Thickness Alteration of Grain-Boundary Amorphous Films during Creep of a Multiphase Silicon Nitride Ceramic

Experimental observations of the creep response of a commercial sintered silicon nitride ceramic are presented. The stable microstructure of this material at high temperature contains secondary crystalline phases which result from partial devitrification of the intergranular phase. The widths of amorphous films along grain boundaries (between silicon nitride grains) and phase boundaries (between silicon nitride and secondary phase grains) are characterized by transmission electron microscopy. The thickness distributions of grain-boundary films before and after creep are analyzed by a statistical method. While the film widths are highly uniform before creep, a bimodal distribution is observed after creep. The results suggest that viscous flow of the boundary amorphous films occurs during creep deformation.     

Grain-Boundary Phase Crystallization of Silicon Nitride with Material Loss During Heat Treatment

An analysis was made of the Si₃N₄· Y₂O₃ crystallization process from a compacted Si₃N₄ powder (composition: 5 wt% Y₂O₃ and 2 wt% Al₂O₃) during heat treatment in various powder beds. X-ray diffraction was used to measure the degree of cyrstallization, which was correlated with weight loss. Crystallization and weight loss were affected significantly by the SiO₂ content in the packing powder. Crystallization correlated strongly with the weight loss. The dominant loss was attributed to SiO volatilization from the Y-Si-Al-O-N liquid. The crystallization mechanism with the loss of material was interpreted using a solubility—supersolubility diagram at constant temperature.     

Low-Frequency Measurements on the Grain-Boundary Internal Friction Peak in Chlorine-Doped Silicon Nitride

A procedure is shown to quantitatively analyze the morphology of the internal friction peak resulting from grain-boundary sliding. A Si₃N₄ polycrystal containing chlorine-doped SiO₂ at grain boundaries is selected as a model system for discussing chemical (e.g., anion) gradients at glassy grain boundaries. In this model material, grain boundaries lodging Cl⁻ anions show nonuniform thickness characteristics, which suggests a non-negligible dependence of the intergranular SiO₂-network structure upon grain misorientation. Both chemical and microstructural inhomogeneities existing in a polycrystalline ceramic body can result in peak broadening. The key for separating broadening contributions of chemical gradients from grain-size/morphology distributions resides in analyzing the peak-width change upon damping frequency. Groups of grain boundaries with different chemical characteristics may produce broadening because different peak components are generated that obey a spectrum of activation energies. On the other hand, microstructural inhomogeneities obey a single activation energy, but they generate a distribution of relaxation times. As a result, when a chemical gradient is present at grain boundaries, the peak may shift upon changing damping frequency with obeying a true activation energy, but its width increases with decreasing damping frequency. When peak broadening results only from microstructural inhomogeneities, the peak width is independent of damping frequency.     

High-Temperature Microstructure of a Hot-Pressed Silicon Nitride

The outstanding question as to the microstructure of silicon nitride at temperatures associated with potential high-temperature applications of the material is addressed experimentally by quenching thin (transmission electron microscopy) samples from 1450°C and examining them in the microscope. The morphology of the microstructure is qualitatively unchanged compared to the materials slowly cooled, for example, after hot-pressing, to room temperature. The most significant difference is that the thickness of the intergranular phase is larger, typically 2 to 10 nm, as compared to the ∼ 1 nm observed in the hot-pressed material. In addition there is an apparent increase in the volume fraction of the intergranular phase at the three-grain junctions. On the basis of a number of supporting experiments including both hot-stage transmission electron microscopy (up to 1000°C) and Auger electron spectroscopy of material fractured and examined at 850°C, the change in microstructure is concluded to occur at temperatures above about 1000°C.     

Shock Synthesis of Cubic Silicon Nitride

The phase transitions of α-Si₃N₄ and β-Si₃N₄ have been investigated by shock compression through the recovery technique and Hugoniot measurements. α- and β-Si₃N₄ are transformed into a cubic spinel structure ( c -Si₃N₄). The yield of c -Si₃N₄ increases with increasing shock pressure and reaches 100% at 63 GPa. The shock-synthesized c -Si₃N₄ powders are nanocrystals and display a high-temperature metastability up to about 1620 K. c -Si₃N₄ is one of the hard materials based on the measured equation of state. c -Si₃N₄ powders have been characterized by electron microscopy and ²⁹Si magic angle spinning NMR spectroscopy. The purification and separation method has been developed to obtain pure c -Si₃N₄ powders.     

