Si3N4/SiC-Whisker Composites without Sintering Aids: II, Fracture Behavior

The fracture behavior of an Si₃N₄/SiC-whisker composite fabricated without sintering aids is investigated using a double approach based on the examination of R -curve behavior and a statistical analysis of crack propagation. In the composite with 20 vol% whisker, a 30% increase in toughness over the matrix value can be attributed to crack-tip phenomena. Strong interfacial bonding prevents any contribution to toughening by mechanisms operating in the wake region of the crack. Based on experimental observations of microfracture in both SiC whiskers and Si₃N₄ grains, toughening caused by crack-tip phenomena is quantitatively discussed in terms of fracture energy and whisker-distribution parameters.     

Si3N4/SiC-Whisker Composites without Sintering Aids: I, Quantitative Evaluation of Microstructure

A microstructural evaluation of Si₃N₄ with 20 vol% SiC whiskers, fully densified by hot isostatic pressing (HIP) without sintering aids, is presented. The grain size and morphology of the matrix, the whisker aspect ratio after sintering, interfacial bonding, and the structural stability of reinforcement up to 2000°C are discussed. Image analysis provides quantitative information about whisker dispersion and orientation. It is pointed out that a whisker dispersion and orientation. It is pointed out that a whisker composite with a high degree of homogeneity and isotropy can be obtained by optimizing the mixing procedure and using HIP.     

Processing and Mechanical Properties of Dense Si3N4-SiC-Whisker Composites without Sintering Aids

Si₃N₄ with 20 vol% SiC whisker was fabricated without sintering aids by hot isostatic pressing. Density higher than 99.5% was attained after sintering at 2000°C and 170 MPa for 1 h. Careful mixing procedures and the use of an appropriate amount of a dispersant was found to be effective in avoiding whisker segregation and inhomogeneity. Mechanical properties of the composite were investigated by measurements of flexural strength, microhardness, frature toughness, and Young's modulus as a function of temperature. At room temerature, Vickers microhardness and Young's modulus increased from the matrix value about 20% and 5%, respectively. Toughness was about 30% higher, without reduction in flexural strength, up to 1400Deg;C.     

Mechanical Properties of Si2N2O/SiC-Whisker Composites

The mechanical and thermal properties of Si₂N₂O/SiC-whisker composites were studied with emphasis on the effect of matrix composition and of whisker content. The fracture toughness of Si₂N₂O was remarkably improved by 90% with a concomitant 70% strength improvement by addition of SiC whiskers of only 10 vol%. Optimum mechanical and thermal properties of Si₂N₂O/SiC-whisker composites were obtained at an equimolar ratio of Si₃N₄/SiO₂, which is the stoichiometric composition for Si₂N₂O. Additional investigation concerning the Si₂N₂O-matrix/SiC-whisker interface by controlling sintering additives is necessary for further improvement of mechanical and thermal properties of Si₂N₂O/SiC-whisker composites.     

Comparison of High-Temperature Crack Growth in SiC-Whisker-Reinforced Mullite and Si3N4

Crack growth behavior under creep conditions was studied in SiC-whisker-reinforced mullite and silicon nitride. Tests of four-point bend specimens with indentation cracks were periodically interrupted to observe the creep behavior. At each interruption the bulk creep strain of the specimen, the growth of the indentation cracks, and the nucleation and growth of creep-induced cracks were measured. A strong linear correlation was observed in both materials between the crack growth rate and the creep strain rate. For a given strain rate, cracks in the silicon nitride composite propagated at velocities about an order of magnitude greater than those in the mullite composite. On the other hand, for similar nominal stresses, creep rates in the silicon nitride composites were about an order of magnitude less than with the mullite composite.     

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.     

Elastic Properties of Al2O3 and Si3N4 Matrix Composites with SiC Whisker Reinforcement

A study of the elastic moduli of Al₂O₃ and Si₃N₄ ceramics reinforced with 0 to 25 wt% SiC whiskers has been performed. The Young's moduli, shear moduli, and longitudinal modulus are compared with calculated predictions for aligned fiber composites by Hill and Hashin and Rosen, and for fibers randomly oriented in three dimensions by Christensen and Waal. The measured values are in excellent quantitative agreement with those derived for the random orientation of the SiC whiskers.     

