AbstractsChemistry

The corrosion behaviour of zirconium based alloys has been primarily investigated by electrochemical impedance spectroscopy (EIS). In-situ autoclave EIS experiments were performed in simulated primary coolant conditions in order to study the high temperature water corrosion of zirconium alloys in PWRs. In-situ impedance response of the corroding material was recorded throughout first kinetic transition.A physical model of the zirconium oxide was proposed in accordance with the microstructural observation made by SEM analysis. Electrical properties of the oxide was evaluated with equivalent circuit model (ECM) which was constructed accord- ing to the physical oxide model. Evolution of various oxide parameters obtained from ECM was analysed in accordance with the microstructure observation made by SEM.A two layer structure consists of a outer porous oxide and an inner barrier oxide, was found to be the most accurate description for the autoclave formed oxide. Support- ing evidence from the SEM cross-section and surface analysis of the oxide had shown cracks and pores that were linked and connected with the environment. This observation is also confirmed by the in-situ EIS measurement which has shown porous electrode behaviour throughout the course of oxidation. The porous oxide behaviour was also confirmed by the ex-situ soaking experiment on samples with incremental exposure time.Evolution of inner barrier layer oxide thickness was found to be correlated with kinetic transition which was determined from weight gain measurement. This indicated that barrier layer maybe the oxidation rate controlling layer and its thickness maybe reduced during transition. Thus, a thinner barrier layer would resulted in a rapid corrosion of zirconium alloys. Furthermore, maintaining the barrier layer thickness maybe the possible route to improve zirconium alloy corrosion resistance.