A review of electrochemistry of relevance to environment-assisted cracking in light water reactors

The electrochemistry of relevance to environment-assisted cracking in high temperature, low conductivity water is critically reviewed. The review covers corrosion potential and electrochemical polarisation measurements, thermodynamics, and also experimental measurements and mathematical modelling of the electrochemistry in cracks and crevices. There is a lack of critical data in relation to the electrode kinetics of relevant cathodic reduction reactions, namely H+, H2O, O2, H2O2 and steady-state anodic reaction data are limited. Transient anodic current measurements, associated with initially film-free metal, have been made for a range of conditions but there is uncertainty regarding the role of fluid flow and transport processes on the current decay characteristics. A number of experimental measurements of potential and pH in crevices and cracks have been made but the experiments are difficult to carry out reliably and hence the range of data of relevance to practical conditions is very limited. Recent developments in mathematical modelling have significantly enhanced the qualitative understanding of the processes controlling the local electrochemistry in cracks and crevices but the reliability of the quantitative predictions is limited by the paucity of reliable input data. (Author)