Modelling the electrochemical transients during repassivation under open-circuit conditions in a neutral solution

Abstract

The responses of the current and the coupled potential to rapid depassivation have been studied on a three-electrode system under open-circuit conditions. Passivated AISI 304 stainless steel in low- and high-conductivity solutions of Na2SO4 has been depassivated with a single, rapid scratch over the small fraction of surface of the working electrode (WE). Single- and dual-WE configurations have been implemented. Once the surface is scratched, the current and potential transients exhibit a delayed maximum and minimum, respectively, in contrast to the outcome of more common potentiostatic scratching experiments. A simple model based on the equivalent circuit has been developed to predict the observed transients and provides clear relations between the features of the transient and the parameters of the electrolyte and the electrodes. The interfacial capacitance of the electrodes’ passive surfaces proves crucial for the shapes of the observed potential and current transients. It is shown that this capacitance temporarily provides the majority of the charge for repassivation under open-circuit conditions. Possible sources of specific discrepancies between the model and the measured transients are indicated.