Preparation and dielectric properties of Si3N4/SiCw composite ceramic

Gelcasting was employed to fabricate Si₃N₄/SiC whisker (SiCw) composite ceramics, and the effects of heat-treatment temperature on the length-to-diameter ratio of the whiskers and SiCw content on microwave dielectric properties were studied. Compared with pure SiCw of spherical structure obtained at temperature of 1,750 °C(Ar), pure SiCw treated at 1,600 °C(Ar) showed rod-like structure, higher dielectric properties and more evenly distribution in Si₃N₄/SiCw composite ceramics. Both the real (ε′) and imaginary (ε″) permittivity of Si₃N₄/SiC whisker (SiCw) composite ceramics decreased with increasing frequency and increased as the whisker content raised owing to the interface and SiCw playing a role of dipole in the frequency range of 8.2–12.4 GHz. In addition, comparing the ceramics with lower content of SiCw, the reflectivity of the composite ceramics moved to a lower frequency; the maximum absorption peak reached ?22.4 dB at the whisker content of 15 wt%.     

Quantitative determination of the stability of SiC whisker in reaction-bonded/hot-pressed Si3N4 composites by X-ray diffraction

A method was developed for the quantitative determination of weight fractions of the phases in SiC whisker-reinforced reaction-bonded Si₃N₄ composites using X-ray diffraction. Composites with different amounts of sintering additives and whiskers were fabricated using reaction bonding followed by hot pressing. The amount of whiskers remaining in each composite after each processing stage was determined. In order to study the degradation mechanism, the microstructural development after each processing step was examined using scanning and transmission electron microscopy. Finally, the effect of sintering additives on the microstructural development and whisker stability was also investigated.     

Toughness enhancement by polycarbosilane coating on SiC whiskers incorporated in Si3N4 matrix composite

Si₃N₄ matrix composite was fabricated by hot pressing with 20% SiC whiskers coated with polycarbosilane (PCS). The preceramic polymer on the whiskers was pyrolysed during sintering to form a carbon-rich layer at the whisker/matrix interface. Mechanical properties were measured, and compared to those of the composites with whiskers purified with HCl and HF. Elastic modulus and bending strength of the composite with PCS-coated whiskers were lower than those of the composites with other whiskers. Fracture toughness was measured by single-edge notched beam (SENB) and single-edge precracked beam (SEPB) methods. The toughness, including crack-growth resistance measured by the SEPB method, increased from 7.2 MPam^1/2 to 7.9 MPam^1/2 by PCS-coating on the whisker, while the toughness measured by the SENB method decreased from 6.5 MPam^1/2 to 5.7 MPam^1/2. The layer derived from PCS facilitated debonding at the whisker/matrix interface and activated the wake-toughening. Optical microscopic observation of the crack propagation near the interface confirmed enhancement of interfacial debonding by the PCS-coating.     

Effect of sintering additives on the behaviour of SiC whisker-reinforced Si3N4 composites

The effects of sintering additives on the microstructural development, whisker stability, oxidation resistance and room-temperature mechanical properties of the SiC whisker-reinforced Si₃N₄ matrix composites were investigated. Seven different combinations of Y₂O₃ and Al₂O₃ were used as sintering additives. The composites containing 20 vol % SiC whiskers were densified by hot pressing. The microstructure of the resulting composites was characterized using X-ray diffraction, scanning and transmission electron microscopy. Oxidation testing of the composite at 1400 °C was conducted to investigate the relationship between matrix compositions and oxidation resistance. The flexural strength, fracture toughness and crack propagation patterns were also characterized and correlated with the microstructural features.     

Microstructural features of sintered Si3N4/SiC-whiskers composites: mechanical integrity of whiskers

A detailed microstructural analysis of slip-cast Si₃N₄/SiC-whisker composites has been made by TEM. In spite of the gentle forming process, SiC whisker breakage constitutes a fundamental feature of this material. The breaking takes place during the sintering process and could be associated with residual thermal stresses, as revealed by the experimental evidence. The dramatic decrease in the whiskers aspect ratio translates into little or no effect of whisker addition on the mechanical properties of the Si₃N₄ matrix.     

