Microstructure Evolution and Mechanism during Nitridation of Carbon-Containing Internal Gelation-Derived Zirconia

Abstract Zirconium nitride is an increasingly attractive material, owning to its wide range of applications. Nitridation with carbon as a reductant is a commonly used process for the preparation of transition metal nitrides. In this study, the nitridation of carbon-containing zirconia gels was studied as a method to synthesize zirconium nitride. The behavior of the gel upon heat treatment was investigated online. The evolution of the microstructure during nitridation was investigated using high-resolution transmission electron microscopy (HRTEM). The relationships between the gaseous species, crystalline phases, microstructure, and chemical elements of the resulting materials were established. The results showed that NH3, CH2O, CO2, CO, H2O, and HCN were the gaseous products in the nitridation process. Nucleation of the nanograins started with zirconium oxynitride. Transformation from oxynitride to nitride led to the occurrence of open-mouth-like defects on the particles. The enrichment of N atoms was accompanied by a core-shell structure. Finally, a systematic nitridation mechanism involving five stages was proposed. This study is important for understanding the nitridation process and controlling the structure and properties of transition metal nitrides.