Shear Thickening Creep in Superplastic Silicon Nitride

A novel shear-thickening phenomenon has been observed in superplastic silicon nitrides compression tested between 1500° and 1600°C. Liquid-enhanced creep of SiAlONs undergoes a transition from Newtonian behavior to shear-thickening behavior at a characteristic stress, with the strain rate sensitivity increasing from unity to around 2. The transition stress is always around 20 MPa, even though the Newtonian flow stress is very sensitive to temperature, grain size, and phase composition. Rheopexic hysteresis, manifested as a slow stress relaxation to a steady-state value after a strain rate decrease, was also observed in the shear-thickening regime. We attribute the cause for shear thickening to a repulsive force between initially wetted SiAlON grains, which form a "dry" and "rigid" bridge in between when pressed above a characteristic stress, possibly due to the contact of the residue Stern layers on the opposing grain/liquid interfaces. A micromechanical model, which takes into account the stress variation among differently oriented grain boundaries, has been formulated to assess the effect of "rigid" grain boundaries. A continual stochastic rearrangement of grain configurations and a relatively thick Stern layer are suggested as the necessary prerequisites for shear thickening in liquid-enhanced creep.     

Superplastic Sinter-Forging of Silicon Nitride with Anisotropic Microstructure Formation

The microstructure and mechanical properties of silicon nitride, produced by a superplastic sinter-forging technique, were investigated. The obtained silicon nitride exhibited a highly anisotropic microstructure, where rod-shaped grains tended to be aligned perpendicular to the forging direction. A very high bending strength of 2108 MPa as well as a high fracture toughness of 8.3 MPam^1/2 were achieved when a stress was applied perpendicularly to the pressing direction. This very high strength was considered to be due to the reduced flaw size by the superplastic sinter-forging process and the steep R -curve behavior caused by the grain alignment.     

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.     

Geometrical Microstructural Development in Superplastic Silicon Nitride with Rod-Shaped Grains

The three-dimensional microstructural development of silicon nitride ceramics that exhibit superplastic elongation (up to ɛ = 1.34) was analyzed using a stereological analysis method. According to the microstructural change from randomly oriented grains to aligned grains along the tensile direction, the average orientation angle between the tensile axis and the major axis of a grain decreased monotonously as the strain increased. The average grain aspect ratio remained almost constant up to ɛ = 0.88 and then started to increase. Based on the microstructural development, three different modes of the change in the grain configuration-i.e., grain rotation, grain elongation, and grain translation-were considered. It is suggested that the contributions of the three modes vary according to the microstructural development during the deformation.     

Superplastic Deformation in Silicon Nitride–Silicon Oxynitride In Situ Composites

Starting with a mixture of ultrafine β-Si₃N₄ and a SiO₂-containing additive, a superplastic Si₃N₄-based composite was developed, using the concept of a transient liquid phase. Significant deformation-induced phase and microstructure evolutions occurred in the nonequilibrium, fine-grained Si₃N₄ material, which led to the in situ development of a Si₃N₄–22-vol%-Si₂N₂O composite and strong texture formation. The unusual ductility of the composites with elongated Si₂N₂O grains was attributed to the fine-grained microstructure, the presence of a transient liquid phase, and the alignment of the elongated Si₂N₂O grains. The mechanical properties of the resultant composite were enhanced rather than impaired by superplastic deformation and subsequent heat treatment; the resultant composite exhibited both high strength (957 MPa) and high fracture toughness (4.8 MPa·m^1/2).     

Strengthening of a Sintered Silicon Nitride by a Post-Fabrication Heat Treatment

The strength improvement of an injection-molded and sintered silicon nitride ceramic (15.5 wt% Y₂O₃+10.1 wt% SiO₂) produced by an oxidation heat treatment at 1500°C is reported. The ceramic retains its strength after prolonged intermediate temperature exposure in air, whereas the untreated material suffers various degrees of cracking.     

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.     

Diffusion Bonding of Silicon Nitride Using a Superplastic β-SiAlON Interlayer

A superplastic β-SiAlON was used as an interlayer to diffusionally bond a hot-pressed silicon nitride to itself. The bonding was conducted in a graphite furnace under a constant uniaxial load of 5 MPa at temperatures varying from 1500° to 1650°C for 2 h, followed by annealing at temperatures in the range of 1600° to 1750^oC for 2 h. The bonds were evaluated using the four-point-bend method at both room temperature and high temperatures. The results indicate that strong, void-free joints can be produced with the superplastic β-SiAlON interlayer, with bond strengths ranging from 438 to 682 MPa, and that the Si₃N₄ joints are heat resistant, being able to retain their strength up to 1000°C (635 MPa), and therefore have potential for high-temperature applications.     

