Role of magnesium ions in modifying oxide growth rate on Zircaloy under breakaway corrosion regimes

General corrosion of nuclear reactor in core material like Zircaloy-2 and breakaway corrosion in particular are of great importance in ensuring its smooth long term operation. Metal ions like Mg²⁺ added to the coolant, to mitigate corrosion of other structural materials like Carbon steel, can get incorporated in the corrosion product oxide on Zircaloy-2 and alter its corrosion behavior. Plasma Electrolytic Oxidation (PEO) method was employed to investigate the effect of Mg²⁺ ions during breakaway corrosion of Zircaloy-2. The main objective was to understand the morphology, protectiveness, semiconducting properties of the Mg modified oxide films on Zircaloy-2 surface. DC potentials 300, 400 and 500 V were used to accelerate corrosion kinetics and form oxide mimicking the breakaway corrosion regime. Borate buffer (pH 9.8) was used as the electrolyte, and Mg acetate was added as Mg source for probing the effect of Mg²⁺ ions. Oxide morphology depended largely on the formation potentials. The presence of magnesium resulted in thinner oxides with lower defect densities. GIXRD of the oxide showed stabilization of tetragonal phase in presence of Mg at 300 and 400 V. Oxide resistance and charge transfer resistances measured by EIS were observed to be higher due to Mg incorporation at these potentials. Mg addition facilitated formation of t-ZrO₂. The electrochemical measurements suggested that the presence of Mg in ZrO₂ could reduce the connected porosity in the oxide thereby stifling the diffusion paths. These factors lead to improved corrosion protectiveness of the oxide formed in the presence of Mg.