Considerations of the Role of the Cathodic Region in Localized Corrosion

Abstract

The ability of wetted cathodes of limited area to support localized corrosion sites on passive materials exposed to atmospheric conditions was studied computationally. The analysis pertains to conditions where metal surfaces are covered by thin layers of moisture in contrast to conditions of full immersion. The moisture may be a continuous layer or in patches with and without particulate on the surface. These conditions are of interest for the surfaces of the waste packages at the proposed Yucca Mountain Repository where waste packages are supported in air. The cathode capacity was characterized by the total net cathodic current, I{sub net}, which the surface surrounding a localized corrosion site (i.e., a pit or crevice) could supply. The cathode capacity increases with increasing cathode area, but it saturates at finite cathode sizes due to the resistance of the thin electrolyte layer. The magnitude of the capacity depends on the water layer thickness, the solution conductivity, and the electrochemical reaction kinetics. The presence of particulates is treated by considering both volume and surface coverage effects. The limited electrolyte volume under thin film conditions can lead to rapid pH changes which decrease the cathode capacity due to the slower electrochemical kinetics at elevated pH. These effects can make localized corrosion less likely to be sustained.