Temperature Dependence of Anelastic Deformation in Polycrystalline Silicon Nitride

The influence of grain-boundary sliding on the evaluation of the apparent Young's modulus and plastic-deformation (flow) stress was investigated by bending tests for two types of silicon nitrides sintered with Y₂O₃-based additives The apparent Young's moduli measured at high temperatures are consistent with those predicated from a theory based on polycrystalline anelasticity due to grain-boundary sliding. The temperature dependence of the critical bending stress for the onset of plastic deformation shows viscoplastic properties of the interglanular glass. The ductile-to-brittle transition of fracture is discussed by the bending strengths normalized by the measured Young's modulus.     

Texture Development in Silicon Nitride–Silicon Oxynitride In Situ Composites via Superplastic Deformation

Silicon nitride–silicon oxynitride (Si₃N₄–Si₂N₂O) in situ composites have been fabricated via either the annealing or the superplastic deformation of sintered Si₃N₄ that has been doped with a silica-containing additive. In this study, quantitative texture measurements, including pole figures and X-ray diffraction patterns, are used in conjunction with scanning electron microscopy and transmission electron microscopy techniques to examine the degree of preferred orientation and texture-development mechanisms in these materials. The results indicate that (i) only superplastic deformation can produce strong textures in the β-Si₃N₄ matrix, as well as Si₂N₂O grains that are formed in situ ; (ii) texture development in the β-Si₃N₄ matrix mainly results from grain rotation via grain-boundary sliding; and (iii) for Si₂N₂O, a very strong strain-dependent texture occurs in two stages, namely, preferred nucleation and anisotropic grain growth.     

Effects of Microstructure on the Deformation Mechanisms in Silicon Nitride

Changes in phase composition and morphology were investigated in silicon nitride (Si₃N₄) both before and after compressive deformation testing. Different additive systems were used to prepare Si₃N₄ specimens, resulting in either an initial alpha-phase or β-phase microstructure. Constant-strain-rate compression tests were used to evaluate the differences in the strain-rate dependency of the flow stress for the two phases. A flow-stress dependency of n = 1 was observed in the β-phase specimens, compared to an n value that approached 2 in the alpha-phase specimens.     

Relationship between Microstructure, Toughening Mechanisms, and Fracture Toughness of Reinforced Silicon Nitride Ceramics

Different microstructures in Si₃N₄ ceramics containing Y₂O₃and Al₂O₃ as sintering additives were prepared by two-step sintering. Pull-out and elastic bridging were most frequently observed as the toughening mechanisms in samples with fine-grained microstructures having needlelike β-Si₃N₄grains with diameters of <1 μm. Crack deflection was the main toughening mechanism observed in samples with coarse-grained microstructures having grains with diameters of >1 μm. The values of fracture toughness were varied from 6.1 to 8.2 MPa·m^1/2 with respect to the microstructural characteristics, characterized by the volume fraction of needlelike grains and their diameter.     

Elementary Mechanisms behind the High-Temperature Deformation Behavior of Lutetium-Doped Silicon Nitride

Intergranular sliding and diffusive mechanisms behind the deformation behavior of a commercially available lutetium-doped silicon nitride were investigated and discussed. A method of locating and separating phenomena critical for mechanical relaxation at elevated temperatures was applied; the method was based on low-frequency forced-vibration damping measurements. The potentiality of lutetium addition for improving the deformation resistance of silicon nitride was clearly reflected in the high-temperature damping behavior of the investigated polycrystal. Softening of intergranular lutetium silicate phases located at multigrain junctions, which resulted in a grain-boundary sliding peak, occurred at remarkably high temperatures (>1725 K). This phenomenon, partly overlapping diffusional flow, was followed by further damping relaxation with the melting of the lutetium silicates. Subsequent grain growth was also detected at temperatures >2100 K. Torsional creep results, collected up to 2100 K, consistently proved the presence of a "locking" effect by lutetium silicates with the sliding of silicon nitride grain boundaries below 1873 K.     

Tensile Strength of Silicon Nitride Whiskers Synthesized by Reacting Amorphous Silicon Nitride and Titanium Dioxide

The tensile strength of α-Si₃N₄ whiskers synthesized by reacting amorphous Si₃N₄ and TiO₂ at 1490°C under a N₂ pressure of 700 torr was measured using a microbalance, and the diameter dependence of the strength was investigated. The Si₃N₄ whiskers had diameters of 0.04 and 0.8 μm and dominant [1011] and [1010] growth directions. Chemical analysis showed that they contained Ti and O impurities. The tensile strength of six Si₃N₄ whiskers increased from 17 to 59 GPa with decreasing whisker diameter.     

