First-principles search for alloying elements that increase corrosion resistance of Mg with second-phase particles of transition metal impurities

Abstract

A significant challenge for applications of Mg alloys is their poor corrosion resistance and hence Mg alloys designs with built-in corrosion resistance are of significant interest. Corrosion can result from the coupling of anodic dissolution of Mg and cathodic reduction of water on impurities such as Iron (Fe)-rich second-phase particles. Experiments have shown that small quantities of Arsenic (As) or Germanium (Ge) can inhibit Mg corrosion, possibly slowing the hydrogen evolution reaction (HER) as the cathodic reaction on Fe surfaces. Since a broader experimental search across the periodic table for other Mg corrosion inhibiting elements is unavailable, we designed thermodynamic and HER criteria, and used high-throughput computations to search a pool of 68 elements including As and Ge that can segregate from bulk Mg to surfaces of Fe particles and impede the HER there. Our computational procedure predicts that six p-block elements meet these criteria, and they rank according to their ability to reduce H adsorption energies and the HER rate as follows: As > Ge > Si > Ga > P ≈ Al. Results for As, the most effective corrosion-inhibiting element, and Ge are in qualitative accord with recent experiments. While none of the 68 elements was found to enhance H adsorption, the six p-block elements reduce H adsorption via strong orbital overlap (Pauli repulsion) between their outer-shell orbitals and the s orbitals of H adsorbates. These p-block elements are also found to have the potential to reduce HER on surfaces of Ni second-phase particles in Mg according to the same criteria, but not on surfaces of Cu second-phase particles.