Evidence of coupling between film growth and metal dissolution in passivation processes

In the anodisation of Nb in acidic fluoride solutions or warm aqueous alkali, and in that of Mo in concentrated phosphoric acid, impedance spectroscopy provides evidence that 3D film growth proceeds already during the active–passive transition. Indeed, linear potential dependences of both the inverse of the high-frequency capacitance and of the product of the high-frequency resistance times the steady-state current are observed already below the peak potential. Simultaneously, a pseudo-inductive loop at intermediate frequencies is detected in the impedance spectra. In the present paper, we propose a kinetic model for the interpretation of these data. The model assumes that the metal is covered with a non-stoichiometric oxide containing at least two oxidation states of the cation. The processes of oxidative dissolution of the lower valence cations and their transformation to cations of higher valence, leading to passivation, explain the shape of the I–E curve. These processes are limited by both charge transfer at the film–solution (F/S) interface and transport of cation vacancies through the film. Thickening of the oxide film is assumed to proceed simultaneously, and is limited by transport of oxygen vacancies accelerated by an interfacial charge of cation vacancies.