title: In situ pH measurement during the formation of conversion coatings on an aluminum alloy (AA2024).
abstract: The measurement of interfacial pH change is important for understanding the formation mechanism of conversion coatings that are used to protect metals from corrosion. In this work, we used a tungsten microelectrode to measure the interfacial pH change near the surface of an aluminium alloy (AA2024) during the formation of two conversion coatings: (i) a trivalent chromium pretreatment (TCP) and (ii) a Ti-based, non-chromium-containing coating. The tungsten microelectrode exhibited an open circuit potential (OCP) that changed linearly as a function of the solution pH with a slope of -64 mV per pH. The microelectrode was positioned near the AA2024-T3 surface and its potential was measured as a function of time along with the OCP of the alloy sample during formation of the two coatings. The microelectrode exhibited a negative shift in potential immediately upon initiation of the coating formation, consistent with a significant increase in the interfacial pH of 2-6 units depending on the coating system. The pH increase is attributed to proton-consuming cathodic reactions that occur on the alloy surface once the passivating oxide layer is dissolved: hydrogen evolution and oxygen reduction. The increased pH causes the hydrolysis of the soluble fluorometalate precursor species in the baths, which precipitate forming a hydrated metal oxide coating (e.g., ZrO2·nH2O).
authors.affiliation: Department of Chemical Engineering & Materials Science, Michigan State University, East Lansing, MI 48824, USA.
authors.forename: Liangliang
authors.initials: L
authors.lastname: Li
authors.forename: Annika Laura
authors.initials: AL
authors.lastname: Desouza
authors.forename: Greg M
authors.initials: GM
authors.lastname: Swain