Temperature sensitivity and transition kinetics of uniform corrosion of zirconium alloys in superheated steam

Abstract

Corrosion transition during uniform corrosion of zirconium alloys receives much attention since it is the major degradation procedure. However, predicting the time and oxide thickness at transition has been hindered by the lack of knowledge about transition kinetics and how it responds to varied temperatures. Current study investigated the temperature-sensitivity of corrosion kinetics, transition behavior and microstructures of various zirconium alloys corroded in superheated steam ranging from 390 °C/10.3 MPa to 455 °C/10.3 MPa by autoclave experiment and microscopy analyses. Transition time was found to follow Arrhenius-type relationship with temperature for the first time. Both the transition oxide thickness and metastable oxide thickness increased with temperature, which was theoretically deduced and experimentally confirmed. In Zr-4 oxides, a transition thickness varying from 3.3 μm at 390 °C to 4.2 μm at 455 °C was observed. Microstructure results presented rather large HCP-ZrO particles (200∼400 nm) at O/M interface and they were even larger at the protruded positions. An intense sub-stoichiometric atmosphere was identified at O/M interface, promoting the growth of metastable oxides. The activation energy of transition kinetics was 86∼114 kJ/mol, which is close to diffusion activation energy of oxygen in tetragonal zirconia. A new model based on parabolic-law empirical relationship was thus proposed to predict transition kinetics. Predictions regarding the time to oxidation breakaway at 900–1000 °C were reported, and the results were in good agreement with the experimental data.