The mechanism of Sn and Nb influence on the fraction of tetragonal ZrO in oxide films on Zr alloys and their influence mechanism on corrosion resistance of Zr alloys, despite decades of research, are ambiguous due to the lack of kinetic knowledge of phase evolution of ZrO with doping. Using stochastic surface walking and density functional theory calculations, we investigate the influence of Nb and Sn on the stability of tetragonal (t) and monoclinic (m) ZrO, and t-m phase transition in oxide films. We found that though Nb and Sn result in similar apparent variation trends in the t-phase fraction in oxide films, their influences on t-m phase transition differ significantly, which is the underlying origin of different influences of the t-phase fraction in oxide films on the corrosion resistance of Zr alloys with Sn and Nb alloying. These results clarify an important aspect of the relationship between the microstructure and corrosion resistance of Zr alloys.
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