J O U R N A L O F M AT E R I A L S S C I E N C E L E T T E R S 1 6 ( 1 9 9 7 ) 1 0 8 0 – 1 0 8 3

Preparation and characterization of nano-structured monolithic SiC and

Si3 N4 SiC composite by hot isostatic pressing
SHAO MING DONG, DONGLIANG JI ANG, SHO U H ONG TAN, JINGKUN GUO
Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, People’s Republic of China

Nano-structured materials are now providing a TA B L E I Characteristics of SiC and Si C N nano-powders

prospective research field in ceramic engineering.
Because of the decrement of particle size, some
physical and mechanical properties of the materials
will be changed greatly. In structural ceramics,
Niihara [1] has proposed a new design concept,
ceramic nano-composite, and divided it into three
categories: intragranular nano-composite and nano
nano composite. According to this classification,
many intragranular and intergranular composites
have been developed in both oxide and non-oxide
ceramics [2 – 6], such as Al2 O3 SiC, Al2 O3 Si3 N4
and Si3 N4 SiC. In these nano-composites, the
second nano-dispersions are mainly dispersed within
the matrix grains, and the fracture toughness and
strength are improved significantly. The remarkable
improvement in hardness and strength even at high
temperature are still observed [5, 7]. Strengthening
and toughening mechanisms of nano-composites
have also been summarized by Niihara [1, 6]. The
other attractive results of nano-structured ceramics
are the machinability and superplasticity. The nano-
scale turbostratic ribbon structure of carbon formed
in the pores in â-phase silicon carbide, provides
good machinability in addition to the porous
structure [8]. The superplasticity of Si3 N4 SiC
nano-composite can probably be related to the
presence of an intergranular liquid phase [9]. Both
these novel properties may allow development useful
for applications.
Although nano-structured materials have been
developed extensively in recent years, nano nano
composites still require much study. As indicated by
previous research results [10, 11], hot isostatic pressing
(HIP) can depress the grain growth so that a fine and
homogeneous microstructure can be otained. The
present work studied the preparation of monolithic
SiC and Si3 N4 SiC nano-composite by encapsulation
HIP. Characterization of the micro- structure
development is presented.
Nano-SiC Nano-Si C Na
C Si molar ratio 0.994
N Si molar ratio 0.445
(0.75 N C) Si molar ratio 1.232
O content (wt %) 0.88 1.48
Particle size (nm) 60 50
a
Part of the Si C N powder was pretreated.
monolithic SiC, amorphous Si C N, and Si3 N4 – SiC
powders were first mixed with adhesive and then
dried, screened, and uniaxally pressed to the cylindrical
green compacts, 15 cm long and 10 cm diameter.
The green compacts were glass-encapsu- lated under
vacuum conditions. The HIP process was conducted
both at 1750 8C, 150 MPa for 1 h for preparing
SiC Si3 N4 composite, and 1850 8C,
200 MPa for 1 h for preparing monolithic SiC
ceramics. The phase compositions of the specimens
prepared by glass-encapsulation HIP were deter-
mined by XRD. Microstructure characterization
was performed by transmission electron micro-
scopy (TEM), high-resolution electron microscopy
(HREM) and energy-dispersive X-ray spectroscopy
(EDS).
Fig. 1 shows the XRD patterns of monolithic SiC
prepared by HIP. It is indicated that in the sintered
specimens, the phase is mainly â-SiC with a trace of
á-SiC. A transmission electron migrograph of the
specimen is illustrated in Fig. 2, showing the fully
dense and homogeneous microstructure with
equiaxed grains. The average grain size is about
100 nm. This result may indicate that grain growth
occurs during HIP of the monolithic nano-SiC
powder. However, the grain size remains at the
nano-scale.
Fig. 3 shows an HREM image of the monolithic
SiC sintered at 1850 8C, 200 MPa pressure. A very
Intensity (Arb. units)

The starting nano-powders used in this experiment

were prepared by the chemical vapour deposition
(CVD) method in our laboratory. The characteristics
of the nano-powders are listed in Table I. X-ray
diffraction pattern (XRD) analysis indicated that the
nano-SiC powder was mainly â-phase, while the
nano-Si C N precursor powder was in the amor- 10 20 30 40 50 60 70 80
phous state. Some of the Si C N powder was 2è (deg)
subjected to pretreatment. The pretreated powder
exhibited the Si3 N4 and SiC compositions, which Figure 1 XRD patterns of monolithic SiC specimen by HIP at
maintained an average particle size of 50 nm. The 1850 8C, 200 MPa for 1 h. (d) â-SiC, (j) á-SiC.

1080 0261-8028 1997 Chapman & Hall

 (a)

Intensity (Arb. units)

(b)

10 20 30 40 50 60 70 80
2è (deg)

Figure 4 XRD patterns of HIP specimens formed by using

Figure 2 Transmission electron micrograph of monolithic SiC speci-
men by HIP.
(a) amorphous Si C N nano-powder, (b) pretreated Si3 N4 – SiC
nano-powder. (m) Si2 ON2 , (j) â-Si3 N4 , (d) â-SiC.
specimens, which makes the amorphous Si C N
nano-powder change to Si2 ON2 , SiC and Si3 N4. For
the Si3 N4 SiC powder, the HIP specimen exhibits
two phases: â-Si3 N4 and â-SiC (Fig. 4b). During the
HIP process, á-Si3 N4 in the nano-powder is
transformed exclusively to â phase, while â-SiC
remains in almost the same phase in the composite
as in the starting powder.
Transmission electron micrographs of the nano-
composite are shown in Fig. 5. It is shown that in the
Si2 ON2 Si3 N4 SiC composite, many larger grains
(more than 100 nm) are present in the microstruc-
ture, probably because of the abnormal grain growth