Microstructural Changes in β-Silicon Nitride Grains upon Crystallizing the Grain-Boundary Glass

Crystallizing the grain-boundary glass of a liquid-phase-sintered Si₃N₄ ceramic for 2 h or less at 1500° led to formation of δ-Y₂Si₂O₇. After 5 h at 1500°, the δ-Y₂Si₂O₇ had transformed to β-Y₂Si₂O₇ with a concurrent dramatic increase in dislocation density within β-Si₃N₄ grains. Reasons for the increased dislocation density are discussed. Annealing for 20 h at 1500° reduced dislocation densities to the levels found in as-sintered material.     

Grain-Boundary Viscosity of Preoxidized and Nitrogen-Annealed Silicon Carbides

Internal friction experiments were conducted on a model SiC polycrystal prepared from preoxidized (high-purity) SiC powder. This material contained high-purity SiO₂ glass at grain boundaries in addition to a free-carbon phase, which was completely removed upon powder preoxidation. Comparative tests were conducted on a SiC polycrystal, obtained from the as-received SiC powder with the addition of 2.5 vol% of high-purity SiO₂. This latter SiC material was also investigated after annealing at 1900°C for 3 h in a nitrogen atmosphere. Electron microscopy observations revealed a glass-wetted interface structure in SiC polycrystals prepared from both as-received and preoxidized powders. However, the former material also showed a large fraction of interfaces coated by turbostratic graphite. Upon high-temperature annealing in nitrogen, partial glass dewetting occurred, and voids were systematically observed at multigrain junctions. The actual presence of nitrogen could only be detected in a limited number of wetted interfaces. A common feature in the internal friction behavior of the preoxidized, SiO₂-added and nitrogen-annealed SiC was a relaxation peak that resulted from grain-boundary sliding. Frequency-shift analysis revealed markedly different characteristics for this peak: both the magnitude of the intergranular glass viscosity and the activation energy for grain-boundary viscous flow were much higher in the nitrogen-annealed material. Results of torsional creep tests were consistent with these findings, with nitrogen-annealed SiC being the most creep resistant among the tested materials.     

Elastic Moduli and Hardness of Cubic Silicon Nitride

The bulk modulus B ₀= 290(5) GPa and its first pressure derivative B '₀= 4.9(6) were obtained for c -Si₃N₄ from volume versus pressure dependence. Measurements were performed under quasi-hydrostatic conditions in a diamond anvil cell to 53 GPa using synchrotron radiation and energy dispersive X-ray powder diffraction. This combined with nanoindentation measurements determined the shear modulus G ₀ of c -Si₃N₄ to be 148(16) GPa. The Vickers microhardness H _V(0.5) for dense, oxygen-free c -Si₃N₄ was estimated to be between 30 and 43 GPa. Both the elastic moduli and microhardness of c -Si₃N₄ exceed those of the hexagonal counterparts, α- and β-phases.     

Bond Energetics at Intergranular Interfaces in Alumina-Doped Silicon Nitride

In Si₃N₄ ceramics sintered with Al₂O₃, the interfacial strength between the intergranular glass and the reinforcing grains has been observed to increase with increases in the aluminum and oxygen content of the epitaxial β-Si_{6- z} Al _z O _z N_{8– z} layer that forms on the Si₃N₄ grains. This has been attributed to the formation of a network of strong bonds (cross bonds) that span the glass-crystalline interface. This proposed mechanism is considered further in light of first-principles atomic cluster calculations of the relative stabilities of bridge and threefold-bonded atomic fragments chosen to represent compositional changes at the glass/Si₃N₄ grain interface. Calculated binding energies indicate Al-N binding is favorable at the Si₃N₄ grain surface, where aluminum occupancy can promote the growth of SiAlON, further enhancing the cross-bonding mechanism of interfacial strengthening.     

Control of Composition and Structure in Laminated Silicon Nitride/Boron Nitride Composites

Based on a biomimetic design, Si₃N₄/BN composites with laminated structures have been prepared and investigated through composition control and structure design. To further improve the mechanical properties of the composites, Si₃N₄ matrix layers were reinforced by SiC whiskers and BN separating layers were modified by adding Si₃N₄ or Al₂O₃. The results showed that the addition of SiC whiskers in the Si₃N₄ matrix layers could greatly improve the apparent fracture toughness (reaching 28.1 MPa·m^1/2), at the same time keeping the higher bending strength (reaching 651.5 MPa) of the composites. Additions of 50 wt% Al₂O₃ or 10 wt% Si₃N₄ to BN interfacial layers had a beneficial effect on the strength and toughness of the laminated Si₃N₄/BN composites. Through observation of microstructure by SEM, multilevel toughening mechanisms contributing to high toughness of the laminated Si₃N₄/BN composites were present as the first-level toughening mechanisms from BN interfacial layers as crack deflection, bifurcation, and pull-out of matrix sheets, and the secondary toughening mechanism from whiskers in matrix layers.     

