Stable pitting corrosion of stainless steel as diffusion-controlled dissolution process with a sharp moving electrode boundary

Abstract

This paper is devoted to explanation and prediction of pit propagation or stable pit growth, governed by ion transport properties in electrolytic solutions. Therefore, we vigorously derive the (3D) mass conservation law for a body hosting a sharp metal/solution interface separating the solid electrode from liquid electrolyte. The model for stable pitting corrosion is completed by Fick’s law of diffusion, governing the behavior of the dissolved metal ions. There are only three model input values, which are directly accessible from experiments, namely the ion concentration in the solid metal, as well as the diffusion coefficient and the saturation concentration of the dissolved metal ions in the electrolyte. The partial differential equations describing stable pitting corrosion as diffusion-controlled dissolution process are solved for boundary conditions related to 1D pencil electrode tests as well as to 2D foil electrode tests. The mathematical solution functions (model predictions) are related to pit growth in terms of depth and width, and to electric current evolution. Such model predictions reasonably agree with corresponding experiments, which shows the relevance of the proposed approach. In the case of pits with lacy covers, the boundary conditions for the ionic flux probably depend on complex depassivation–repassivation phenomena. However, once the extent of perforation of the lacy cover is known, the entire pit propagation characteristics, in particular the pit shape, can be predicted by the proposed model, relating to a classical Stefan problem.