Mechanism and Kinetics of Oxidation of ZrN Ceramics

Oxidation of ZrN ceramics from 973–1373 K under static conditions reveals parabolic rate behavior, indicative of a diffusion-controlled process. In-situ high temperature powder XRD found the oxidation mechanism begins with destabilization of ZrN through formation of a ZrN1−x phase with oxide peaks initially detected at around 773 K. The zirconium oxide layer was found to be monoclinic by in-situ XRD with no evidence of tetragonal or cubic polymorphs present to 1023 K. Bulk ceramic samples oxidized at 1173 and 1273 K underwent slower oxidation than those oxidized at 973 and 1073 K. This change in oxidation rate and hence mechanism was due to formation of a denser c-ZrO2 polymorph stabilized by nitrogen defects. This N-doped dense ZrO2 layer acts as a diffusion barrier to oxygen diffusion. However, at an oxidation temperature of 1373 K this layer is no longer protective due to increased diffusion through it resulting in grain boundary oxidation.