Accommodation of Tin in Tetragonal ZrO2

Abstract

Atomic scale computer simulations using density functional theory were used to investigate the behaviour of tin in the tetragonal phase oxide layer on Zr-based alloys. The $S{n}_{Zr}^{\times }$ site defect was shown to be dominant across most oxygen partial pressures, with $S{n}_{Zr}^{"}$ charge compensated by fully charged oxygen vacancies occurring at partial pressures below $10^{-31}$ atm. Insertion of additional positive charge into the system was shown to significantly increase the critical partial pressure at which $S{n}_{Zr}^{"}$ is stable. Recently developed low-Sn nuclear fuel cladding alloys have demonstrated an improved corrosion resistance and a delayed transition compared to Sn-containing alloys, such as Zircaloy-4. The interaction between the positive charge and the tin defect is discussed in the context of alloying additions, such as niobium and their influence on corrosion of cladding alloys.