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.     

Tetragonal Zirconia Polycrystals Reinforced with SiC Whiskers

The microstructure and the mechanical properties of hot-pressed tetragonal ZrO₂ polycrystals (TZP) reinforced with up to 30 vol% SiC whiskers were studied. The SiC whisker-TZP composites were stable under the hot-pressing conditions at 1450°C. Annealing in an oxidizing atmosphere at ∼1000°C resulted in glass formation and microcracking caused by whisker oxidation and transformation of the ZrO₂ grains near the whiskers to monoclinic symmetry. The fracture toughness was markedly improved by the dispersed whiskers (∼12 Mpa·m^1/2 at 30 vol% SiC) compared to the values measured for the matrix (∼6 Mpa·m^1/2). The flexural strength of the hot-pressed TZP-30 vol% SiC whisker composite at 1000°C (∼400 MPa) was twice that of the TZP matrix.     

Thermal Conductivity of Vapor-Liquid-Solid and Vapor-Solid Silicon Carbide Whisker-Reinforced Lithium Aluminosilicate Glass-Ceramic Composites

The thermal conductivities of two lithium aluminosilicate glass-ceramic matrix composites reinforced with 30 vol% of either SiC VS (rice hull) whiskers or SiC VLS (vapor-liquid-solid) whiskers were determined from room temperature to 500°C. Because of the preferred alignment of the whiskers, the thermal conductivity values normal to the hot-pressing direction were found to be significantly higher than those in the parallel direction. The composites with the VLS whiskers exhibited higher thermal conductivity values than those with the VS whiskers. An analysis of the room-temperature data showed that the thermal conductivity values parallel to the hot-pressing direction were higher than those predicted from theory, even for whiskers with infinite thermal conductivity and perfect interfacial thermal contact. This effect was attributed to a significant contribution of percolation to the total heat flow as a result of direct whisker-to-whisker contact. For both types of whiskers, the interfacial thermal conductance and thermal conductivity values (at ∼6.5 × 10⁵ W/(m²-K) and 200 W/(m·K), respectively) inferred from the composite thermal conductivity values perpendicular to the hot-pressing direction were essentially the same. It was concluded that the order of magnitude difference in thickness for the two whisker types was primarily responsible for the differences in thermal conductivity measured for these two composites.     

Preparation and Mechanical Properties of SiC Whisker and Nanosized Mullite Particulate Reinforced TZP Composites

The influence of the addition of nanometer mullite particulates and SiC whiskers coated with alumina on the mechanical properties of tetragonal zirconia polycrystals (TZP) was studied. With increasing mullite( p ) content the high-temperature flexural strength increased, and a maximum value of 360 MPa at 1000°C was reached at 15 vol% mullite( p . Furthermore, 10 vol% SiC( w ) reinforced 15 vol% mullite/TZP composites improved the high-temperature strength up to 490 MPa at 1000°C, 2.7 times that of pure TZP matrix. This high-temperature strengthening is attributed to load transfer from TZP matrix to SiC( w ) and mullite particulates. Significant whisker pull-out and interface debonding were also observed on the fractured surfaces when SiC( w ) was coated with Al₂O₃ film.     

High-Temperature Creep Deformation of Alumina — SiC-Whisker Composites

The creep resistance at temperatures between 1200° and 1300°C in air of alumina—SiC-whisker composites was investigated via four-point flexure to examine (1) the effect of whisker content and (2) the influence of densification additives (i.e., Y₂O₃ (plus MgO)). The creep resistance of polycrystalline alumina is greatly improved with the addition of ≤ 20 vol% SiC whiskers. The interlocking/pinning of grains by whiskers which limits grain-boundary sliding contributes to the improvement in creep resistance. However, the creep rates of alumina composites in air increase at whisker contents ≥ 30 vol%. Electron microscopy observations suggested that the degradation in creep resistance for whisker content ≥ 30 vol% originated from (1) the promotion of creep cavitation and subsequent microcrack generation from the higher number density of nucleation sites and (2) more extensive formation of grain-boundary amorphous phase(s) associated with an observed increased oxidation rate. Along this one, the excellent creep resistance of alumina composites containing 20 vol% SiC whiskers was significantly degraded by the presence of the intergranular amorphous phases introduced by the addition of the Y₂O₃ densification additive.     