Slurry processing for fabrication of SiC whisker-reinforced Si3N4 composites

In order to solve the major problems of processing whisker-reinforced ceramic composites, such as agglomeration of whiskers, correlation between pH and viscosity has been carefully investigated in a mixed slurry of whiskers and matrix powder. SiC whiskers and Si₃N₄ powder were dispersed homogeneously by controlling pH in aqueous suspension, and the state was successfully fixed by a sudden change of pH to make the slurry more viscous. The slurry was then filtrated rapidly and dried. The strength of hot pressed composites obtained by this procedure was scarcely lowered, with increased whisker loading in the range 0–30 wt% and fracture toughness increased more than 75%.     

Influence of whisker toughening and microstructure on the wear behavior of Si3N4- and Al2O3-matrix composites reinforced with SiC

A comparative study of the influence of randomly-oriented SiC whiskers on the abrasive wear behavior of several commercially-produced Si₃N₄- and Al₂O₃-based ceramics suggested that the residual stress states present within the materials can be important in predicting their wear resistance. The addition of SiC whiskers to the Si₃N₄ matrix created residual tensile stresses at the whisker-matrix interfaces which led to enhanced bulk fracture toughness, but which degraded the fracture toughness at the microstructural level, and thus the abrasive wear resistance, by promoting easier whisker debonding and removal by the abrasive particles. The addition of SiC whiskers to an alumina matrix, on the other hand, led to the creation of residual compressive stresses at whisker-matrix interfaces, producing a locally tougher interface that was more able to withstand the rigors of the abrasive wear environment. These results indicate that in brittle materials, improved bulk mechanical properties do not always translate directly to improved performance in a tribological environment.     

Sintering anisotropy in slip-cast SiC-whisker/Si3N4-powder compacts

Sintering anisotropy in slip-cast SiC-whisker/Si₃N₄-powder compacts was studied at 1750°C in 0.1 MPa N₂ or at 1825°C in 1.0 MPa N₂. It was shown that whiskers oriented parallel to the mould surface and nearly 1.5-dimensionally along the slip flow direction when the whisker content was 10 wt%. Linear shrinkage was largest perpendicular to the mould surface and smallest perpendicular to the whisker alignment. It was shown that the retardation of densification by whiskers is due to the formation of a rigid network along the whisker alignment, which is in accordance with percolation theory. The addition of up to 20 wt% whisker did not affect sintering kinetics but lowered sinterability by 2-dimensional alignment of the whiskers. The anisotropy in fracture toughness is related to the orientation of the whiskers.     

Formation of SiC whiskers from silicon nitride

Attempts have been made to produce SiC whiskers through vacuum pyrolysis of Si₃N₄ without any addition of extraneous carbon. Vacuum pyrolysis of Si₃N₄ granules and powder compacts, has been carried out at 1550 and 1700°C using a graphite resistance furnace. The products of pyrolysis have been identified through XRD and SEM as SiC whiskers and particles. Small amounts of elemental silicon at 1550°C and free carbon at 1700°C have been detected through X-ray diffraction. Detection of elemental silicon through X-ray diffraction and solidified silicon droplets at the whisker tips in the SEM provide important clues regarding the mechanism of SiC_w formation, as the one involving the reaction 2Si(l) + CO(g) SiC(s) + SiO(g) Silicon carbide whiskers, 3–4 mm long, have been grown from Si₃N₄ compacts at 1550°C over a short period of 0.5 h. It has been shown in the present study that Si₃N₄ can be completely converted to SiC_w, when a loose bed of Si₃N₄ in the form of granules is pyrolysed in the presence of CO at about 1550°C.     

Synthesis of Si3N4 whiskers in porous SiC bodies

Si₃N₄ whiskers were synthesized by the carbothermal reduction process in porous SiC bodies. The SiC bodies had a sponge microstructure with pore sizes of approximately 600 μm. The raw materials for the Si₃N₄ whiskers were powder mixtures of Si₃N₄, SiO₂ and Si for silicon and phenolic resin for carbon. Cobalt was used as a metal catalyst. The carbothermal reaction was performed at 1400 °C or 1500 °C for 1 or 2 h. The α-Si₃N₄ whiskers grew inside the SiC pores by the VLS process, and their diameters ranged from 0.1 to 1.0 μm. The length of the grown Si₃N₄ whiskers was over 100 μm and their growth direction was [100].     

