Silicon Carbide Whisker Stability During Processing of Silicon Nitride Matrix Composites

The effects of two different sources of SiC whiskers on the chemistry and microstructure of the SiC-whisker—Si₃N₄ composites were evaluated using scanning transmission electron microscopy. Analyses were performed after presintering in N₂ and after encapsulated hot isostatic pressing. Significant differences in the porosity, α- to β-Si₃N₄ conversion, and whisker degradation were observed after presintering. It was also noted that whiskers containing surface iron impurities were converted to Si₃N₄ during processing. Whiskers from the source having low surface iron exhibited little reaction. After hot isostatic pressing, some oxidation of the cleaner whiskers was observed.     

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.     

Impact Damage and Strength Degradation in a Silicon Carbide Reinforced Silicon Nitride Composite

Adding SiC particles to Si₃N₄ and subjecting the mixture to a sinter-hot-isostatic-pressing process increases both the strength and elastic modulus. It also decreases the hardness but maintains the fracture toughness, which results in a higher resistance to crack initiation and propagation during spherical particle impact. Sinter-hot-isostatically-pressed composites exhibit elastic response as their dominant behavior. They also display a high resistance to Hertzian cone crack initiation and extension. This is due to the increased degree of inelastic deformation of sinter-hot-isostatically-pressed composites.     

Effect of Silicon Carbide Whisker and Titanium Carbide Particulate Additions on the Friction and Wear Behavior of Silicon Nitride

A Si₃N₄/TiC composite was previously demonstrated to exhibit improved wear resistance compared to a monolithic Si₃N₄ because of the formation of a lubricious oxide film containing Ti and Si at 900°C. Further improvements of the composite have been made in this study through additions of SiC whiskers and improved processing. Four materials—Si₃N₄, Si₃N₄/TiC, Si₃N₄/SiC_wh, and Si₃N₄/TiC/SiC_wh— were processed to further optimize the wear resistance of Si₃N₄ through improvements in strength, hardness, fracture toughness, and the coefficient of friction. Oscillatory pin on flat wear tests showed a decrease in the coefficient of friction from ∼0.7 (Si₃N₄) to ∼0.4 with the addition of TiC at temperatures reaching 900°C. Wear track profiles illustrated the absence of appreciable wear on the TiC-containing composites at temperatures above 700°C. Microscopic (SEM) and chemical (AES) characterization of the wear tracks is also included to deduce respective wear and lubricating mechanisms.     

Mechanical Properties of Alumina/Silicon Carbide Whisker Composites

The improvement of mechanical properties of Al₂O₃/SiC whisker composites has been studied with emphasis on the effects of the whisker content and of the hot-pressing temperature. Mechanical properties such as fracture toughness and fracture strength increased with increasing whisker content up to 40 wt%. In the case of the high SiC whisker content of 40 wt%, fracture toughness of the sample hot-pressed at 1900° decreased significantly, in spite of densification, compared with one hot-pressed at 1850°. Fracture toughness strongly depended on the microstructure, especially the distribution of SiC whiskers rather than the grain size of the Al₂O₃ matrix.     

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.     

Spherical-Impact Damage and Strength Degradation in Silicon Nitrides for Automobile Turbocharger Rotors

Spherical-impact damage to two silicon nitrides is investigated. Gas-pressure-sintered silicon nitride exhibits an elastic response to impact by spherical partially stabilized zirconia particles, resulting in Hertzian cone-crack initiation in the sintered body. Pressureless-sintered silicon nitride, on the other hand, demonstrated an elastic/plastic response, with median/radical-crack initiation. These differences in behavior are due to their microstructural differences as well as to the different hardness values of the silicon nitrides in relation to those of the PSZ spheres. The postimpact bend strength of silicon nitrides is also degraded when crack length exceeds the inherent flaw size.     

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.     

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.     

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.     

Silicon Carbide Whisker/Alumina Matrix Composites: Effect of Whisker Surface Treatment on Fracture Toughness

The fracture toughness of a 30 vol% SiC whisker/Al₂O₃ matrix composite was evaluated as a function of whisker surface chemistry. Two types of SiC whiskers (Silar-SC-9 and Tateho-SCW-1-S) were investigated. Modification of the whisker surface chemistry was achieved by subjecting the whiskers to thermal treatments under controlled atmospheres. Whisker surface chemistry, as determined by X-ray photoelectron spectroscopy, was correlated to the fracture toughness of the composites.     

Effect of Vapor—Liquid—Solid and Vapor—solid Silicon Carbide Whiskers on the Effective Thermal Diffusivity/Conductivity of Silicon Nitride Matrix Composites

A study was conducted of the relative effect of vapor—liquid—solid (VLS) and vapor—solid (VS) SiC whiskers on the effective thermal diffusivity and conductivity of pressed-densified silicon nitride. It was found that VLS whiskers cause an increase in the thermal diffusivity/conductivity, whereas the opposite effect was found for the VS-SiC whiskers. Comparison with composite theory suggests that the VS-SiC whiskers have a thermal conductivity as low as 25 to 30 W/(m·K). In contrast the VLS-SiC whiskers appear to have a value for the thermal conductivity of at least about 100 W/(m·K) to as high as 250 W/(m·K). These large differences in thermal conductivity for these two types of SiC whiskers are attributed to the much larger density of structural defects in the VS-SiC whiskers, which act as phonon scatterers, thereby lowering the thermal conductivity.     