Self-Crack-Healing Behavior of Mullite/SiC Particle/SiC Whisker Multi-Composites and Potential Use for Ceramic Springs

To improve fracture toughness and encourage excellent self-crack-healing ability, mullite/SiC particle/SiC whisker multi-composites and mullite/SiC whisker composites were hot pressed. The crack-healing abilities and mechanical properties of these sintered composites were investigated. Based on the obtained results, the usefulness of the mullite composite as a material for springs was discussed. The part of mullite/15 vol% SiC whisker/SiC 10 vol% particle containing healed cracks retained high reliability over the whole measured temperature range. When the crack-healing ability was endowed by SiC whiskers alone, the parts containing the healed pre-cracks were found to have a heat-resistance limit temperature. Mullite/15 vol% SiC whisker/10 vol% SiC particle multi-composite had the best potential as a material for springs used at high temperatures, because it had an adequate crack-healing ability as well as shear deformation ability almost two times stronger than that of monolithic mullite.     

Mechanical Properties and Microstructure of Whisker-Reinforced Alumina–30 vol% Glass Matrix Composite

High-density whisker-reinforced composites of an alumina-30 vol% glass matrix material were produced by hot-pressing in the temperature range 1350° to 1400°C in air. Significant improvement was observed in the strength of composites containing 15 vol% SiC whiskers, up to ∼550 MPa, but with only a small effect on the fracture toughness. In composites containing Si₃N₄ whiskers, no reinforcement was achieved. Transmission electron microscopy showed the formation of a protective layer of amorphous silica on the SiC whiskers, while the Si₃N₄ whiskers were found to react with the matrix. The mechanical properties were related to the microstructure and the density of the samples.     

Suspension Processing of Al2O3/SiC Whisker Composites

Homogeneous Al₂O₃ powder/SiC whisker compacts were prepared by suspension processing. By optimizing the conditions for particle/whisker codispersion, castable suspensions could be prepared at total-solids concentrations 50 vol%. Green bodies with high relative density (∼66% to 70%) were obtained with SiC whisker contents in the range of 5 to 30 vol%. Although densification was severely inhibited by the SiC whiskers, significantly higher sintered densities were obtained by suspension processing compared to dry processing.     

Colloidal Processing of SiC Whisker Composites

In the present study, the dispersion processing and the characterization of the dispersity of SiC whiskers for reinforced ceramic-based composites were studied. Two kinds of methods were used to determine the dispersity of SiC whiskers. First, the sedimentation density was employed to directly characterize the dispersity of the SiC whiskers. The other is an indirect characterization. The dispersity and the distribution of the SiC whisker in a ceramic matrix were analyzed and characterized indirectly with SEM observation and the determination of the relative density. By means of the colloidal processing of the whiskers in which electrostatic and steric interaction were used to counteract the attractive forces between whiskers, four dispersion processing routes were used to mix the SiC whisker into the Al₂O₃ powder. The sedimentation results indicated that, with aluminum alkoxide as a dispersant, SiC whiskers were completely deflocculated and the sedimentation density increased twofold from 8.5% to 24% of theoretical density, and both the homogeneous distribution of SiC whiskers and densification of the 30 vol% SiC whisker-reinforced Al₂O₃ (AS) were achieved by hot pressing. The relative density of the AS composites was more than 99.7%. SEM observation showed no agglomeration of SiC whiskers.     

Creep Deformation in an Alumina–Silicon Carbide Composite Produced via a Directed Metal Oxidation Process

Flexural creep studies were conducted in a commercially available alumina matrix composite reinforced with SiC particulates (SiC_p) and aluminum metal at temperatures from 1200° to 1300°C under selected stress levels in air. The alumina composite (5 to 10 μm alumina grain size) containing 48 vol% SiC particulates and 13 vol% aluminum alloy was fabricated via a directed metal oxidation process (DIMOX(tm))† and had an external 15 μm oxide coating. Creep results indicated that the DIMOX Al₂O₃–SiC_p composite exhibited creep rates that were comparable to alumina composites reinforced with 10 vol% (8 (μm grain size) and 50 vol% (1.5 μm grain size) SiC whiskers under the employed test conditions. The DIMOX Al₂O₃–SiC_p composite exhibited a stress exponent of 2 at 1200°C and a higher exponent value (2.6) at ≥ 1260°C, which is associated with the enhanced creep cavitation. The creep mechanism in the DIMOX alumina composite was attributed to grain boundary sliding accommodated by diffusional processes. Creep damage observed in the DIMOX Al₂O₃-SiC_p composite resulted from the cavitation at alumina two-grain facets and multiple-grain junctions where aluminum alloy was present.     