Analysis of Si3N4+β-Si3N4 whisker ceramics

Dense Si₃N₄+-Si₃N₄ whisker composite ceramics were fabricated by hot pressing powder-whisker mixtures. Addition of -Si₃N₄ whiskers had no significant influence on the densification behaviour for up to 20 wt% addition. Light microscopy and scanning and transmission electron microscopy were used to study their microstructure and fracture behaviour. An increase in fracture toughness was observed for -Si₃N₄ whisker additions of up to 10 %. The main toughening mechanisms observed were crack deflection, crack branching, whisker-matrix debonding and whisker pull-out.     

Mechanical properties Of Si3N4 cerarnics reinforced with SiC whiskers and SiC platelets

Silicon nitride ceramics reinforced with SiC whiskers and SiC platelets were fabricated by hot pressing and their mechanical properties were studied. They showed higher fracture energy than conventional composites, particularly when they were consolidated by gas-pressure hot pressing at high temperature. A high fracture toughness (10.7 MPa m^1/2) which was measured by the single-edge pre-cracked beam method was achieved. Furthermore, a unique method to observe the crack propagation behaviours directly in a scanning electron microscope with loading devices was developed. As a result, much bridging and pull-out of the whiskers and the elongated Si₃N₄ grains, and crack deflection along the platelets, were observed behind the crack tip. This means that these grains are effective in enhancing the fracture resistance during crack propagation.     

Manufacture of fibrous β-Si3N4-reinforced biomorphic SiC matrix composites for bioceramic scaffold applications

The manufacturing of the Si₃N₄ reinforced biomorphic microcellular SiC composites for potential medical implants for bone substitutions with good biocompatibility and physicochemical properties was performed in a two step process. First, wood-derived porous Si/SiC ceramics with various porosities were produced by liquid silicon infiltration (LSI) at 1550 °C with static nitrogen atmosphere protection (0.1 MPa), followed by subsequent partial removing of the Si in vacuo at 1700 °C for different periods of time. Secondly, the final porous Si₃N₄ fiber/SiC composite was obtained by further chemical reaction of nitrogen with the infiltrated residual silicon at 1400 °C for 4 h under high concentration flowing nitrogen atmospheres (0.5 MPa). The bending strengths of the porous Si₃N₄ fiber/SiC composite at axial and radial direction were measured as 180.03 MPa and 90 MPa respectively. The improvement in bending strength was primarily attributed to grain pull-out and bridging enhanced by the elongated β-Si₃N₄ grains cross-linked in the depth of the pore channels. The TG analysis showed an obvious improvement in oxidation resistance of the nitride specimens.     

Effect of gas phase on SiC and Si3N4 formations from SiO2

During the synthesis of SiC, Si₃N₄ and sialon whiskers by carbothermal reduction of SiO₂, a localized formation of amorphous phases or Si₂N₂O powders was observed beneath these whiskers. Because these whiskers were formed by the vapour/solid mechanism, the controlling gas phase was of primary importance to obtain whiskers of tailored morphology and chemistry. To elucidate the effect of the gas phase composition on the reaction mechanisms of SiC and Si₃N₄, the oxygen partial pressure was measured during the synthesis with a ZrO₂ solid electrolyte. The carbothermal reduction of SiO₂, as well as evolution of gases, were accelerated by a formation of a molten fluorosilicate with an auxiliary halide bath. The oxygen partial pressure steadily increased with increasing temperature and reached a maximum level of 10^–1110^–12 atm in the early stage of reaction at 1623 K, then decreased again towards the end of reaction in both cases. Effects of the gas phase on the SiC and Si₃N₄ formations were not the same: p _CO and and their ratio were important factors in the SiC formation, while the higher formed an oxynitride phase in the Si₃N₄ formation.     

Effect of microstructure on the high temperature strength of nitride bonded silicon carbide composite

Four compositions of nitride bonded SiC were fabricated with varying particle size of SiC of ∼ 9.67, ∼ 13.79, ∼ 60 μ and their mixture with Si of ∼ 4.83 μ particle size. The green density and hence the open porosity of the shapes were varied between 1.83 to 2.09 g/cc and 33.3 to 26.8 vol.%, respectively. The effect of these parameters on room temperature and high temperature strength of the composite up to 1300°C in ambient condition were studied. The high temperature flexural strength of the composite of all compositions increased at 1200 and 1300°C because of oxidation of Si₃N₄ phase and blunting crack front. Formation of Si₃N₄ whisker was also observed. The strength of the mixture composition was maximum.     

