High-Temperature Strength and Cavitation Threshold of Silicon Nitride–Silica Ceramics

The role of high-purity silica in the fracture of Si₃N₄ at high temperatures has been investigated. The flexural strength at 1400°C was found to be greater than that at room temperature. Little plastic deformation was observed even when 10 wt% SiO₂ was added and the strain rate was decreased 2 orders of magnitude from that for a standard bend test. Microstructural observations revealed that the glassy phase was localized at intergranular pockets when SiO₂ additions were ≤ 10 wt%. High strength at 1400°C despite the presence of a fairly large amount of glassy phase is attributed to a high cavitation threshold in such glassy pockets consisting of high-purity SiO₂. However, the deformation behavior changed abruptly for SiO₂ additions of 10 and 20 wt%, which is explained by the morphological change of the glassy phase to thicker intergranular layers which allow macroscopic viscous flow.     

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).     

Densification and Microstructural Development of Silicon Nitride–Silica During Hot Isostatic Pressing

The influence of SiO₂ addition on the densification and microstructural development of high-purity Si₃N₄ during hot isostatic pressing (HIP) was studied. During HIP, densification was promoted, but the phase transformation from α -Si₃N₄ to β -Si₃N₄ was impeded by SiO₂. Analysis using a simple model shows that the enhanced densification was mainly due to the viscous flow of SiO₂. The microstructure changed remarkably at between 10 and 20 wt% SiO₂ additions. Analysis of the phase transformation kinetics suggests that the diffusion of Si₃N₄ through SiO₂ glass is the ratecontrolling step for the transformation.     

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.     

Reaction-Bonded and Superplastically Sinter-Forged Silicon Nitride–Silicon Carbide Nanocomposites

Silicon nitride–silicon carbide (Si₃N₄–SiC) nanocomposites were fabricated by a process involving reaction bonding followed by superplastic sinter-forging. The nanocomposites exhibited an anisotropic microstructure, in which rod-shaped, micrometer-sized Si₃N₄ grains tended to align with their long axes along the material-flow direction. SiC particles, typically measuring several hundred nanometers, were located at the Si₃N₄ grain boundaries, and nanosized particles were dispersed inside the Si₃N₄ grains. A high bending strength of 1246 ± 119 MPa, as well as a high fracture toughness of 8.2 ± 0.9 MPa·m^1/2, was achieved when a stress was applied along the grain-alignment direction.     

Microstructural Control of a 70% Silicon Nitride– 30% Barium Aluminum Silicate Self-Reinforced Composite

The processing response of a 70% silicon nitride–30% barium aluminum silicate (70%-Si₃N₄–30%-BAS) ceramic-matrix composite was studied using pressureless sintering, at temperatures ranging from 1740°C, which is below the melting point of BAS, to 1950°C. The relationship between the processing parameters and the microstructural constituents, such as morphology of the β-Si₃N₄ whisker and crystallization of the BAS matrix, was evaluated. The mechanical response of this array of microstructures was characterized for flexural strength, as well as fracture behavior, at test temperatures up to 1300°C. The indentation method was used to estimate the fracture resistance, and R -curves were obtained from modified compact-tension samples of selected microstructures at room temperature.     

Mechanical and Electrical Properties of Silicon Nitride–Silicon Carbide Nanocomposite Material

Mechanical and electrical properties of nanocomposite materials composed of a Si₃N₄ matrix and nanometer-sized SiC particles are described. Composites containing less than 10 vol% SiC particles have the same order of resistivity and dielectricity as the non-SiC material as well as highly improved mechanical properties. The composites are promising materials for use under harsh conditions.     

High-Temperature Creep and Microstructural Evolution of Chemically Vapor-Deposited Silicon Carbide Fibers

The creep behavior of three types of silicon carbide fibers that have been fabricated via chemical vapor deposition is described. The fibers exhibit only primary creep over the range of conditions studied (1200°–1400°C, 190–500 MPa). A transmission electron microscopy study of the microstructural development that is induced by the creep deformation of SCS-6 silicon carbide fibers at 1400°C is presented. Significant grain growth occurs in all silicon carbide regions of the fiber during creep, in contrast to the reasonably stable microstructure that is observed after annealing at the same temperature and time.     

