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.     

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.     

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.     

Effect of Sintering Additive Composition on the Processing and Thermal Conductivity of Sintered Reaction-Bonded Si3N4

Two compositions of the Y₂O₃–MgO (YM) and Yb₂O₃–MgO (YbM) systems were chosen to study the effect of the sintering additive composition on the processing and thermal conductivity of sintered reaction-bonded silicon nitride (SRBSN). The nitridation, postdensification, microstructural evolution, and thermal conductivity of SRBSN were found to depend strongly on the sintering additive composition. The RBSN materials with YbM exhibited a poor sinterability, whereas those with YM exhibited an excellent sinterability. However, the SRBSN materials with YbM showed a higher thermal conductivity than those with YM. This was associated primarily with the isolated distribution and lower amount of secondary phase and the higher percentage of large grains in the former materials.     

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.     

Superplasticity of Liquid-Phase-Sintered β-SiC with Al2O3–Y2O3–AlN Additions in an N2 Atmosphere

Compression and tension tests were performed on liquid-phase-sintered β-SiC fabricated by hot-pressing, using ultrafine powders, at 1973–2048 K in an N₂ atmosphere. Amorphous phases were observed at the grain boundaries and at multigrain junctions in the as-sintered material. Strain hardening was observed under all experimental conditions. Stress exponents in the compression test were 1.7–2.1 in the temperature range 1973–2023 K. A maximum tensile elongation of 170% was achieved at the initial strain rate of 2 × 10⁻⁵ s⁻¹ at 2048 K.     

Effect of Dynamic Microstructural Change on Deformation Behavior in Liquid-Phase-Sintered Silicon Carbide with Al2O3–Y2O3–CaO Additions

Nanocrystalline β-SiC with additions of 7 wt% Al₂O₃, 2 wt% Y₂O₃, and 1 wt% CaO was subjected to tensile deformation to study its microstructural behavior under the dynamic process. The liquid-phase-sintered body had a relative density of >97% and an average grain size of 170 nm. Tension tests were conducted at initial strain rates ranging from 2 × 10⁻⁵ to 5 × 10⁻⁴ s⁻¹, in the temperature range 1973–2023 K, in both argon and N₂ atmospheres. Although grain-boundary liquids formed by the additions vaporized concurrently with the decomposition of SiC and extensive grain growth, the maximum tensile elongation of 48% was achieved in argon. Annealing experiments under the same conditions revealed that vaporization and grain growth were both dependent on experimental time. Therefore, high strain rates suffered less from the hardening effect when cavitation damage was more severe. Testing in an N₂ atmosphere brought about crystallization of the grain-boundary phase and prevented severe vaporization; however, fracture occurred at only 8% elongation. Grain-boundary sliding was still the dominant mechanism for deformation.     

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.     

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.     

Oxidation Effects on the Mechanical Properties of a SiC-Fiber-Reinforced Reaction-Bonded Si3N4 Matrix Composite

The room-temperature mechanical properties of a SiC-fiberreinforced reaction-bonded silicon nitride composite were measured after 100 h treatment in nitrogen and oxygen environments to 1400°C. The composite heat-treated in nitrogen to 1400°C showed no appreciable loss in properties. In contrast, composites heat-treated in oxygen from 600° to 1000°C retained ∼65% and 35% of the matrix fracture and ultimate strength, respectively, of the as-fabricated composites, and those heat-treated from 1200° to 1400°C retained greater than 90% and 65% of the matrix fracture and ultimate strength, respectively, of the as-fabricated composites. For all nitrogen and oxygen treatments, the composite displayed strain capability beyond the matrix fracture strength. Oxidation of the fiber surface coating, which caused degradation of bond between the fiber and matrix and reduction in fiber strength, appears to be the dominant mechanism for property degradation of the composites oxidized from 600° to 1000°C. Formation of a protective silica coating at external surfaces of the composites at and above 1200°C reduced oxidation of the fiber coating and hence degrading effects of oxidation on their properties.     

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.     

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.     

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.     

Formation Mechanism of AlN–SiC Solid Solution by Combustion Nitridation in Si3N4–Si-Al-C System

The synthesis of solid solutions of AlN–SiC was investigated through the combustion reaction between Si₃N₄, aluminum, and carbon powders and nitrogen gas at pressures ranging from 0.1 to 6.0 MPa. The combustion reaction was initiated locally and then the wave front propagated spontaneously, passing through the cylindrical bed containing the loose powder. In the presence of Si₃N₄ as a reactant, it was feasible to synthesize solid solutions at an ambient pressure (0.1 MPa). The relationship between nitrogen pressure and full-width at half-maximum of the (110) peak of the product showed that lower pressures produced more-homogeneous solid solutions. Some aspects of formation of the AlN–SiC solid solutions were discussed with special emphasis on the influence of nitrogen pressure and reactant stoichiometry.     

Si3N4/SiC-Whisker Composites without Sintering Aids: III, High-Temperature Behavior

The fracture behavior at high temperature of a Si₃N₄-based SiC-whisker composite fabricated by hot isostatic pressing without sintering aids is compared with that of other highly refractory materials. Particular attention is directed toward evaluating the slow-crack-growth resistance of the composite up to 1440°C and relating this resistance to the microfracture behavior of Si₃N₄ grains, SiC whiskers, and the intergranular, glassy SiO₂ phase. Only thick whiskers operate to bridge the wake of the crack; these whiskers may make a positive contribution to the slow-crack-growth resistance. Impurities detected by EDX microanalysis at the grain boundary, however, apparently degrade the high-temperature properties, a finding supported by internal-friction measurements. Nevertheless, the high potential of the system without sintering aids for high-temperature structural applications has been demonstrated by the time to failure estimated from the measured slow-crack-growth resistance for a fixed flaw size.     

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.