Effects of Nitrogen Deficiency on the Kinetics and Mechanism of Electrolytic ZrNxOxidation

Abstract

Use has been made of potentiodynamic polarization curves, XRD, and scanning electron microscopy (SEM) in the electrolytic oxidation in 3% NaCl solution for specimens of nitrogen-deficient zirconium nitride (ZrN0.67, ZrN0.77, ZrN0.87, and ZrN0.97), as well as pure zirconium. In all cases, the anodic polarization curves have several stages which characterize during oxidation both active dissolution of ZrN x and Zr in the electrolyte as well as the formation of surface layers of ZrOCl2, ZrN x O y , and α‐ZrO2 of monoclinic form. The corrosion resistance of single-phase ZrN x specimens in 3% NaCl solution decreases in the sequence ZrN0.97 → ZrN0.87 → ZrN0.77, and the initial stages of interaction between the specimen surface and the electrolyte largely determine the subsequent behavior of specimens. It is found that ZrN x containing a large number of nitrogen atom vacancies, in particular ZrN0.77, is closer in corrosion behavior to metallic zirconium than it is to stoichiometric ZrN (the reduction in the corrosion resistance is undoubtedly due to the reduction in the ionic-covalent components of the bonds in ZrN x ).