Microstructure evolutions of SiC whiskers at high temperature and its effects on silicon carbide ceramics

SiC whisker with a single-crystal structure is promising in enhancing the strength and toughness of advanced structural ceramics, owing to its excellent properties. However, studies on its microstructure evolution at high temperature (>2000 °C) are scarce. Herein, SiC whiskers were calcined at 2100 °C, and XRD, SEM, and TEM were employed to analyze microstructure evolutions. Compared with raw whiskers, XRD results indicated serious annihilation of stacking faults after calcination. The annihilation led to the fracture of whiskers and the formation of β-SiC grains, and then partial grains underwent the phase transformation to form hexagonal prism and triangular prism α-SiC grains with diameters of about 10 μm, according to SEM and TEM results. Furthermore, SiC ceramics containing different whisker contents were innovatively fabricated by pressureless solid-state sintering. The flexural strength and fracture toughness of SiC ceramic containing 10 vol% whiskers were 540 MPa and 5.1 MPa m^0.5, resulting in 38% and 11% higher values than those without whiskers, respectively.     

Processing and Characterization of SiC-Whisker-Reinforced Alumina-Matrix Composites

Brittle monolithic alumina can be reinforced with highstrength single-crystal SiC whiskers with the effect of increasing fracture toughness. In this study, well-mixed and nearly fully dense SiC whisker/alumina composites were fabricated by wet-blending the constituents and uniaxially hot-pressing the resulting powder. The alumina-matrix grain size depended on whisker volume fraction, whisker surface-oxygen content, and hot-pressing environment. Fracture toughness, measured by an indentation-fracture method, increased from 3.0 MPa·m^1/2 for the hot-pressed unreinforced alumina to 10.7 MPa·m^1/2 for the composite containing 25 vol% SiC whiskers. Fracture surfaces revealed evidence of toughening by the mechanisms of crack deflection, pullout, and crack bridging by the whiskers. The observed increase in fracture toughness of alumina due to the addition of SiC whiskers was correlated with existing models of toughening mechanisms.     

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.     

Toughening Behavior Involving Multiple Mechanisms: Whisker Reinforcement and Zirconia Toughening

Since the contribution of transformation toughening increases with the loca crack resistance (which is proportional to the toughness of the matrix), ZrO₂ particles were added to a toughened, whisker-reinforced ceramic matrix. Analysis revealed that the combination of these multiple toughening agents should result in ceramic composites tougher than (1) that achieved by either mechanism by itself or (2) the sum of the two processes. The toughness of mullite could be increased 1.8-and 2.4-fold with a 20 vol% addition of ZrO₂ particles or SiC whiskers, respectively. However, when 20 vol% of both ZrO₂ particles and SiC whiskers were added, the toughness was increased at least 3-fold with monoclinic m -ZrO₂ and by >5-fold with tetragonal t -ZrO₂. The differences in the toughening achieved when t -ZrO₂ vs m -ZrO₂ is present in the SiC-whisker-reinforced mullite are attributed to differences in their interdependencies upon the whisker reinforcement.     

Slip Casting of SiC-Whisker-Reinforced Si3N4

Si₃N₄ composite materials containing up to 20 vol% SiC whiskers were slip cast and pressureless sintered at 1820°C and 0.13 MPa of N₂. Viscosimetry showed no influence of whisker loading on the rheology of the highly concentrated aqueous slips up to 15 vol% whiskers. During casting the whiskers were preferentially aligned parallel to the mold surfaces. Depending on the whisker loading, green densities of 0.64 to 0.69 fractional density could be achieved. Strong anisotropic shrinkage occurred during sintering with a maximum linear shrinkage of 21% perpendicular but only 7% parallel to the whisker plane. With increasing whisker content from 0 to 20 vol% sintered densities decreased from 0.98 to 0.88, respectively.     

Combined role of SiC particles and SiC whiskers on the characteristics of spark plasma sintered ZrB2 ceramics

In this research work, the effects of silicon carbide (SiC) as the most important reinforcement phase on the densification percentage and mechanical characteristics of zirconium diboride (ZrB₂)-matrix composites were studied. In this way, a monolithic ZrB₂ ceramic (as the baseline) and three ZrB₂ matrix specimens each of which contains 25 vol% SiC as reinforcement in various morphologies (SiC particulates, SiC whiskers, and a mixture of SiC particulates/SiC whiskers), have been processed through spark plasma sintering (SPS) technology. The sintering parameters were 1900 °C as sintering temperature, 7 min as the dwell time, and 40 MPa as external pressure in vacuum conditions. After spark plasma sintering, a relative density of ~96% was obtained (using the Archimedes principles and mixture rule for evaluation of relative density) for the unreinforced ZrB₂ specimen, but the porosity of composites containing SiC approached zero. Also, the assessment of sintered materials mechanical properties has shown that the existence of silicon carbide in ZrB₂ matrix ceramics results in fracture toughness and microhardness improvement, compared to those measured for the monolithic one. The simultaneous addition of silicon carbide particulates (SiC_p) and whiskers (SiC_w) showed a synergistic effect on the enhancement of mechanical performance of ZrB₂-based composites.     

