Mechanisms of Growth and Hydrogen Permeation of Zirconium Nitride Film on Zirconium Hydride

Nitride film as a hydrogen permeation barrier on zirconium hydride has seldom been studied. In this work, the zirconium nitride films were prepared on zirconium hydride in an atmosphere of N2 and N2 + H2 at 500~800 °C, with a holding time of 5 h and 20 h, and the mechanisms of film growth and hydrogen permeation were analyzed. The results showed that the film growth was mostly influenced by the temperature, followed by the reaction atmosphere and the holding time. The hydrogen could increase the nitrogen diffusivity during the formation of zirconium nitride films. The in situ nitriding conditions were optimized as 800 °C, N2 + H2 atmosphere, and 5~20 h. The chemical composition of ZrN-based films was mainly comprised of Zr and N, with a minor content of O. In addition, the film exhibited a major phase of ZrN, accompanied by the coexistence of ZrO2, ZrO, ZrN(NH2), and ZrN0.36H0.8, as well as O-H and N-H bonds based on the XPS analysis. The as-prepared ZrN base films in the present study exhibited superior hydrogen permeation resistance to other ZrO2 films previously reported. The hydrogen permeation resistance of the films could be attributed to the following mechanisms, including the chemical capture of hydrogen by the above-mentioned compounds and bonds; the physical barrier of continuous and dense film incurred from the volume effect of different compounds based on Pilling–Bedworth model and the different nitrogen diffusion coefficients at different temperatures.