Phase Relations and Microstructural Development of Aluminum Nitride–Aluminum Nitride Polytypoid Composites in the Aluminum Nitride–Alumina–Yttria System

AlN–AlN polytypoid composite materials were prepared in situ using pressureless sintering of AlN–Al₂O₃ mixtures (3.7–16.6 mol% Al₂O₃) using Y₂O₃ (1.4–1.5 wt%) as a sintering additive. Materials fired at 1950°C consisted of elongated grains of AlN polytypoids embedded in equiaxed AlN grains. The Al₂O₃ content in the polytypoids varied systematically with the overall Al₂O₃ content, but equilibrium phase composition was not established because of slow nucleation rate and rapid grain growth of the polytypoid grains. The polytypoids, 24 H and 39 R , previously not reported, were identified using HRTEM. Solid solution of Y₂O₃ in the polytypoids was demonstrated, and Y₂O₃ was shown to influence the stability of the AlN polytypoids. The present phase observations were summarized in a phase diagram for a binary section in the ternary system AlN–Al₂O₃–Y₂O₃ parallel to the AlN–Al₂O₃ join. Fracture toughness estimated from indentation measurements gave no evidence for a strengthening mechanism due to the elongated polytypoids.     

Preparation and Properties of Porous Aluminum Nitride–Silicon Carbide Composite Ceramics

Microporous two-phase AlN–SiC composites were prepared using Al₄C₃ and either Si (N₂ atmosphere) or Si₃N₄ (Ar atmosphere) as precursors. The reaction mechanisms of the two synthesis routes and the effect of processing conditions on reaction rate and the material microstructures were demonstrated. The exothermic reaction between Si and Al₄C₃ under N₂ atmosphere was shown to be a simple processing route for the preparation of porous two-phase AlN–SiC materials. The homogeneous two-phase AlN–SiC composites had a grain size in the range of 1–5 μm, and the porosity varied in the range of 36%–45%. The bending strength was 50–60 MPa, in accordance with the high porosity.     

Mechanochemical Polishing of Silicon Carbide Single Crystal with Chromium(III) Oxide Abrasive

In order to clarify the mechanism of mechanochemical polishing of SiC with Cr₂O₃ abrasive, 6H-wurtzite single-crystal specimens were dry-polished. A significant anisotropic polishing rate difference was found between Si(0001) and C(000 1 ) surfaces. The C(000 1 ) surface was removed 10 times as fast. Polished surfaces were observed from cross-sectional and plan-view directions by high-voltage TEM. There was no trace of mechanical effects such as residual strain or scratches. The polishing debris was analyzed by X-ray diffraction, high-resolution TEM, and analytical TEM. No crystalline phases were identified from X-ray diffraction patterns except for Cr₂O₃, while it was found from TEM observation that a large amount of an amorphous phase consisting of Si, C, and O was contained in the debris. These results indicated that the surface of SiC was removed mechanochemically by the aid of a catalytic oxidation effect of Cr₂O₃.     

Chemical and Structural Widths of Interfaces and Grain Boundaries in Silicon Nitride–Silicon Carbide Whisker Composites

The extent of chemical distributions into crystals bounding whisker/matrix interfaces and matrix grain boundaries and the lateral continuity of the distributions was investigated by analytical electron microscopy methods and compared to their structural widths determined by high-resolution TEM. The extent of the distributions into the bounding crystals, defined as chemical widths, was 10 to 120 times the structural widths; this ratio was larger for grain boundaries than for the interfaces. Further, the chemical distributions were laterally discontinuous at interfaces but continuous at grain boundaries. The elements from the sintering aids, Y₂O₃ and Al₂O₃, were the primary chemical distribution constituents. The distributions were examined by the new position-resolved electron energy loss spectroscopy and Z-contrast scanning TEM methods. Microstructural observations indicated that chemical widths resulted from solid-state diffusion into the bounding crystals and that lateral discontinuities in the distributions resulted from preferential Gibbs–Thompson solution effects of the whisker surfaces at interfaces. These nonequilibrium distributions are process-dependent, and are expected to affect composite properties.     

Fracture Toughness and Thermal Shock Behavior of Silicon Nitride–Boron Nitride Ceramics

Fracture toughness behavior, stress–strain behavior, and flaw resistance of pressureless-sintered Si₃N₄-BN ceramics are investigated. The results are discussed with respect to the reported thermal shock behavior of these composites. Although the materials behave linear-elastic and exhibit no R -curve behavior, their flaw resistance is different from that of other linear-elastic materials. Whereas the critical thermal shock temperature difference (Δ T _c) is enhanced by adding BN, the content of BN has no influence on the strength loss during severe thermal shocks.     

Scandium(III) Triflate‐Catalyzed anti‐Markovnikov Hydrothiolation of Functionalized Olefins

Scandium(III) triflate promoted highly selective addition of thiols to functionalized olefins under mild conditions. The addition follows anti‐Markovnikov regioselectivities, which are unusual for Lewis acids‐catalyzed hydrothiolation. This reaction marks broad functional groups tolerance, which opens a beneficial synthetic route to functionalized and biologically active thio‐compounds. This method is broadly applicable and offers a simple work‐up in the green manner.

     

Development of a High-Temperature Deformation and Life Prediction Model for an Advanced Silicon Nitride Ceramic

A new deformation model inclusive of life prediction capability is introduced for describing general thermal-mechanical loading behavior of an advanced structural ceramic at high temperatures. The model is formulated using the state variable approach. Two internal state variables, namely, "hardening" and "damage" variables, are employed to characterize the current state of the material. The model consists of three rate equations: a flow rule describes the creep rate as a function of the hardening state variable, applied stress, and temperature; and two evoluton rules describe the rate changes of the two internal variables. Material history is accounted for through the evolution of the internal variables. The model was characterized and evaluated based on experimental creep and creep rupture data of an advanced silicon nitride ceramic tested under constant and stepwise-varied loading conditions. A unique strength of the model, not empowered in conventional approaches such as the Norton power-law creep and Monkman-Grant creep rupture relations, is demonstrated with the aid of the hardening variable, which enables the effcts of thermal annealing on subsequent creep and creep rupture behavior to be delineated.     

Residual Stress and Microstructural Evolution in Tantalum Oxide Coatings on Silicon Nitride

Due to its coefficient of thermal expansion (CTE) and phase stability up to 1360°C, tantalum oxide (Ta₂O₅) was identified and investigated as a candidate environmental barrier coating for silicon nitride-based ceramics. Ta₂O₅ coatings were plasma sprayed onto AS800, a silicon nitride ceramic from Honeywell International, and subjected to static and cyclic heat treatments up to 1200°C in air. Cross-sections from coated and uncoated substrates were polished and etched to reveal the effect of heat treatments on microstructure and grain size. As-sprayed coatings contained vertical cracks that healed after thermal exposure. Significant grain growth that was observed in the coatings led to microcracking due to the anisotropic CTE of Ta₂O₅. High-energy X-ray diffraction was used to determine the effect of heat treatment on residual stress and phases. The uncoated substrates were found to have a surface compressive layer before and after thermal cycling. Coating stresses in the as-sprayed state were found to be tensile, but became compressive after heat treatment. The microcracking and buckling that occurred in the heat-treated coatings led to stress relaxation after long heat treatments, but ultimately would be detrimental to the function of the coating as an environmental barrier by affording open pathways for volatile species to reach the underlying ceramic.     

Reactive Synthesis and Phase Stability Investigations in the Aluminum Nitride–Silicon Carbide System

The effect of AlN on the structure formation of SiC was investigated. SiC was synthesized in the presence of AlN under vacuum at 1500°C, and the result was cubic SiC. The synthesis of AlN–SiC composites through the reaction Si₃N₄+ 4Al + 3C = 3SiC + 4AlN was also investigated and compared with synthesis via field-activated self-propagating combustion (FASHS). Reactants were heated in a vacuum furnace at temperatures ranging from 1130° to 1650°C. Below 1650°C, the reaction is not complete and at this temperature the product phases are AlN and cubic SiC. At 1650°C, the product contained an outer layer which contained β-SiC only and an inner region which contained AlN and cubic SiC. 2H-SiC and AlN composites synthesized via field-activated self-propagating combustion were annealed at 1700°C under vacuum. The AlN dissociated and evaporated and the 2H-SiC transformed to the cubic β phase. Reasons for the differences in products of furnace heating and FASHS are discussed.     

Reactions of Silicon Carbide and Silicon(IV) Oxide at Elevated Temperatures

The reaction between SiC and SiO₂ has been studied in the temperature range 1400–1600 K. A Knudsen cell in conjunction with a vacuum microbalance and a high-temperature mass spectrometer was used for this study. Two systems were studied—1:1 SiC (2 wt% excess carbon) and SiO₂; and 1:1:1 SiC, carbon, and SiO₂. In both cases the excess carbon forms additional SiC within the Knudsen cell and adjusts to the direct reaction of stoichiometric SiC and SiO₂ to form SiO( g ) and CO( g ) in approximately a 3:1 ratio. These results are interpreted in terms of the SiC-O stability diagram.