Modelling the formation and growth of anodic passive films on metals in concentrated acid solutions

Abstract

Two model approaches to the formation of passive films as adsorbed layers during the active anodic dissolution of a metal in acid and their subsequent growth are presented. The first depicts passivation as proceeding in parallel to active dissolution. Adsorption of water on active surface sites leads to passivation, whereas adsorption of acid leads to active dissolution of the metal. The model is consistent with the impedance response during passivation of Fe and an Fe-20%Mo alloy in concentrated H3PO4. The second model is an updated version of the so-called surface charge approach to the mechanism of conduction of anodic passive films. It is based on the assumptions that oxygen vacancies are the main ionic charge carriers and the field strength in the barrier layer is constant. A negative surface charge built up at the film/solution interface via accumulation of metal vacancies accelerates oxygen vacancy transport, thus explaining the pseudoinductive behaviour of the metal/film/electrolyte system under small amplitude a.c. perturbation. The model describes the growth of thin anodic films on Fe, Mo and an Fe-20%Mo alloy in concentrated H3PO4.