High-resolution interface analysis of SiC-whisker-reinforced Si3N4 and Al2O3 ceramic matrix composites

Whisker/matrix interfaces between -SiC whiskers and -Si₃N₄ or -Al₂O₃ matrices in composites were examined by high-resolution electron microscopy (HREM), and electron energy loss (ELS) and energy dispersive X-ray (EDS) spectroscopies. Most whisker/matrix interfaces were crystalline, with whiskers directly bonded to matrix crystals. Some whisker/matrix interface regions contained amorphous thin films and these occurred more often in the Si₃N₄ composite, which contained sintering additives, than in the Al₂O₃ matrix composite, which did not. No evidence for light element segregation at crystalline whisker/matrix interfaces was detected by ELS or EDS at 5 nm spatial resolution. Impurities were concentrated in glassy regions in matrix grain boundaries, triple junctions, or at infrequent whisker/matrix interfaces containing amorphous films.     

Strength,toughness and R-curve behaviour of SiC whisker-reinforced composite Si3N4 with reference to monolithic Si3N4

The flexural strength and fracture toughness of 30 vol% SiC whisker-reinforced Si₃N₄ material were determined as a function of temperature from 25 to 1400°C in an air environment. It was found that both strength and toughness of the composite material were almost the same as those of the monolithic counterpart. The room-temperature strength was retained up to 1100°C; however, appreciable strength degradation started at 1200°C and reached a maximum at 1400°C due to stable crack growth. In contrast, the fracture toughness of the two materials was independent of temperature with an average value of 5.66 MPam^1/2. It was also observed that the composite material exhibited no rising R-curve behaviour at room temperature, as was the case for the monolithic material. These results indicate that SiC whisker addition to the Si₃N₄ matrix did not provide any favourable effects on strength, toughness and R-curve behaviour.     

Mechanical properties of Si3N4/BN fibrous monolithic ceramics at elevated-temperature

The mechanical properties at high temperature of Si₃N₄/BN fibrous monolithic ceramics were tested. The flexural strength of SiC whisker reinforced Si₃N₄/BN fibrous monolithic ceramics from 25°C to 1200°C were investigated. The strength degraded slowly from 1000°C to 1200°C which was different to Si₃N₄ monolithic ceramics. The creep behaviors of the material at different temperatures were characterized. Si₃N₄/BN fibrous monolithic ceramics possess high creep resistance. The chemical composition and microstructure of the composites were analyzed by XRD and SEM.     

Preparation of Si3N4-SiC composites by microwave route

Si₃N₄-SiC composites have been microwave sintered using β-Si₃N₄ and β-SiC as starting materials. Si₃N₄ rich compositions (95 and 90 vol.% Si₃N₄) have been sintered above 96% of theoretical density without using any sintering additives in 40 min. A monotonic decrease in relative density is observed with increase in SiC proportion in the composite. Decrease in relative density has manifested in the reduction of fracture toughness and microhardness values of the composite with increase in SiC content although the good sintering of matrix Si₃N₄ limits the decrease of fracture toughness. Highest value of fracture toughness of 6.1 MPa m^1/2 is observed in 10 vol.% SiC composite. Crack propagation appears to be transgranular in the Si₃N₄ matrix and the toughening of the composites is through crack deflection around hard SiC particles in addition to its debonding from the matrix.     

Characterization of plasma-sprayed and whisker-reinforced alumina coatings

We have strengthened plasma-sprayed alumina coatings by incorporating SiC or Si₃N₄ whiskers. As a result, we found that the whisker-reinforced coatings were greatly improved in properties such as thermal shock resistance and adhesion. Major features of the plasma-sprayed Al₂O₃–5.0 wt % Si₃N₄, coating were investigated by means of scanning electron microscopy, secondary ion mass spectroscopy, X-ray diffraction, X-ray fluorescence spectroscopy and thermal radiation measurements.