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).     

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.     

Whisker Toughening: A Comparison Between Aluminum Oxide and Silicon Nitride Toughened with Silicon Carbide

Two whisker-toughened materials have been studied, with the objective of identifying the mechanisms that provide the major contribution to toughness. It is concluded that, for composites with randomly oriented whiskers, bending failure of the whiskers obviates pullout, whereupon the major toughening mechanisms are the fracture energy consumed in creating the debonded interface and the stored strain energy in the whiskers, at failure, which is dissipated as acoustic waves. The toughening potential is thus limited. High toughness requires extensive pullout and, hence, aligned whiskers with low fracture energy interfaces.     

High-Temperature Toughness and Tensile Strength of Whisker-Reinforced Silicon Nitride

The R -curve behavior of hot-pressed silicon nitride reinforced with silicon carbide whiskers is investigated from room temperature to 1300°C using the chevron-notch bend test. The bridging stress, estimated from increment of fracture resistance in the rising R -curve, is discussed in relation to tensile strength measured with various displacement rates at 1300°C. The reinforcing whiskers provide most of the tensile strength in the creep-deformation range at 1300°C. The whiskers appear to bear a great deal of the applied tensile stress during slow crack growth.     

R-Curve Behavior in a Silicon Carbide Whisker/Alumina Matrix Composite

R -curve measurements were performed on a SiC whisker/Al₂O₃ matrix composite. A controlled flaw/strength technique was utilized to determine fracture resistance as a function of crack extension. Rising R -curve behavior with increasing crack extension was observed, confirming the operation of wake toughening effects on the crack growth resistance. Observations of crack/microstructure interactions revealed that bridging by intact whiskers in the crack wake was the mechanism responsible for the rising R -curve behavior.     

Some New Perspectives on Oxidation of Silicon Carbide and Silicon Nitride

This study provides new perspectives on why the oxidation rates of silicon carbide and silicon nitride are lower than those of silicon and on the conditions under which gas bubbles can form on them. The effects on oxidation of various rate-limiting steps are evaluated by considering the partial pressure gradients of various species, such as O₂, CO, and N₂. Also calculated are the parabolic rate constants for the situations when the rates are controlled by oxygen and/or carbon monoxide (or nitrogen) diffusion. These considerations indicate that the oxidation of silicon carbide and silicon nitride should be mixed controlled, influenced both by an interface reaction and diffusion.     

Preparation of Ultrafine Silicon Nitride, and Silicon Nitride and Silicon Carbide Mixed Powders in a Hybrid Plasma

Ultrafine Si₃N₄ and Si₃N₄+ SiC mixed powders were synthesized through thermal plasma chemical vapor deposition (CVD) using a hybrid plasma which was characterized by the superposition of a radio-frequency plasma and an arc jet. The reactant, SiCl₄, was injected into an arc jet and completely decomposed in a hybrid plasma, and the second reactant, CH₄ and/or NH₃, was injected into the tail flame through multistage ring slits. In the case of ultrafine Si₃N₄ powder synthesis, reaction effieciency increased significantly by multistage injection compared to single-stage injection. The most striking result is that amorphous Si₃N₄ with a nitrogen content of about 37 wt% and a particle size of 10 to 30 nm could be prepared successfully even at the theoretical NH₃/SiCl₄ molar ratio of ∼ 1.33, although the crystallinity depended on the NH₃/SiCl₄ molar ratio and the injection method. For the preparation of Si₃N₄+ SiC mixed powders, the N/C composition ratio and particle size could be controlled not only by regulating the flow rate of the NH₃ and CH₄ reactant gases and the H₂ quenching gas, but also by adjusting the reaction space. The results of this study provide sufficient evidence to suggest that multistage injection is very effective for regulating the condensation process of fine particles in a plasma tail flame.     

Electrokinetic Behavior of Aqueous Silicon Carbide Whisker Suspensions

Repulsive forces that promote dispersion arise from electrostatic repulsion between charged surfaces on the particles. Particles in aqueous suspensions develop surface charge through acid-based surface reactions. This study examines the dispersion of silicon carbide whiskers in the presence of a dispersing agent and coupling agents. The dispersion was investigated from zeta potential measurements. The presence of sodium polyacrylate increases the zeta potential to high negative values. The increase is due to hydrogen-bond formation between carboxylate groups on the polyacrylate chain and the silanol groups on the SiC _w surfaces. Coupling agent A-1100 shows a shift on the surface charge as a function of concentration. In general, the amino functional group of A-1100 silane is electron donating and has a natural tendency to form hydrogen bonds with silanol groups. The other two coupling agents, i.e., A-172 and A-187, do not exhibit any interaction with hydroxylated SiC _w surfaces.