An RDE Approach to Investigate the Influence of Chromate on the Cathodic Kinetics on 7XXX Series Al Alloys under Simulated Thin Film Electrolytes

Abstract

The effect of sodium chromate on the cathodic current availability pertinent to the micro-galvanic-induced corrosion of high-strength AA7XXX alloys under simulated thin electrolyte films representative of atmospheric conditions was investigated utilizing a combination of electrochemical and surface characterization techniques. The rotating disk electrode technique provided a means to simulate the effects of water layer thickness to differentiate thin film conditions from full immersion conditions, and enabled the study of the mass-transport-limited oxygen reduction reaction (ORR) on AA7XXX alloys as a function of chromate concentration. The ORR current density decreased by up to two orders of magnitude upon addition of 10 mM chromate, however, the degree of inhibition was observed to depend on the Cu content of the alloy. Chromate was reduced irreversibly to form a Cr3+-rich film on the alloy surface that blocked cathodic sites and hindered ORR. This film was confirmed by X-ray photoelectron spectroscopic characterization of the chemistry and thickness of the chromate-induced layer formed on the specimens after exposure to chromate. The layer was approximately 13 nm in thickness and consisted of mixed Cr3+/Cr6+ oxides with some metallic Cr. Studies on a Pt electrode demonstrated the intrinsic ability of chromate as an effective inhibitor for ORR.