High-Temperature Properties of Si3N4 Ceramics

Silicon nitride is a highly covalent bonded compound which decomposes at 1877°C. Therefore, it is impossible to densify Si3N4 without sintering additives. Densification is achieved by liquid-phase sintering usually using metal oxides such as MgO, Y2O3, A12O3, and most of the rare-earth oxides as sintering additives. The oxides react with SiO2—always present at the surface of Si3N4 particles—to form an oxide melt and, with increasing temperature, an oxynitride melt by dissolution of Si3N4. The resulting microstructure consists of elongated Si3N4 needles embedded in a matrix of smaller equiaxed Si3N4 grains and a grain boundary phase, as shown in Figure 1. The amount and chemistry of the sintering aids determine the volume fraction of the grain boundary phase. The content required for complete densification depends on the sintering techniques: 2–5 vol% additives are sufficient if densification is supported by a high external pressure (hot pressing [HP] or hot isostatic pressing [HIP]); pressureless-sintered and gas-pressure-sintered (10-MPa nitrogen pressure) materials have additive contents of up to 15 vol%. Today, silicon nitride ceramics are regarded as a class of material comparable to steel. Different qualities depend on the size and shape of the silicon nitride grains and the amount and chemistry of the grain boundary phase. Materials with a high room-temperature strength exhibit a finegrained, elongated microstructure, while materials with a high fracture toughness are more coarse-grained. In both cases, a weak interface is required to induce transgranular fracture. (See Becher et al. in this issue.) Since all Si3N4 grains are completely wetted by the grain boundary phase, the interface strength is determined by the additive composition. Nevertheless, a contradiction arises between the development of high-strength and high-toughness Si3N4 ceramics and high-temperature resistant materials because the grain boundary phase is responsible for the excellent properties at low temperatures, but limits the properties at temperatures above its softening point.