Microstructure and Densification of Pressureless-Sintered Al2O3/Si3N4-Whisker Composites

Composite densification was studied by performing slip casting and sintering experiments on an Al₂O₃ matrix and Si₃N₄ whisker system. Even though all the slip-cast powder compacts exhibited high green densities (up to 70% of the theoretical) and narrow pore-size distribution (pore radius around 15 to 30 nm), significant differential densification on a microscopic scale was found due to the existence of local whisker agglomeration. The inhomogeneous whisker distribution resulted in a binary mixture of large and small pores in the sintered composites, in which whisker-associated flaws remained stable even after prolonged sintering. The sintered microstructures showed that the spatial distribution as well as the volume fraction of the Si₃N₄ affect composite densification. Inhomogeneous whisker distribution dominated the complete densification of the composites.     

R-Curve Behavior of Si3N4–BN Composites

R -curve behavior of Si₃N₄–BN composites and monolithic Si₃N₄ for comparison was investigated. Si₃N₄–BN composites showed a slowly rising R -curve behavior in contrast with a steep R -curve of monolithic Si₃N₄. BN platelets in the composites seem to decrease the crack bridging effects of rod-shaped Si₃N₄ grains for small cracks, but enhanced the toughness for long cracks as they increased the crack bridging scale. Therefore, fracture toughness of the composites was relatively low for the small cracks, but it increased significantly to ∼8 MPa·m^1/2 when the crack grew longer than 700 μm, becoming even higher than that of the monolithic Si₃N₄.     

Mechanical Properties of β-Si3N4-Whisker/Si3N4-Matrix Composites

Composites containing 30 vol%β-Si₃N₄ whiskers in a Si₃N₄ matrix were fabricated by hot-pressing. The composites exhibited fracture toughness values between 7.6 and 8.6 MPa · m^1/2, compared to 4.0 MPa · m^1/2 for unreinforced polycrystalline Si₃N₄. The improvements in fracture toughness were attributed to crack wake effects, i.e., whisker bridging and pullout mechanisms.     

Measurement of Interfacial Shear Strength in SiC-Fiber/Si3N4 Composites

An indentation method for measuring shar strength in brittle matrix composites was applied to SiC-fiber/Si₃N₄-matrix samples. Three methods were used to manufacture the composites: reaction bonding of a Si/SiC preform, hot-pressing, and nitrogen-overpressure sintering. An indentation technique developed by Marshall for thin specimens was used to measure the shear strength of the interface and the interfacial friction stresses. This was done by inverting the sample after the initial push through and retesting the pushed fibers. SEM observations showed that the shear strength was determined by the degree of reaction between the fiber and the matrix unless the fiber was pushed out of its (well-bonded) sheath.     

Tribological Behavior of a Si3N4/Carbon Short Fiber Composite under Water Lubrication

The tribological behavior of monolithic Si₃N₄ and a Si₃N₄/carbon fiber composite has been assessed under high load and low speeds in an aqueous environment. The results showed that the friction coefficient of the Si₃N₄ was not significantly reduced when compared with dry sliding, and this was attributed to the failure to maintain a lubricating layer between the solid–solid surfaces. In the case of the composite, the initial high friction coefficient was reduced shortly after the beginning of the wear test and maintained a low value (about 0.03) throughout. This was attributed to the solid lubricating effect of the composite resulting in lower stress at the contact asperities, preventing the removal of the lubricating layer.     

Microstructure and Mechanical Properties of Sinter–Post-HIPed Si3N4–SiC Composites

The microstructural evolution and mechanical properties of Si₃N₄–SiC composites obtained by the sinter–post-HIP process were investigated. SiC addition prohibited β-Si₃N₄ grain growth; however, the grain growth followed the empirical growth law, with exponents of 3 and 5 for the c - and the a -axis directions, respectively. Mechanical properties were strongly influenced by SiC addition and sintering conditions. Short-crack propagation behavior was measured and analyzed by the indentation-strength in-bending (ISB) method. The present composites had high short-crack toughness, compared with the values for monolithic Si₃N₄. The enhanced short-crack toughness was attributed to crack-tip bridging by the SiC particles.     

Delayed-Failure Resistance of High-Purity Si3N4 at 1400°C

Delayed failure and creep behavior of high-purity Si₃N₄ sintered without additives with a mean grain size of 1 μm has been measured at 1400°C. Lifetime under 300 MPa was >240 h, which showed good agreement with the value predicted in our previous report. Creep strain rate ranged from 1 × 10⁻⁵ to 3 × 10⁻⁵ h⁻¹ between 200 and 360 MPa. These values demonstrate the excellent potential of high-purity Si₃N₄ materials for structural application up to 1400°C.     

