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Journal of the Electrochemical Society, Vol.163, No.13, C759-C767, 2016
One-Dimensional Pit Experiments and Modeling to Determine Critical Factors for Pit Stability and Repassivation
Experiments on stainless steel artificial pit electrodes in sodium chloride were used to inform a diffusion model developed based on the mass transport behavior within a one-dimensional corroding pit. Measurable estimates of the dissolution flux as well as the potential describing the conditions of interest were obtained from experiment as the one-dimensional pit stability product under a salt film (i . x)(saltfilm) and the repassivation potential Erp, respectively. These parameter estimates were acquired as a function of pit depth and were related to the concentration of the metal cation at the corroding surface at each depth via a one-dimensional mass transport model. These results allowed for the construction of a quantitative framework relating the various electrochemical parameters describing the transition from pit stability to repassivation. Such an analysis permitted the straightforward estimate of the critical surface concentration associated with this transition, which resulted in a single conservative lower bound of 50% of the saturation concentration for the minimum aggressive chemistry to sustain stable pitting and prevent repassivation. Along with published data, these results were utilized to advance the idea that the critical pit solution chemistry is independent of bulk chloride concentration up to 4 M, a range frequently encountered in atmospheric conditions. (C) The Author(s) 2016. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons. org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited.