The processes of passive oxidation, deposit-induced corrosion, active oxidation, scale/substance interactions, and scale volatility are presently studied in the case of high-purity SiC and Si3N4 in pure oxygen, giving attention to such secondary elements in the ceramics as water and CO2 oxidants, combustion environment impurities, and thermal cycling. Deposit-induced corrosion is discussed for the cases of NaSO4 as well as vanadate and oxide-slag deposits; issues associated with the active-to-passive oxidation transition are noted.

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Corrosion of Silicon-Based Ceramics in Combustion Environments

Some aspects of processing, microstructure and properties of the various types of silicon nitride are discussed. Special emphasis is placed on the relationships between powder properties, process conditions, densification and microstructure, as well as the interdependence between microstructure and properties. After summarizing the areas of crystal structure and thermodynamic properties, and processing of the different types of Si3N4, the state-of-the-art of dense and reaction-bonded silicon nitride is given. For both types the formation mechanisms and microstructure, relationships between powder properties, additives (in the case of dense Si3N4), process conditions, and densification and microstructure, as well as data and microstructural effects of various mechanical, thermal and thermo-mechanical properties, are outlined. Advanced processing techniques, such as sintering, gas-pressure sintering, post-sintering, and the different routes of hot-isostatic pressing (starting with powder compacts, reaction-bonded Si3N4 or pre-sintered Si3N4 and the resulting properties, are discussed.

Relationships between processing, microstructure and properties of dense and reaction-bonded silicon nitride

The theme of the review is the construction of a model embracing the mechanism of formation of reaction-bonded silicon nitride, the development of microstructure and mechanical properties. Possible nitridation reactions are discussed, with emphasis on kinetics and on phase composition and microstructure of the reaction product. The influence of Fe, a common impurity in silicon powders, and of H2, as an additive to the nitriding atmosphere, is considered in some detail. The optical, electrical and thermal properties are briefly discussed and areas for further research and development studies identified.

Reaction-bonded silicon nitride: its formation and properties

Influence of Microstructure on Fracture Propagation in Rock
This paper describes the results of research to correlate the fracture resistance with microstructural features of Salem limestone and Berea sandstone. Tests were conducted on wedge-loaded double-cantilever-beam specimens containing machined slots as crack starters. The fracture resistance of Salem limestone measured in terms ofR, the energy dissipated per unit area of projected surface, was found to increase in the initial stage of crack extension but finally reached a constant value which was strongly dependent on crack orientation with respect to the bedding plane. For this limestoneR ranges from about 50 joules/m2 to 230 joules/m2 (1 joule/m2 = 104 erg/cm2). The sandstone which is a more compliant rock exhibited similar fracture behavior while theR values ranged from 465 joules/m2 to 1580 joules/m2. In addition, tests in liquid nitrogen which were aimed at eliminating plastic deformation in the rocks during fracture showed little difference inR for the limestone but a substantial reduction inR for the sandstone which, in the latter case, may be caused by differential thermal expansion between the quartz grains and the calcite cement. Acoustic emissions were detected in both rocks at very early stages in the tests indicating the occurrence of microcracking near the initial slot tip at low loads. The mode of fracture and the fracture path in both materials were identified by fractography over a broad range of magnifications. The evidence gained from this work strongly points to the existence of an extensive array of microcracks produced in a region surrounding the main crack tip and which advances with it. The energy dissipated in fracturing of rock is associated with the creation of the large amount of surface area contained in this microcrack array. This picture provides a self-consistent explanation for the puzzling discrepancy between the measured tensile strength of rocks and the strengths predicted from measuredR values.

Influence of Microstructure on Fracture Propagation in Rock

Overview no. 5: Fracture-mechanism maps for materials which cleave: F.C.C., B.C.C. and H.C.P. metals and ceramics

The structure of reaction-sintered silicon nitride is studied using scanning electron and optical microscopy at various stages during nitriding, for a range of nitriding and compacting conditions. The strength is then evaluated and interpreted in terms of the microstructure. It is found that fracture always occurs in a brittle manner by the extension of the largest pores. The effects of prolonged annealing in air above 1000† C on both the structure and strength are investigated. At 1400† C, cristobalite is formed. If the temperature is then maintained above 250† C, the strength is enhanced, but below this temperature the oxide layer cracks and reduces the strength.

R. W. Davidge

Papers

The strength and oxidation of reaction-sintered silicon nitride