Theoretical Prediction of Post-Spinel Phases of Silicon Nitride

New phases of Si₃N₄ that may be stable at higher pressure than spinel have been searched using a first-principles plane-wave pseudopotential method. The CaTi₂O₄-type phase is found to be the prime candidate for the post-spinel phase among six phases selected on the analogy to high-pressure oxides. The phase transformation from the spinel is predicted to occur at 210 GPa. All silicon atoms of the new phase are coordinated by six anions, similar to the case of the high-pressure forms of SiO₂ and SiC. Because of its high energy at zero pressure, this new phase may be difficult to quench. The bandgap increases with an increase of pressure when compared in the same polymorph. However, the bandgap and the net charge decrease in the order of β, spinel, and CaTi₂O₄-type phases at zero pressure. The theoretical bulk modulus of the CaTi₂O₄-type phase is comparable with that of spinel.     

Reactivity of Aluminum Nitride Powder in Aqueous Silicon Nitride and Silicon Carbide Slurries

The reactivity of AlN powder with water in supernatants obtained from centrifuged Si₃N₄ and SiC slurries was studied by monitoring the pH versus time. Various Si₃N₄ and SiC powders were used, which were fabricated by different production routes and had surfaces oxidized to different degrees. The reactivity of the AlN powder in the supernatants was found to depend strongly on the concentration of dissolved silica in these slurries relative to the surface area of the AlN powder in the slurry. The hydrolysis of AlN did not occur if the concentration of dissolved silica, with respect to the AlN powder surface, was high enough (1 mg SiO₂/(m² AlN powder)) to form a layer of aluminosilicates on the AlN powder surface. This assumption was verified by measuring the pH of more concentrated (31 vol%) Si₃N₄ and SiC suspensions also including 5 wt% of AlN powder (with respect to the solids).     

Effects of Grain-Boundary Structure on the Strength, Toughness, and Cyclic-Fatigue Properties of a Monolithic Silicon Carbide

An in situ -toughened silicon carbide (ABC-SiC) has been examined in the as-processed condition, where the grain-boundary films are predominantly amorphous, and following thermal exposure at a temperature of 1300°C, where the films become fully crystalline. Previous work has shown that, at elevated temperatures (up to 1300°C), after the grain-boundary films crystallize in situ , only a marginal reduction in strength, fracture toughness, and cyclic-fatigue crack-growth properties is observed, in comparison with those of the as-processed microstructure at 25°C. In the present study, the effect of such crystallization on the subsequent strength, toughness, and fatigue properties at 25°C is examined. Little or no degradation is observed in the room-temperature properties with the crystallized grain-boundary films/phase; in fact, although the strength shows a small reduction (∼3%), the fracture toughness and fatigue-crack-growth threshold both increase by ∼20%, compared with that of the as-processed structure with amorphous grain-boundary films.     

Silicon Nitride Joining Using Silica and Yttria Ceramic Interlayers

Dense hot-pressed β-Si₃N₄ blocks were joined using both SiO₂ and SiO₂-Y₂O₃ powder slurries as bonding interlayers. The assembled specimens (Si₃N₄/interlayer/Si₃N₄) were heated in a flowing N₂ atmosphere in the temperature range of 1500°–1650°C. The joining interlayer was clearly distinguished from the Si₃N₄ bulk. The microstructure and the reaction products found in the bonding interlayer were very different in both compositions. Reactions occurring between the Si₃N₄ and the ceramic joining compositions have been explained based on existing diagrams of the YN–Si₃N₄-Y₂O₃-SiO₂ system.     

Texture in Silicon Nitride Seeded with Silicon Nitride Whiskers of Different Sizes

Silicon nitride ceramics seeded with 3 wt%β-Si₃N₄ whiskers of two different sizes were prepared by a modified tape casting and gas pressure sintering. The fine whiskers had a higher aspect ratio than the coarse whiskers. Quantitative texture analysis including calculation of the orientation distribution function (ODF) was used for obtaining the degrees of preferred orientation of sintered samples. The maximum multiples of random distribution (mrd) values of samples seeded with the fine and coarse whiskers were large, greater than 15 and 9, respectively. Meanwhile, the mrd value of a sample seeded with fine whiskers was only 9 when it was prepared by conventional tape casting. The microstructures and the XRD data revealed that the well-aligned whiskers grew significantly after sintering and dominated the texture. Differences among the degrees of preferred orientation of the samples were explained using Jeffrey's model on rotation of elliptical particles carried by a viscous fluid.     

