Understanding the Mechanisms of Early Stage Aluminum Corrosion

Abstract

Aluminum alloys are widely used in many applications due to their inherent corrosion resistance, which is attributed to the formation of a protective oxide layer. However, the strength and durability of many Al-based materials is reduced in humid environments. Consequently, detailed mechanistic understanding of corrosion reactions over time is necessary to predict the cost, safety, and performance. Most of the current knowledge of atmospheric aluminum corrosion is built on response relationships upon extensive corrosion and typically involve a first-order correlation of corrosion data with environmental conditions. However, mechanistic understanding of corrosion processes is still limited, particularly at the early stages of exposure to humid environments. In addition, the effects of electrolytes such as sodium chloride present in the environment are still not fully understood. This presentation will focus on our recent efforts to reveal the mechanistic dependence of electrochemical aluminum corrosion in humid air in the presence of NaCl. The rate of corrosion is explored through complimentary experimental and theoretical analyses relating corrosion rate to electrolyte chemistry, mass uptake and corrosion products. As an experimental platform, we use quartz crystal microbalance (QCM) electrodes coated with aluminum and sodium chloride using sputtering techniques. Structure, composition, and surface morphology of the samples were characterized by grazing-incidence X-ray diffraction, FTIR spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, scanning transmission electron microscopy, and electron energy loss spectroscopy. The QCM provides operando data with nanogram resolution on the formation of the corrosion product layer, from which we can derive rate constants for aluminum surface reactions. We find that the reaction rate in dry air is negligible, but a dramatic acceleration is observed at 50% RH and above. In addition, this study provides additional insight into: 1) the influence of the sodium chloride film thickness on the rate and reaction products; 2) the role of surface termination and roughness on aluminum oxide/hydroxide formation; and 3) the electrochemical corrosion reaction rate acceleration as a function of temperature. Finally, based on the interplay between theory and experiment we achieved preliminary understanding of the rate-limiting steps, which we will use to develop validated computational models of early-stage (hours to several days) aluminum corrosion. Figure 1