Modelling of Zircaloy-4 accelerated degradation kinetics in nitrogen-oxygen mixtures at 850 °C

Zirconium-based alloys used in PWR cladding show an acceleration of their oxidation kinetics in air at high temperature compared to their behaviour under oxygen or steam alone. This paper presents an analysis of the oxidation kinetics in order to explain the role of nitrogen during the accelerated corrosion. Isothermal thermogravimetry on alloy thin plates was used to collect kinetic data during the reaction of Zircaloy-4 at 850 °C in oxygen and nitrogen mixtures. The influence of oxygen and nitrogen partial pressure on the degradation kinetics was studied by a jump method. The presence of nitrogen in the reacting gas enables the formation of zirconium nitride near the oxide-metal interface which acts as a catalytic phase. A three steps reaction path composed of nitride oxidation, α-Zr(O) nitridation and oxidation is proposed. A detailed mechanism and the rate-determining step of the overall process are proposed that account for the experimentally observed dependence of the kinetic rate with the oxygen and nitrogen partial pressures; a kinetic model based on surface nucleation and growth of regions attacked by nitrogen was successful in describing the mass variations with time of exposure at 850 °C.