Grain-Boundary Microstructure and Chemistry of a Hot Isostatically Pressed High-Purity Silicon Nitride

Two high-purity Si₃N₄ materials were fabricated by hot isostatic pressing without the presence of sintering additives, using an amorphous laser-derived Si₃N₄ powder with different oxygen contents. High-resolution transmission electron microscopy and electron energy-loss spectroscopy (EELS) analysis of the Si₃N₄ materials showed the presence of an amorphous SiO₂ grain-boundary phase in the three-grain junctions. Spatially resolved EELS analysis indicated the presence of a chemistry similar to silicon oxynitride at the two-grain junctions, which may be due to partial dissolution of nitrogen in the grain-boundary film. The chemical composition of the grain-boundary film was SiN_xO_y, (x ∼ 0.53 and y ∼ 1.23), and the triple pocket corresponded to the amorphous SiO₂ containing ∼2 wt% nitrogen. The equilibrium grain-boundary-film thickness was measured and found to be smaller for the material with the lower oxygen content. This difference in thickness has been explained by the presence of the relatively larger calcium concentration in the material with the lower amount of SiO₂ grain-boundary phase, because the concentration of foreign ions has been shown to affect the grain-boundary thickness.     

Preparation of Ultrafine Silicon Nitride, and Silicon Nitride and Silicon Carbide Mixed Powders in a Hybrid Plasma

Ultrafine Si₃N₄ and Si₃N₄+ SiC mixed powders were synthesized through thermal plasma chemical vapor deposition (CVD) using a hybrid plasma which was characterized by the superposition of a radio-frequency plasma and an arc jet. The reactant, SiCl₄, was injected into an arc jet and completely decomposed in a hybrid plasma, and the second reactant, CH₄ and/or NH₃, was injected into the tail flame through multistage ring slits. In the case of ultrafine Si₃N₄ powder synthesis, reaction effieciency increased significantly by multistage injection compared to single-stage injection. The most striking result is that amorphous Si₃N₄ with a nitrogen content of about 37 wt% and a particle size of 10 to 30 nm could be prepared successfully even at the theoretical NH₃/SiCl₄ molar ratio of ∼ 1.33, although the crystallinity depended on the NH₃/SiCl₄ molar ratio and the injection method. For the preparation of Si₃N₄+ SiC mixed powders, the N/C composition ratio and particle size could be controlled not only by regulating the flow rate of the NH₃ and CH₄ reactant gases and the H₂ quenching gas, but also by adjusting the reaction space. The results of this study provide sufficient evidence to suggest that multistage injection is very effective for regulating the condensation process of fine particles in a plasma tail flame.     

Machinability of Silicon Nitride/Boron Nitride Nanocomposites

The machinability and deformation mechanism of Si₃N₄/BN nanocomposites were investigated in the present work. The fracture strength of Si₃N₄/BN microcomposites remarkably decreased with increased hexagonal graphitic boron nitride ( h -BN) content, although machinability was somewhat improved. However, the nanocomposites fabricated using the chemical method simultaneously had high fracture strength and good machinability. Hertzian contact tests were performed to clarify the deformation behavior by mechanical shock. As a result of this test, the damage of the monolithic Si₃N₄ and Si₃N₄/BN microcomposites indicated a classical Hertzian cone fracture and many large cracks, whereas the damage observed in the nanocomposites appeared to be quasi-plastic deformation.     

氮化硅薄膜制备方法现状综述

氮化硅薄膜是一种多功能材料，在许多领域有着广泛的应用。本文系统综述氮化硅薄膜的性质、结构、应用及各种制备方法，并对今后的研究作了展望。     

Fabrication and Microstructure of Silicon Nitride/Boron Nitride Nanocomposites

A chemical process for fabrication of Si₃N₄/BN nanocomposite was devised to improve the mechanical properties. Si₃N₄/BN nanocomposites containing 0 to 30 vol% hexagonal BN ( h -BN) were successfully fabricated by hot-pressing α-Si₃N₄ powders, on which turbostratic BN ( t -BN) with a disordered layer structure was partly coated. The t -BN coating on α-Si₃N₄ particles was prepared by reducing and heating α-Si₃N₄ particles covered with a mixture of boric acid and urea. TEM observations of this nanocomposite revealed that the nanosized hexagonal BN ( h -BN) particles were homogeneously dispersed within Si₃N₄ grains as well as at grain boundaries. As expected from the rules of composites, Young's modulus of both micro- and nanocomposites decreased with an increase in h -BN content, while the fracture strength of the nanocomposites prepared in this work was significantly improved, compared with the conventional microcomposites.