Electric field strength effects on time-dependent passivation of metal surfaces

This paper presents further results and extensions of our previous point defect model for time-dependent growth of passive oxide films on metal surfaces. Specifically, by accounting for vacancies as material species rather than just holes in the oxide lattice, the model incorporates more plausible expressions for interfacial reactions and associated kinetic rate expressions. We use the model to explore the general effects of varying metal valence and electrolyte pH on passive film growth. Furthermore, we examine key assumptions concerning the thickness dependence of the electric field within the film. When the electric field inside the film remains constant and the rate constant for oxygen vacancy production varies with applied potential, the model predicts trends in thickness versus potential in reasonable agreement with experimental data for a variety of metal/metal oxide systems. This represents a considerable improvement upon the previous high-field form of the model which assumed rate constants independent of potential and electric field in the film varying with thickness. © 2002 Elsevier Science Ltd. All rights reserved.