= 5.0 or
6.2 cm, L=20 cm). The codeposition was onto
mechanically polished polycrystalline graphite sub-
strate (thickness 1 mm) heated in the range
950-1150°C by an electric current, the substrate
shape being designed to obtain a uniformly heated
zone of 25 × 5 mm 2. Vaporized liquid TiCI4, gaseous
C4H10 and SiHzC1 z in H 2 gas were used as reactant
sources at different concentrations. The H 2 gas flow
rate was 30 1h- l or 40 1h- t. Samples of different com-
positions were prepared by varying both the codeposi-
tion temperature and concentrations of the input gas
species. The codeposition time was 0.5 h. Coating
thicknesses ranged from 100 to 600/~m, depending on
the experimental conditions.
0921-5093/93/$6.00 © 1993 - Elsevier Sequoia. All rights reserved