Plastic Deformation Mechanisms in SiC-Whisker-Reinforced Alumina

SiC-whisker-reinforced Al₂O₃ samples (SiC_w/Al₂O₃), obtained from three different manufacturers, containing 0–30 vol% SiC have been crept under compression at 1400°C in flowing argon. Compressive creep tests and microstructural observations have been used to characterize the plastic deformation mechanisms. The presence of whiskers decreased the creep rate by reducing grain-boundary sliding. Damage formation was increased, however, because the whiskers acted as stress concentration sites. For specimens with whisker loadings greater than 15%, the absolute creep rate was not strongly dependent on whisker concentration, and the formation of cavitation damage was negligible below a critical stress that depended on the fabrication procedure of the specimen. This creep regime was characterized by a stress exponent of approximately 1, in which deformation occurred primarily by diffusional flow. For the materials with less SiC, the deformation occurred primarily by grain-boundary sliding.     

Synthesis of Mullite Whiskers and Their Application in Composites

Mullite whiskers were synthesized by a vapor-solid reaction. Mullite composition xerogels were fired at 900° to 1600°C with AlF₃ in an airtight container. An average whisker increased in length from 7 μm at 1100°C to 10 μm at 1600°C, whereas an average whisker decreased in aspect ratio from 25 to 10 with increased firing temperature. The whiskers elongated to the c -axis and the side planes were the {110}. A clear lattice image corresponding to (110) lattice spacing up to the edges of the whiskers was observed with high-resolution electron microscopy, and no droplet was observed on the tips of the whiskers. The chemical composition of the whiskers synthesized below 1100°C showed an apparent Al₂O₃-rich composition of about 72 mol%. Composites reinforced by 15 vol% of mullite whiskers in the matrix of 75 vol% mullite/25 vol% Y-TZP enhanced the fracture toughness compared with those materials without mullite whiskers.     

Mechanical Properties, Thermal Shock Resistance, and Thermal Stability of Zirconia-Toughened Alumina-10 vol% Silicon Carbide Whisker Ceramic Matrix Composite

Zirconia-toughened alumina (Al₂O₃–15 vol% Y-PSZ (3 mol% Y₂O₃)) reinforced with 10 vol% silicon carbide whiskers (ZTA-10SiC _w ) ceramic matrix composite has been characterized with respect to its room-temperature mechanical properties, thermal shock resistance, and thermal stability at temperatures above 1073 K. The current ceramic composite has a flexural strength of ∽550 to 610 MPa and a fracture toughness, K _IC , of ∽5.6 to 5.9 MPa·m^1/2 at room temperature. Increases in surface fracture toughness, ∽30%, of thermally shocked samples were observed because of thermal-stress-induced tetragonal-to-monoclinic phase transformation of tetragonal ZrO₂ grains dispersed in the matrix. The residual flexural strength of ZTA–10 SiC _w ceramic composite, after single thermal shock quenches from 1373–1573 to 373 K, was ∽10% higher than that of the unshocked material. The composite retained ∽80% of its original flexural strength after 10 thermal shock quenches from 1373–1573 to 373K. Surface degradation was observed after thermal shock and isothermal heat treatments as a result of SiC whisker oxidation and surface blistering and swelling due to the release of CO gas bubbles. The oxidation rate of SiC whiskers in ZTA-10SiC _w composite was found to increase with temperature, with calculated rates of ∽8.3×10⁻⁸ and ∽3.3×10⁻⁷ kg/(m²·s) at 1373 and 1573 K, respectively. It is concluded that this ZTA-10SiC _w composite is not suitable for high-temperature applications above 1300 K in oxidizing atmosphere because of severe surface degradation.     

Sintering and mechanical behavior of SiC and WC co-added TiC-based composites densified by hot-pressing

In this investigation, the individual and synergetic influences of the SiC whiskers and WC particles on the various features of TiC were studied. Fully dense specimens were secured when 40 vol% SiC additive was added to the TiC and TiC-WC systems. The nucleation and growth of the new SiC grains were found as the two main mechanisms positively affecting the sinterability of TiC. Although WC particles were completely dissolved into the TiC matrix in the TiC-WC system, they were entrapped in the newly grown SiC grains in the TiC-WC-SiC system, contributing to strengthening of the specimen. The highest values of flexural strength (590 MPa) and Vickers hardness (2525 HV_0.5 kg) were attained for the sample codoped with SiC whiskers and WC particles.