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.     

Tribological Behavior of SiC-Whisker/Al2O3 Composites against Carburized 8620 Steel in Lubricated Sliding

Mineral oil lubricated sliding tests of Sic-whisker (SiC_w,)/A1₂0₃ composites and monolithic alumina against carburized 8620 steel were conducted on a cylinder-on-cylinder machine. The wear rate of the composites was one or two orders of magnitude less than that of pure alumina. Hot-pressed 25 wt% SiC_w,/A1₂0₃ composite had a lower wear rate than sintered and HIPed 7.5 wt% SiC/Al₂O₃ composite under the same conditions. The weight loss of the steel mating ring against the 25 wt% SiC_w, composite was a factor of four lower than against the 7.5 wt% SiC_w, composite, but the former was a factor of 50 to 60 less than that against pure alumina. The composites showed lower friction coefficients than alumina during the run-in stage. The friction coefficients decreased with initial wear. The steady-state friction coefficient decreased with increasing load up to 500 N for hot-pressed 25 wt% SiC,/Al₂0₃ composite. Further, SEM observation showed much less microfracture in composites than in alumina. EDAX analysis revealed less Fe transfer from the steel ring to the composites than to pure alumina. Wear by microfracture and by adhesion in composites was suggested to be suppressed by SIC whiskers. This in turn reduced wear of the steel because of the generation of fewer hard particles.     

Stepwise-Graded Si3N4–SiC Ceramics with Improved Wear Properties

The processing of stepwise graded Si₃N₄/SiC ceramics by pressureless co-sintering is described. Here, SiC (high elastic modulus, high thermal expansion coefficient) forms the substrate and Si₃N₄ (low elastic modulus, low thermal expansion coefficient) forms the top contact surface, with a stepwise gradient in composition existing between the two over a depth of ∼1.7 mm. The resulting Si₃N₄ contact surface is fine-grained and dense, and it contains only 2 vol% yttrium aluminum garnet (YAG) additive. This graded ceramic shows resistance to cone-crack formation under Hertzian indentation, which is attributed to a combined effect of the elastic-modulus gradient and the compressive thermal-expansion-mismatch residual stress present at the contact surface. The presence of the residual stress is corroborated and quantified using Vickers indentation tests. The graded ceramic also possesses wear properties that are significantly improved compared with dense, monolithic Si₃N₄ containing 2 vol% YAG additive. The improved wear resistance is attributed solely to the large compressive stress present at the contact surface. A modification of the simple wear model by Lawn and co-workers is used to rationalize the wear results. Results from this work clearly show that the introduction of surface compressive residual stresses can significantly improve the wear resistance of polycrystalline ceramics, which may have important implications for the design of contact-damage-resistant ceramics.     

Combustion Synthesis of Si3N4–SiC Composite Powders

Fine Si₃N₄-SiC composite powders were synthesized in various SiC compositions to 46 vol% by nitriding combustion of silicon and carbon. The powders were composed of α-Si₃N₄, β-Si₃N₄, and β-SiC. The reaction analysis suggested that the SiC formation is assisted by the high reaction heat of Si nitridation. The sintered bodies consisted of uniformly dispersed grains of β-Si₃N₄, β-SiC, and a few Si₂N₂O.     

Fabrication of TiN/Si3N4 Ceramics by Spark Plasma Sintering of Si3N4 Particles Coated with Nanosized TiN Prepared by Controlled Hydrolysis of Ti(O-i-C3H7)4

TiN-coated Si₃N₄ particles were prepared by depositing TiO₂ on the Si₃N₄ surfaces from Ti(O- i -C₃H₇)₄ solution, the TiO₂ being formed by controlled hydrolysis, then subsequently nitrided with NH₃ gas. A homogeneous TiO₂ coating was achieved by heating a Si₃N₄ suspension containing 1.0 vol% H₂O with the precursor at 40°C. Nitridation successfully produced Si₃N₄ particles coated with 10–20 nm TiN particles. Spark plasma sintering of these TiN/Si₃N₄ particles at 1600°C yielded composite ceramics with a relative density of 96% at 25 vol% TiN and an electrical resistivity of 10⁻³Ω·cm in compositions of 17.5 and 25 vol% TiN/Si₃N₄, making these ceramics suitable for electric discharge machining.