Evaluating the Critical Chemistry for Repassivation at the Corroding Surface Using Mass Transport Model-Based Artificial Pit Experiments

One-dimensional mass transport model calculations were utilized to design experiments with stainless steel artificial pit electrodes to determine the critical concentration of cations at the corroding surface representing the transition between stable pitting and repassivation. Rapid polarization scans following salt film precipitation and consequent open circuit dilution to different surface concentrations permitted the evaluation of kinetics at various degrees of saturation. These experiments showed a distinct change in kinetics as the surface concentration decreased, thus identifying the critical pit chemistry for the onset of repassivation. Chemical modeling of oxide precipitation from solution permitted the investigation of oxide nucleation across varying surface concentration as a function of pH as the cause of repassivation. This analysis enabled the estimation of the pH at which the first oxide would precipitate in the critical pit solution chemistry, which when combined with cation hydrolysis calculations, resulted in the evaluation of the critical pH at the transition between pit stability and repassivation. A mixed potential theory-based analysis of these results was utilized to provide mechanistic support to the quantitative framework describing critical factors for pitting stability and repassivation.