In Situ Synthesis of Silicon Carbide Whiskers from Silicon Nitride Powders

Silicon carbide whiskers were synthesized in situ by direct carbothermal reduction of silicon nitride with graphite in an argon atmosphere. Phase evolution study reveals that the formation of β-SiC was initiated at 1400° to 1450°C; above 1650°C silicon was formed when carbon was deficient. Nevertheless, Si₃N₄ could be completely converted to SiC with molar ratio Si₃N₄:C = 1:3 at 1650°C. The morphology of the SiC whiskers is needlelike, with lengths and diameters changing with temperature. SiC fibers were produced on the surface of the sample fired at 1550°C with an average diameter of 0.3 μm. No catalyst was used in the syntheses, which minimizes the amount of impurities in the final products. A reaction mechanism involving the decomposition of silicon nitride has been proposed.     

Effect of Reinforcement of a Silicon Nitride Matrix by Silicon Carbide Whiskers

A fine-grain high-density tough matrix is a general prerequisite for synthesis of high-strength and crack-resistant composite materials, as well as its self-reinforcement with extended grains of β-Si₃N₄ and reinforcement with β-SiC crystals. Both approaches are used simultaneously in the present work. It is shown that the reinforcement of a silicon nitride matrix based on ultradisperse powder compositions by SiC whiskers of grade TWS provides hot-pressed ceramics with a high ultimate bending strength (950 MPa) and crack resistance (10 MPa · m^1/2). Reinforcement by fine or coarse whiskers increases the crack resistance by 30% with respect to monolithic Si₃N₄. Composites reinforced by TWS silicon carbide whiskers preserve their high strength up to 1500°C.     

Microstructure of Silicon Carbide Whiskers Synthesized by Carbothermal Reduction of Silicon Nitride

The microstructure of silicon carbide whiskers synthesized by carbothermal reduction of silicon nitride has been studied using transmission electron microscopy. All of the whiskers examined are single crystals, and grow in the (111) crystallographic direction. Two different forms of stacking faults and microtwins were observed; in one the planar defects are normal to the whisker growth direction, and the other has the defect planes at an angle of about 70° to the growth axis, while both forms of the defects are on the [111] closed-packed planes. Without the addition of catalyst, droplets containing metallic impurities were not found at the tips of the whiskers synthesized by the present process. A core and outer regions were observed in the single-crystal whiskers, which may be evidence that the whiskers were formed by a two-stage mechanism.     

Toughening of Silicon Nitride Matrix Composites by the Addition of Both Silicon Carbide Whiskers and Silicon Carbide Particles

Si₃N₄ matrix composites reinforced by SiC whiskers, SiC particles, or both were fabricated using the hot-pressing technique. The mechanical properties of the composites containing various amounts of these SiC reinforcing materials and different sizes of SiC particles were investigated. Fracture toughness of the composites was significantly improved by introducing SiC whiskers and particles together, compared with that obtained by adding SiC whiskers or SiC particles alone. On increasing the size of the added SiC particles, the fracture toughness of the composites reinforced by both whiskers and particles was increased. Their fracture toughness also showed a strong dependence on the amount of SiC particles (average size 40 μm) and was a maximum at the particle content of 10 vol%. The maximum fracture toughness of these composites was 10.5 MPa·m^1/2 and the flexural strength was 550 MPa after addition of 20 vol% of SiC whiskers and 10 vol% of SiC particles having an average particle size of 40 μm. These mechanical properties were almost constant from room temperature to temperatures around 1000°C. Fracture surface observations revealed that the reinforcing mechanisms acting in these composites were crack deflection and crack branching by SiC particles and pullout of SiC whiskers.     

Diamond-Coated Silicon Carbide Whiskers

Colloidal techniques have been used to seed SiC whiskers with submicrometer-sized diamond particles. The diamond and SiC particulates are co-suspended in an aqueous medium and cast to form highly porous bodies. Electron cyclotron resonance chemical vapor deposition is used to grow dense, polycrystalline diamond coatings on the seeded whiskers. The low packing density of the cast green bodies allows for infiltration of the growth zone beneath the exposed surface. Electron microscopy is used to estimate the coating thickness and depth of growth infiltration.     