Effect of Sintering Additives on Superplastic Deformation of Nano-Sized β-Silicon Nitride Ceramics

The effect of sintering additives on superplastic deformation of nano-sized β-Si₃N₄ ceramics has been studied by compression tests at 1500°C. The sintering additives were (i) Y₂O₃+Al₂O₃; (ii) Y₂O₃+MgO; and (iii) Y₂O₃. Nano-sized Si₃N₄ ceramics with different sintering additives had similar microstructures. For the first two sintering additives, the stress exponents were determined to be ∼2 at a lower stress region and ∼1 at a higher stress region, where the strain rate was dependent on sintering additives only at the higher stress region, and was independent at the lower stress region. Nano-ceramics with Y₂O₃ additives had only one region, which had a stress exponent of ∼1 within the stress range that we studied. The results could be explained by the different deformation mechanisms at the higher and lower stress regions and the influence of viscosity of liquid phase on the transition stress.     

Effects of Microstructure on Superplastic Behavior and Deformation Mechanisms in β-Silicon Nitride Ceramics

The influence of grain shape and size on superplastic behavior and deformation mechanisms was investigated in annealed β-silicon nitride materials and compared with the results for hot-pressed material. The microstructure of the annealed materials consisted of fine equiaxed β-grains together with some elongated ones. Similar to the deformation behavior in the hot-pressed material, strain hardening did not occur in these annealed materials. Moreover, in contrast to the deformation behavior under tension, grain alignment under compression resulting from the development of a mild texture did not give rise to strain hardening. An annealed material with small elongated grains had a flow-stress dependency of n = 1, whereas other annealed materials with large elongated grains exhibited a flow-stress dependency of n = 1.6. In terms of texture development and the effect of grain shape on the creep rate when diffusion was the rate-controlling mechanism, a single curve with a stress exponent of ∼1 and a grain-size exponent of 3 were obtained for all materials. This suggests that the deformation mechanism in these annealed materials was the same as that of fine equiaxed β-silicon nitride.     

Anisotropy of Silicon Nitride with Aligned Silicon Nitride Whiskers

A model based on anisotropic sintering shrinkage of silicon nitride with aligned silicon nitride whisker seeds was built in order to provide an easy way to obtain information on how the large elongated grains were aligned. The method requires a simple measuring device for the information. XRD analysis showed a good correlation with predictions of the model. Both predictions of the model and experimental results indicated that the fraction of aligned large elongated grains increased as the whisker content increased.     

Synthesis of Silicon Nitride/Silicon Carbide Nanocomposite Powders through Partial Reduction of Silicon Nitride by Pyrolyzed Carbon

An alternative method to incorporate nanometer-sized silicon carbide (SiC) particles into silicon nitride (Si₃N₄) powder was proposed and investigated experimentally. Novolac-type phenolic resin was dissolved in ethanol and mixed with Si₃N₄ powder. After drying and curing, the resin was converted to reactive carbon via pyrolysis. Si₃N₄ powder was partially reduced carbothermally using the pyrolyzed carbon, and nanometer-sized SiC particles were produced in situ at 1530°-1610°C in atmospheric nitrogen. At temperatures <1550°C, the reduction rate was low and the SiC particles were very small; no SiC whiskers or barlike SiC was observed. At 1600°C, the reduction rate was high and the reaction was close to completion after only 10 min, with the appearance of SiC whiskers as well as curved, barlike, and equiaxial SiC, all of which were dozens of nanometers in diameter; this size is greater than that at observed temperatures <1550°C. A longer soaking time at 1600°C led to agglomerates. SiC particles were close to the surface of the Si₃N₄ particles. The SiC content could be adjusted by changing the carbon content before reduction and the reduction temperature. A reaction mechanism that involved the decomposition of Si₃N₄ has been proposed.     

Coating of Fine-Grained Silicon Nitride Whiskers on Fiber-like Silicon Nitride

Fine-grained silicon nitride (Si3N4) whiskers were coated on Si3N4 fibers through a vapor-liquid-solid mechanism under the following process. After the oxide glass of a Si-Al-Y-O system was coated on seed Si3N4 fibers, the coated fibers were heated at 1490°C and 700° in the vapor of the Si-N system which was generated by decomposition of amorphous Si3N4. The resulting specimens looked just like rose twigs. The Si3N4 whiskers were precipitated by nucleation in a liquid phase generated by melting of the oxide glass layers on the Si3N4 fibers.     

Decomposition Suppression of Silicon Nitride by Hexagonal Boron Nitride Nanocoatings

We report a stabilized Si₃N₄ simply with nanocoatings of h-BN. Very thin BN coatings are enough for suppressing the decomposition of Si₃N₄ particles. This approach should open up a new potential way to prepare stabilized Si₃N₄. Reduced nitridation of H₃BO₃-coated Si₃N₄ powder at 1050°C in a flowing mixed 40% N₂+60% H₂ atmosphere, and then following heat-treatment at 1500°C in a flowing N₂ atmosphere can realize the nanocoating of BN on Si₃N₄ particles. Compared with the Si₃N₄ powder without nanocoatings of h-BN, TG and XRD analysis showed that the obtained h-BN nanocoated Si₃N₄ powder demonstrated obviously improved stability in argon atmosphere.