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
SHAOMING DONG, DONGLIANG JIANG, SHOUHONG TAN, JINGKUN GUO Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, Peoples Republic of China

C Si molar ratio N Si molar ratio (0.75 N C) Si molar ratio O content (wt %) Particle size (nm)

0.994 0.445 1.232 1.48 50

0.88 60

monolithic SiC, amorphous Si C N, and Si3 N4 SiC powders were rst 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-encapsulated 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 determined by XRD. Microstructure characterization was performed by transmission electron microscopy (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 -SiC with a trace of -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
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Figure 1 XRD patterns of monolithic SiC specimen by HIP at 1850 8C, 200 MPa for 1 h. (d) -SiC, (j) -SiC.

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Part of the Si C N powder was pretreated.

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1997 Chapman & Hall

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Nano-structured materials are now providing a prospective research eld 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 classication, many intragranular and intergranular composites have been developed in both oxide and non-oxide ceramics [26], 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 signicantly. 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 nanoscale turbostratic ribbon structure of carbon formed in the pores in -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 ne 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 microstructure development is presented. 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 -phase, while the nano-Si C N precursor powder was in the amorphous state. Some of the Si C N powder was subjected to pretreatment. The pretreated powder exhibited the Si3 N4 and SiC compositions, which maintained an average particle size of 50 nm. The

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TA B L E I Characteristics of SiC and Si C N nano-powders Nano-Si C Na

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Figure 4 XRD patterns of HIP specimens formed by using (a) amorphous Si C N nano-powder, (b) pretreated Si3 N4 SiC nano-powder. (m) Si2 ON2 , (j) -Si3 N4 , (d) -SiC.

Figure 3 HREM image of monolithic nano-SiC sintered at 1850 8C, 200 MPa for 1 h, showing the very thin grain-boundary lm.

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thin amorphous intergranular lm exists at the grain boundary. The occurrence of a grain-boundary lm in monolithic nano-SiC ceramics may be attributed to the presence of SiO2 in the starting powder particles. Because nano-powders have a large specic 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 nanopowder 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 -SiC and -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 ne 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 SiOSi, NSiO and CSiO, which have been conrmed from the infrared (IR) spectrum [12]. The absorption of oxygen into the lattice of SiCN will obviously affect the nal phase composition of the HIP

Figure 5 Transmission electron micrographs of HIP specimens using (a) amorphous Si C N nano-powder, (b) pretreated Si3 N4 SiC nanopowder.

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Figure 2 Transmission electron micrograph of monolithic SiC specimen by HIP.

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: -Si3 N4 and -SiC (Fig. 4b). During the HIP process, -Si3 N4 in the nano-powder is transformed exclusively to phase, while -SiC remains in almost the same phase in the composite as in the starting powder. Transmission electron micrographs of the nanocomposite 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 microstructure, probably because of the abnormal grain growth

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oxidized powder may be described by the following equations: 2SiC CO (1a) Si O Si 3C SiC Si3 N4 4CO (1b) 4N Si O 5C C Si O C SiC CO (1c) The reaction product of CO in Equations 1ac may be substituted by CO2. Either way, in this process, part of the oxidized amorphous nano-powder may be puried 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 crystallization 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 grain size after the HIP process, as indicated in Fig. 5b, and therefore, the Si3 N4 SiC nano nano composite is obtained. In summary, nano-structured monolithic SiC ceramics can be prepared by hot isostatic pressing. At 1850 8C, 200 MPa pressure for 1 h, dense and homogeneous microstructure with a grain size of about 100 nm can be obtained. The starting powder materials may affect the microstructure of the nal composites signicantly. The use of nano-Si C N amorphous precursor powder will lead to the formation of Si2 ON2 because of the oxidation of Si C N during material preparation. The formation of Si2 ON2 can also lead to abnormal grain growth. Si3 N4 SiC nano-composite can be prepared by using the pretreated Si3 N4 and SiC nano-powder. At 1750 8C, 150 MPa pressure for 1 h, dense and homogeneous microstructure with an average grain size of 50 nm can be obtained. The depression of grain growth in this composite may be ascribed to

Figure 6 HREM image of HIP Si2 ON2 Si3 N4 SiC composite showing a large amount of amorphous phase in the grain boundary.

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Figure 7 EDS analysis of the grain-boundary phase in Si2 ON2 Si3 N4 SiC composite.

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of Si2 ON2 (Fig. 5a). In Si3 N4 SiC composite, very ne, 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 phase was found either at the grain boundary or at 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 pretreatment. The reactions between carbon and

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Figure 8 HREM image of Si3 N4 SiC composite showing the clean grain boundaries and triple-grain junction.

the heterophase compositions and HIP conditions. The existence of carbon in the nano-powder will benet the removal of the oxide in grain boundaries.

5. K . N I I H A R A , K . I Z A K I and A . N A K A H I R A , J. Jpn Soc.

Powder Powder Metall. 37 (1990) 352.

6. K . N I I H A R A , ibid. 37 (1990) 348. 7. K . I Z A K I , A . N A K A H I R A and K . N I I H A R A , ibid. 38

(1991) 357.
8. K . S A G U N A M A , G . S A S A K I , T. F U J I TA , M . O K U -

Acknowledgements The authors thank Ms M. L. Yan for her helpful work in microstructure analysis. The nancial support by the National Natural Science Foundation of China is also appreciated.

M U R A , A . N A K A Z A R A and K . N I I H A R A , ibid. 38

(1991) 374.
9. F. WA K A I , Y. KO D A M A , S . S A K A G U C H I , N . M U R AYA M A , K . I Z A K I and K . N I I H A R A , Nature 344 (1990)

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Received 27 November 1996 and accepted 3 April 1997

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