In this work, a rotating disk electrode was used to measure the cathodic kinetics on stainless steel as a function of diffusion layer thickness (6 to 60 μm) and chloride concentration (0.6 to 5.3 M NaCl). It was found that, while the cathodic kinetics followed the Levich equation for large diffusion layer thicknesses, the Levich equation overpredicts the mass-transfer limited current density for diffusion layer thicknesses less than 20 μm. Also, an unusual transitory response between the activation and mass-transfer controlled regions was observed for small diffusion layer thicknesses that was more apparent in lower concentration solutions. The presence and reduction of an oxide film and a transition in the oxygen reduction mechanism were identified as possible reasons for this response. The implications of these results on atmospheric corrosion kinetics under thin electrolyte layers is discussed.

The natural convection boundary layer ( δ n c ) and its influence on cathodic current in a galvanic couple under varying electrolytes as a function of concentration (1 − 5.3 M NaCl) and temperature (25 °C−45 °C) were understood. Polarization scans were obtained under quiescent conditions and at defined boundary layer thicknesses using a rotating disk electrode on platinum and stainless steel 304L (SS304L); these were combined to determine δ n c . With increasing chloride concentration and temperature, δ n c decreased. Increased mass transport (Sherwood number) results in a decrease in δ n c , providing a means to predict this important boundary. Using Finite Element Modeling, the cathodic current was calculated for an aluminum alloy/SS304L galvanic couple as a function of water layer (WL) thickness and cathode length. Electrolyte domains were delineated, describing (i) dominance of ohmic resistance over mass transport under thin WL, (ii) the transition from thin film to bulk conditions at δ n c , and (iii) dominance of mass transport under thick WL. With increasing chloride concentration, cathodic current decreased due to decreases in mass transport. With increasing temperature, increased cathodic current was related to increases in mass transport and solution conductivity. This study has implications for sample sizing and corrosion prediction under changing environments.

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Calculated maximum pit sizes for stainless steel 304L (SS304L) are presented for atmospheric conditions with elevated chloride concentrations and temperatures. These calculations were carried out by experimentally determining the pit stability product ((i • x) s f ), repassivation potential (E r p ), and cathodic kinetics. These results were aided by determination of a solubility curve as a function of temperature for a stoichiometric metal salt mixture of iron chloride (FeCl 2 ), chromium chloride (CrCl 3 ), and nickel chloride (NiCl 2 ). Based on these newly measured saturation concentrations, metal ion diffusivities were calculated. Overall, it was found that (i • x) s f decreases with increasing chloride concentration and increases with increasing temperature. E r p was determined to decrease with increasing concentration and increase with increasing temperature. When incorporated into the maximum pit size model, these experimental results yielded a small increase in maximum pit size with increasing bulk chloride concentrations and/or increasing temperature.

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