Figure 3 HREM image of monolithic nano-SiC sintered at 1850 8C,

200 MPa for 1 h, showing the very thin grain-boundary film.

thin amorphous intergranular film exists at the grain

boundary. The occurrence of a grain-boundary film
in monolithic nano-SiC ceramics may be attributed
to the presence of SiO2 in the starting powder particles.
Because nano-powders have a large specific
surface area, they are very reactive and easy to
oxidize. The oxide will be present on the surface
of the particles, and after the HIP process, this oxide
becomes the amorphous grain-boundary phase.
Fig. 4 shows XRD patterns of HIP specimens
prepared using both amorphous Si C N nano-
powder and pretreated Si3 N4 – SiC nano-powder. As
indicated by the peak locations, the main phase of
HIP specimens using Si C N powder is Si2 ON2, and
á-SiC and â-Si3 N4 are also present with very low
diffraction peaks (Fig. 4a). The formation of Si2 ON2
may be attributed to oxidation during material
preparation. The very fine and active Si C N
amorphous powder is also easy to oxidize when it
is exposed to air. As a result, the oxidation process may
lead to the formation of Si – O – Si, N – Si – O and C – Si
– O, which have been confirmed from the infrared
(IR) spectrum [12]. The absorption of oxygen
into the lattice of Si – C – N will obviously affect Figure 5 Transmission electron micrographs of HIP specimens using
the final phase composition of the HIP (a) amorphous Si C N nano-powder, (b) pretreated Si3 N4 – SiC nano-
powder.

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of Si2 ON2 (Fig. 5a). In Si3 N4 SiC composite, very
fine, homogeneous microstructure is obtained, as
indicated in Fig. 5b. The average grain size is about
50 nm and the morphology of the grains is ball-like.
In this composite, grain growth is greatly depressed
by both the heterophase compositions and HIP
conditions, which are at relatively low sintering
temperature at high pressure.
Fig. 6 shows the HREM image of the Si2 ON2
Si3 N4 SiC composites. A large amount of residual
amorphous phase is present at the grain boundaries
in this composite. EDS analysis indicated that the
main composition of this grain-boundary phase is
silicon and oxygen, as shown in Fig. 7. This result
implies that Si C N amorphous nano-powder may
react with the absorbed oxygen and partly form Si2
ON2 , as mentioned previously, and the others
remain as amorphous phase in the grain boundaries,
which coexist with Si3 N4 and SiC to form the
composite. Fig. 8 shows the HREM image of
Si3 N4 SiC nano-composite. No residual amorphous Figure 8 HREM image of Si3 N4 SiC composite showing the clean
phase was found either at the grain boundary or at grain boundaries and triple-grain junction.
the triple-grain junction. This is because the excess
carbon content in the precursor Si C N powder, as
listed in Table I, may remove the oxide during the oxidized powder may be described by the following
pretreatment. The reactions between carbon and equations:

Si O Si 3C 2SiC CO (1a)
4N Si O 5C SiC Si3 N4 4CO (1b)
C Si O C SiC CO (1c)
The reaction product of CO in Equations 1a – c may
be substituted by CO2. Either way, in this process,
part of the oxidized amorphous nano-powder may be
purified and crystallized to SiC and Si3 N4 .
Not only can carbon react with the absorbed
oxygen in the Si C N lattice during pretreatment,
but, it can also react with the oxide, SiO2 during the
HIP process. In addition, carbon may also play an
important role in separating particles during crystal-
lization from amorphous Si C N nano-powder to the
nano-powder composed of Si3 N4 and SiC, so that
grain growth is deeply depressed. The crystallized
Si3 N4 and SiC powders will retain their original
Figure 6 HREM image of HIP Si2 ON2 Si3 N4 SiC composite show-
grain size after the HIP process, as indicated in Fig.
ing a large amount of amorphous phase in the grain boundary.
5b, and therefore, the Si3 N4 SiC nano nano com-
posite is obtained.
In summary, nano-structured monolithic SiC
Si
ceramics can be prepared by hot isostatic pressing.
At 1850 8C, 200 MPa pressure for 1 h, dense and
10 homogeneous microstructure with a grain size of
about 100 nm can be obtained. The starting powder
(Counts s21)

materials may affect the microstructure of the final

composites significantly. The use of nano-Si C N
amorphous precursor powder will lead to the
5
formation of Si2 ON2 because of the oxidation of
Si C N during material preparation. The formation
O
of Si2 ON2 can also lead to abnormal grain growth.
Si3 N4 SiC nano-composite can be prepared by using
0 the pretreated Si3 N4 and SiC nano-powder. At
0 1 2 3 1750 8C, 150 MPa pressure for 1 h, dense and
Energy (keV) homogeneous microstructure with an average grain
Figure 7 EDS analysis of the grain-boundary phase in Si2 ON2
size of 50 nm can be obtained. The depression of
Si3 N4 SiC composite. grain growth in this composite may be ascribed to
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the heterophase compositions and HIP conditions.
The existence of carbon in the nano-powder will
benefit the removal of the oxide in grain boundaries.
Acknowledgements
The authors thank Ms M. L. Yan for her helpful
work in microstructure analysis. The financial
support by the National Natural Science Foundation
of China is also appreciated.
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Received 27 November 1996
and accepted 3 April 1997
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