A first-principles analysis of the charge transfer in magnesium corrosion

Magnesium is the lightest structural engineering material and bears high potential to manufacture automotive components, medical implants and energy storage systems. However, the practical use of untreated magnesium alloys is restricted as they are prone to corrosion. An essential prerequisite for the control or prevention of the degradation process is a deeper understanding of the underlying corrosion mechanisms. Prior investigations of the formation of gaseous hydrogen during the corrosion of magnesium indicated that the predominant mechanism for this process follows the Volmer–Heyrovský rather than the previously assumed Volmer–Tafel pathway. However, the energetic and electronic states of both reaction paths as well as the charge state of dissolved magnesium have not been fully unraveled yet. In this study, density functional theory calculations were employed to determine these parameters for the Volmer, Tafel and Heyrovský steps to gain a comprehensive understanding of the major corrosion mechanisms responsible for the degradation of magnesium.