Anisotropy of Silicon Nitride with Aligned Silicon Nitride Whiskers

A model based on anisotropic sintering shrinkage of silicon nitride with aligned silicon nitride whisker seeds was built in order to provide an easy way to obtain information on how the large elongated grains were aligned. The method requires a simple measuring device for the information. XRD analysis showed a good correlation with predictions of the model. Both predictions of the model and experimental results indicated that the fraction of aligned large elongated grains increased as the whisker content increased.     

Coating of Fine-Grained Silicon Nitride Whiskers on Fiber-like Silicon Nitride

Fine-grained silicon nitride (Si3N4) whiskers were coated on Si3N4 fibers through a vapor-liquid-solid mechanism under the following process. After the oxide glass of a Si-Al-Y-O system was coated on seed Si3N4 fibers, the coated fibers were heated at 1490°C and 700° in the vapor of the Si-N system which was generated by decomposition of amorphous Si3N4. The resulting specimens looked just like rose twigs. The Si3N4 whiskers were precipitated by nucleation in a liquid phase generated by melting of the oxide glass layers on the Si3N4 fibers.     

Characterization of Silicon Carbide Whiskers

SiC whiskers from six manufacturers were characterized by bulk chemical techniques, X-ray photoelectron spectroscopy, X-ray diffraction, and scanning transmission electron microscopy or scanning electron microscopy. Major component (C, Si, and O) surface chemistries of the whiskers fell into four general categories: high oxygen content with oxide resembling a SiO₂, high oxygen content with oxide resembling a Si-O-C glass, and hydrocarbon. Several whiskers exhibited significant surface impurities—in particular, Fe. From a morphological viewpoint, significant differences in diameter, debris level, straightness, and types and quantities of defects were observed from one manufacturer to another.     

Defects in Silicon Carbide Whiskers

Defects in silicon carbide whiskers made from rice hulls were identified and analyzed using transmission electron microscopy. The whiskers were characterized by a high density of planar faults lying on close-packed planes perpendicular to the whisker axis. The faulting resulted in complex mixtures of β and α polytypes arranged in thin lamellae normal to the whisker axis. Core regions of whiskers were often filled with small cavities ranging in size from 1 to 20 nm. Partial dislocations accompanied the cavities and were analyzed through specimen tilting experiments.     

Silicon Carbide Monofilament-Reinforced Silicon Nitride or Silicon Carbide Matrix Composites

SiC-monofilament-reinforced SiC or Si₃N₄ matrix composites were fabricated by hot-pressing, and their mechanical properties and effects of filaments and filament coating layers were studied. Relationships between frictional stress of filament/matrix interface and fracture toughness of SiC monofilament/Si₃N₄ matrix composites were also investigated. As a result, it was confirmed experimentally that in the case of composites fractured with filament pullout, the fracture toughness increased as the frictional stress increased. On the other hand, when frictional stress was too large (>about 80 MPa) for the filament to be pulled out, fracture toughnesses of the composites were almost the same and not so much improved over that of Si₃N₄ monolithic ceramics. The filament coating layers were found to have a significant effect on the frictional stress of the SiC monofilament/Si₃N₄ matrix interface and consequently the fracture toughness of the composites. Also the crack propagation behavior in the SiC monofilament/Si₃N₄ matrix composites was observed during flexural loading and cyclic loading tests by an in situ observation apparatus consisting of an SEM and a bending machine. The filament effect which obstructed crack propagation was clearly observed. Fatigue crack growth was not detected after 300 cyclic load applications.     

Texture in Silicon Nitride Seeded with Silicon Nitride Whiskers of Different Sizes

Silicon nitride ceramics seeded with 3 wt%β-Si₃N₄ whiskers of two different sizes were prepared by a modified tape casting and gas pressure sintering. The fine whiskers had a higher aspect ratio than the coarse whiskers. Quantitative texture analysis including calculation of the orientation distribution function (ODF) was used for obtaining the degrees of preferred orientation of sintered samples. The maximum multiples of random distribution (mrd) values of samples seeded with the fine and coarse whiskers were large, greater than 15 and 9, respectively. Meanwhile, the mrd value of a sample seeded with fine whiskers was only 9 when it was prepared by conventional tape casting. The microstructures and the XRD data revealed that the well-aligned whiskers grew significantly after sintering and dominated the texture. Differences among the degrees of preferred orientation of the samples were explained using Jeffrey's model on rotation of elliptical particles carried by a viscous fluid.     

