Elevated-Temperature-Delayed Failure of Alumina Reinforced with 20 vol% Silicon Carbide Whiskers

Alumina composites reinforced with 20 vol% SiC whiskers were exposed to applied stresses in four-point flexure at temperatures of 1000°, 1100°, and 1200°C in air for periods of up to 14 weeks. At 1000° and 1100°C, an "apparent" fatigue limit was established at stresses of ∼ 75% of the fast fracture strength. However, after long-term (>6 weeks) tests at 1100°C, some evidence of crack generation as a result of creep cavitation was detected. At 1200°C applied stresses as low as 38% of the 1200°C fracture strength were sufficient to promote creep deformation and accompanying cavitation and crack generation and growth resulting in failures in times of <250 h.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Microstructure and Mechanical Properties of Mullite–Silicon Carbide Composites

Mullite-SiC-whisker composites were prepared by powder processing using two commercial SiC whiskers. These composites were prepared by sintering rather than hot-pressing. A mulliteSlC-powder composite and a base line mallite material were also prepared for comparison with the two whisker composite materials. Fracture toughness measurements showed significant enhancement in only one of the whisker composite materials. The microstructure of the four materials was examined by scanning electron microscopy and transmission electron microscopy to assist in the explanation of the mechanical behavior of these composites. The examinations suggested that most of the toughening results from second-phase particles, with only limited toughening from effects associated with whiskers per se. In one case, higher toughness was partially associated with the formation of sialon phase by reaction with the whiskers and the furnace environment.     

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.     

催化剂对以硅溶胶为硅源合成碳化硅晶须的影响

以硅溶胶和炭黑为原料,金属硅、三氧化二铁和硅铁合金为催化剂,采用碳热还原法合成碳化硅晶须,通过XRD及SEM对合成产物的物相及形貌进行分析,探讨了合成温度、催化剂种类、催化剂加入量对合成碳化硅晶须的影响.结果表明:在原料中加入催化剂,合成碳化硅晶须的最佳温度为1550℃;以Si-Fe合金为催化剂合成碳化硅晶须的效果明显好于以Fe2O3和金属硅为催化剂合成效果;Si-Fe合金加入量(占SiO2质量分数)为1％时,晶须生成率高,成直线形,长度10 ～ 50μm,直径0.1 ～0.3 μm.     

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.     

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.     

Dependence of Silicon Carbide Product Morphology on the Degree of Mechanical Activation

Mechanical activation before carbothermic reduction can substantially enhance the formation of SiC from SiO₂and carbon mixtures. However, the morphology (e.g., particles or whiskers) of SiC formed from mechanically activated SiO₂and carbon mixtures is dependent of the degree of mechanical activation and the condition of the subsequent carbothermic reduction. These phenomena are investigated and rationalized based on the increased reactivity of the reactants and SiC formation mechanisms.     

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.     

Brittle-to-Ductile Transition in Silicon Carbide

Observations of the microstructure and creep behavior of two commerical silicon carbides are presented. A combination of techniques has been used to characterize the microstructures. Sequential creep rupture testing has been carried out and scanning electron microscopy used to observe creep-crack propagation and damage development. Basic theory for stress fields and creep rates around a crack tip is relatd to the observed brittle-to-ductile transition in these materials. Analogy with the brittle-to-ductile transition in steels is made and used to interpret the present observation.     

Formation and Morphology of 2H-SiC Whiskers by the Decomposition of Silicon Nitride

α-SiC whiskers were synthesized by decomposition of Si₃N₄ at 1900°C in a graphite vessel under a pressure of 10 atm (1.0 − 10⁶ Pa) of N₂. The fibrous crystal produced was identified as 2H-SiC by X-ray diffraction. The whiskers take the shape of straight needles colored white, gray, or green. The average length of the whiskers is about 100 μm and the width is about 8 μm. The morphology and structure of the fibrous SiC were observed by means of scanning electron microscopy, transmission electron microscopy, and optical microscopy, and were found to have four types of cross-sectional shapes: (A) tetragonal bar, (B) flat plate, (C) hexagonal bar, and (D) triangular bar. The lateral surfaces of types A and D and the lateral plane of type B consist largely of grooves or growth lines. These types grew in zones around the column of Si₃N₄, corresponding to the degree of supersaturation of silicon in the ambient atmosphere. That is, the change in the degree of supersaturation of Si, which became higher from the lower to the upper part of the growth vessel, resulted in the whiskers growing from hexagonal to flat plate to tetragonal shapes.     

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.     

碳化硅木质陶瓷的显微结构及力学性能

以汉麻秆芯碳化后的碳粉为原料,分别采用注浆和干压成型工艺制备素坯,通过反应烧结制备出碳化硅木质陶瓷.研究了注浆成型工艺中悬浮稳定剂的种类和添加量对浆料性能的影响.采用激光共聚焦显微镜、扫描电子显微镜和X射线衍射仪等分析了碳化硅木质陶瓷的显微结构、物相组成及力学性能.结果表明:采用注浆成型制备的碳化硅木质陶瓷力学性能优异,实测的游离硅含量同理论计算结果一致,说明渗硅过程中硅碳反应充分,烧结体显微硬度、弯曲强度、弹性模量和断裂韧性分别为22.3 GPa、397 MPa、290 GPa和3.0 MPa·m1/2.     

Processing, Fracture Toughness, and Vickers Hardness of Allylhydridopolycarbosilane-Derived Silicon Carbide

Bulk specimens of precursor-derived silicon carbide (SiC) suitable for mechanical-property measurements were prepared from allylhydridopolycarbosilane (AHPCS), which is a commercially available, hyperbranched polycarbosilane. Crack-free pellets were obtained by cold-pressing mixtures of finely ground, 1000°C pyrolyzed, "AHPCS-SiC" with neat AHPCS, followed by pyrolysis to 1000°C and ten subsequent reinfiltration/pyrolysis steps with the neat liquid AHPCS. Then, these pellets were heat-treated to 1200°, 1400°, and 1600°C, followed by additional reinfiltration/pyrolysis cycles to the final respective maximum temperatures. This fabrication process simulated the production of the matrix phase for ceramic-matrix composites via successive infiltration/pyrolysis cycles. The density of the material processed at these temperatures, measured via the Archimedes method, was 2.3, 2.5, 2.6, and 2.9 g/cm³, respectively, and the average open porosities of the samples were 2, 0.2, 1, and 9 vol%, respectively. The fracture toughness was measured using the single-edge V-notched-beam method, and the hardness was measured via Vickers indentation. The samples had an average toughness of 1.40 ± 0.08, 1.65 ± 0.09, 1.67 ± 0.07, and 1.46 ± 0.08 MPa·m^1/2 for the samples that were treated at 1000°, 1200°, 1400°, and 1600°C, respectively. The Vickers hardness for these samples, measured at a load of 1000 g, was 12 ± 1, 13 ± 2, 11 ± 1, and 9 ± 1 GPa, respectively.