New heat treatment methods for glass removal from silicon nitride and sialon ceramics

Sialon ceramics were discovered simultaneously (but independently) in late 1971 at Newcastle University and also at the Toyota Research Laboratories in Japan. During the 30 years since their original discovery, the Newcastle laboratory has made a significant contribution to current understanding of the science and technology of these materials. Sialons are of interest as engineering materials for high temperature (>1000°C) applications because they can be pressureless-sintered to high density and be designed to retain good mechanical properties even up to ≈1350°C, whereas competing metallic materials are weaker and prone to corrosion. A characteristic disadvantage of all nitrogen ceramics is that an oxide additive is always included in the starting mix to promote densification, and this remains in the final product as a glassy phase distributed throughout the grain boundaries of the final microstructure. Since the glass melts at ≈1000°C, the high temperature properties of the final ceramic are in fact determined by the properties of the grain-boundary glass. The most common method of improving high-temperature performance is to heat-treat the material at temperatures of 1100–1350°C in order to devitrify the glass into a mixture of crystalline phases. More specifically it is desirable to convert the glass into a sialon phase plus only one other crystalline phase, the latter having a high melting point and also displaying a high eutectic temperature (max ≈1400°C) in contact with the matrix sialon phase. Previous studies have shown that there are a limited number of possible metal-silicon-aluminium-oxygen-nitrogen compounds which satisfy these requirements. The present paper gives an overall review of this subject area and then summarises recent work at Newcastle aimed at total removal of residual grain boundary glass. This has been achieved by: (1) a post-preparative vacuum heat treatment process to remove the grain boundary glass from silicon nitride based ceramics in gaseous form, (2) above-eutectic heat-treatment (AET) of sialon-based ceramics to crystallize grain-boundary liquid into five-component crystalline sialon phases.