Aluminum and its alloys are extensively utilized in various applications due to their high thermal and electrical conductivity and inherent resistance to corrosion, primarily due to the formation of a protective oxide layer. However, the strength, durability and electrical properties of many aluminum-based materials and aluminum/gold contacts tend to diminish in humid environments. Therefore, a thorough understanding of the mechanistic aspects of atmospheric corrosion reactions over time in pure Al and galvanic Al/Au couples is crucial for predicting degradation and optimizing performance. Presently, much of our knowledge regarding atmospheric aluminum corrosion is derived from empirical correlations based on extensive corrosion data, typically involving a simplistic relationship between corrosion rates and environmental factors. However, the mechanistic understanding of corrosion processes, particularly during in the presence of electrolytes like sodium chloride found in the environment is not fully elucidated.Here we propose a new surface approach to obtain mechanistic insights into atmospheric corrosion of Al and Al/Au thin films in the presence of NaCl. The corrosion rate is investigated through a combination of experimental and theoretical approaches, correlating corrosion kinetics with electrolyte chemistry, mass changes, and corrosion byproducts. Quartz crystal microbalance with dissipation (QCM-D) electrodes coated with aluminum and aluminum/gold contacts and sodium chloride serve as the experimental platform. The structure, composition, and surface morphology of the samples are analyzed using various techniques including grazing-incidence X-ray diffraction, FTIR spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, transmission electron microscopy, and electron energy loss spectroscopy. Operando data with nanogram resolution provided by the QCM-D technique allows real-time monitoring of corrosion product formation, facilitating the derivation of rate constants for corrosion surface reactions. It is observed that the reaction rate in dry air is negligible, but a significant acceleration occurs at relative air humidity levels of 50% and above. Additionally, this study delves into the impact of sodium chloride on the corrosion rate and reaction products, the influence of surface termination on aluminum oxide/hydroxide formation, and the temperature-dependent acceleration of electrochemical corrosion rates. Finally, by integrating theoretical insights with experimental findings, preliminary understanding of the rate-limiting steps has been achieved, paving the way for the development of validated computational models to simulate early-stage atmospheric corrosion processes.
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