Atomic scale understanding of initial Cu-Ni oxidation from machine-learning accelerated first-principles simulations and in situ TEM experiments

Abstract: The development of accurate methods for determining how alloy surfaces spontaneously restructure under reactive and corrosive environments is a key, long-standing, grand challenge in materials science. Current oxidation models, such as Cabrera-Mott, are based on macroscopic empirical knowledge that lacks fundamental insight at the atomic level. Using machine learning-accelerated density functional theory with in situ environmental transmission electron microscopy (ETEM), we examine the interplay between surface reconstructions and preferential segregation tendencies of CuNi(100) surfaces under oxidation conditions. Our modeling approach based on molecular dynamics and grand canonical Monte Carlo simulations shows that oxygen-induced Ni segregation in CuNi alloy favors Cu(100)-O c(2x2) reconstruction and destabilizes the Cu(100)-O missing row reconstruction. The underpinnings of these stabilization tendencies are rationalized based on the similar atomic coordination and bond lengths in NiO rock salt and Cu(100)-O c(2x2) structures. In situ ETEM experiments show Ni segregation followed by NiO nucleation and growth in regions without MRR, with secondary nucleation and growth of Cu2O in MRR regions. This further corroborates the simulated surface oxidation and segregation modelling outcomes. Our findings are general and are expected to extend to other alloy systems.