Mechanism of formation of thin oxide coatings and nano powders at the anodic oxidation of zirconium in molten salts

The mechanism of thin oxide film formation on zirconium is studied, and physicochemical fundamentals are developed for the preparation of zirconium dioxide nano powders in the reaction between zirconium and molten alkali metals with sodium nitrate additives. In the process of zirconium oxidation in molten salts at temperatures 813 to 1073 K, the growth of oxide phases is found to proceed chiefly due to the diffusion of oxygen ions via the oxide film toward the metal-oxide interface. An oxide film formed in the initial period of zirconium oxidation in a chloride-nitrate melt decelerates the process but does not prevent the ion exchange at the metal-melt interface. As the oxide formation proceeds and the steady-state conditions of the corrosion process are reached, the oxidation rate becomes controlled by the diffusion of oxygen ions from the film surface deep into the metal. Along with the diffusion of O2- ions at temperatures 813 to 1073 K, zirconium ions can also migrate in the metal, which makes interpreting the whole process much more complicated. In the oxidation, the films of various colors (from black to light gray) with diverse corrosion and protective properties, as well as fine-dispersed powder of zirconium dioxide with a mean size of particles up to 30 nm, are formed