Complex Impedance Analysis on the Orientation Effect of Whiskers in Oriented Silicon Carbide Whisker/Silicon Nitride Composites

The effect of whisker orientation on the electrical properties of SiC_w/Si₃N₄ composites was investigated, using the principle of complex impedance. The impedance spectra of the composites exhibited significant dependence on whisker orientation. Based on the experimental results and the microstructure of the composites, the impedance mechanisms were discussed and a corresponding equivalent-circuit model was presented, which agreed well with the experiments.     

Microwave Synthesis of Ultrafine Silicon Carbide Whiskers

Silicon carbide (SiC) whiskers were formed by microwave and conventional heating in the present study. SiC whiskers with diameters in the nanometer range were synthesized by reducing silica (SiO₂) with various forms of carbon in a microwave furnace. Ultrafine SiO₂ powder, char, phenolformaldehyde resin, and carbon black were used as starting materials. The effects of temperature and type of heating on the production of SiC whiskers, as well as the role of carbon, are discussed here.     

Chemical-Vapor-Infiltrated Silicon Nitride, Boron Nitride, and Silicon Carbide Matrix Composites

Composites of carbon/chemical-vapor-deposited (CVD) Si₃N₄, carbon/CVD BN, mullite/CVD SiC, and SiC yarn/CVD SiC were prepared to determine if there were inherent toughness in these systems. The matrices were deposited at high enough temperatures to ensure that they were crystalline, which should make them more stable at high temperatures. The fiber-matrix bonding in the C/Si₃N₄ composite appeared to be too strong; the layers of BN in the matrix of the C/BN were too weakly bonded; and the mullite/SiC composite was not as tough as the SiC/SiC composites. Only the SiC yarn/CVD SiC composite exhibited both strength and toughness.     

Tensile Strength of Silicon Nitride Whiskers Synthesized by Reacting Amorphous Silicon Nitride and Titanium Dioxide

The tensile strength of α-Si₃N₄ whiskers synthesized by reacting amorphous Si₃N₄ and TiO₂ at 1490°C under a N₂ pressure of 700 torr was measured using a microbalance, and the diameter dependence of the strength was investigated. The Si₃N₄ whiskers had diameters of 0.04 and 0.8 μm and dominant [1011] and [1010] growth directions. Chemical analysis showed that they contained Ti and O impurities. The tensile strength of six Si₃N₄ whiskers increased from 17 to 59 GPa with decreasing whisker diameter.     

Reactivity of Aluminum Nitride Powder in Aqueous Silicon Nitride and Silicon Carbide Slurries

The reactivity of AlN powder with water in supernatants obtained from centrifuged Si₃N₄ and SiC slurries was studied by monitoring the pH versus time. Various Si₃N₄ and SiC powders were used, which were fabricated by different production routes and had surfaces oxidized to different degrees. The reactivity of the AlN powder in the supernatants was found to depend strongly on the concentration of dissolved silica in these slurries relative to the surface area of the AlN powder in the slurry. The hydrolysis of AlN did not occur if the concentration of dissolved silica, with respect to the AlN powder surface, was high enough (1 mg SiO₂/(m² AlN powder)) to form a layer of aluminosilicates on the AlN powder surface. This assumption was verified by measuring the pH of more concentrated (31 vol%) Si₃N₄ and SiC suspensions also including 5 wt% of AlN powder (with respect to the solids).     

轮胎半焦制备碳化硅晶须的研究

以轮胎半焦和石英砂为原料,采用碳热还原法制备出碳化硅晶须.利用X射线衍射仪(XRD)和扫描电镜(SEM)对制得的产物进行物相组成和形貌分析,探究反应温度(1300～1500℃)、反应时间(120～300 min)、升温程序以及半焦粒度对合成碳化硅晶须的影响规律.结果表明:温度控制在1350℃左右,且采用先升至1500℃...     

Foreign Object Damage Resistance of Silicon Nitride and Silicon Carbide

To clarify the foreign object damage (FOD) resistance of ceramics, chipping fracture mode and flexural fracture mode were investigated using several types of Si₃N₄ and Sic. The critical velocity which is the threshold impact velocity of the projectile for chipping fracture and flexural fracture was determined. The critical velocity of the chipping fracture mode is explained as a function of K ^5/2_IC a ^–5/4, and depends on the hardness and the shape of the projectile. The critical velocity of the flexural fracture mode is explained as a function of σ^5/6_C t ^5/3. The mechanisms of impact damage are discussed.