Oxidation behaviour of Si3N4–TiN ceramics under dry and humid air at high temperature

The oxidation in air of Si₃N₄-based ceramics containing 35 vol.% of TiN secondary phase and different amounts of sintering additives has been studied at different temperatures up to 1400 °C in dry or humid environment. The oxidation starts by crystal growth of TiO₂ at the surface, then a multilayered scale develops under the rutile layer from 1000 °C. This subscale is composed of silicon nitride in which TiN particles are oxidized to agglomerates of rutile, glass and pores. The oxidation process is controlled by the matter transports, which take place in the intergranular phase. These transport phenomena are affected by the changes in distribution and composition of the glassy phase and by humidity which modifies the glass network structure and thus the in-diffusion rate. From 1200 °C, Si₃N₄ grains are also oxidized, the additional glass formed closes the residual porosities yielding scales more compact and developing an autoprotective behavior. At 1400 °C, glass phase crystallizes into cristobalite and the rutile top layer becomes discontinuous. Only composites with low amounts of sinter additives keep an autoprotective oxidation mode.