Why are Zn-rich Zn–Mg nanoalloys optimal protective coatings against corrosion? A first-principles study of the initial stages of the oxidation process

ZnMg alloys of certain compositions in the Zn-rich side of the phase diagram are particularly efficient, and widely used, as anticorrosive coatings, but a sound understanding of the physico-chemical properties behind such quality is still far from being achieved. The present work focuses on the first stage of the corrosion process, namely the initial growth of a sacrificial surface oxide layer, whose characteristics will condition the next stages of the corrosion. A comprehensive ab initio study, based on density functional theory, is carried out on ZnMg nanoalloys with 20 atoms and different compositions, which serve as model systems to simulate the complex processes that occur in extended granular surfaces. The structural and electronic properties, when progressive oxidation of the nanoalloys takes place, are analyzed in detail with the help of structural descriptors, energetic descriptors such as the oxygen adsorption energies and excess adsorption energies, as well as with electronic ones based on the topological analysis of the electron density and the electron localization function, from which a detailed analysis of the bonding patterns is extracted. We explain why small amounts of Mg create a very positive synergy between Zn and Mg that increases the reactivity to oxygen while reducing, at the same time, the stress induced on the cluster substrate, both facts working in favor of promoting the growth of the oxide crust whilst protecting the core. Moreover, we also show that stoichiometries close to the Mg2Zn11 and MgZn2 compositions are the best candidates to optimize the protection against corrosion in Zn-Mg alloys, in agreement with the experimental observations.