A thermogravimetric comparative study of the high temperature steam oxidation of bare and pre-oxidized Zircaloy-4, M5Framatome and Optimized ZIRLO™

Abstract

For Loss of Coolant Accident (LOCA) analysis, high-temperature oxidation kinetics in steam of Zircaloy-4 and the two Nb-bearing alloys used in French Pressurized Water Reactors (PWRs), M5Framatome11M5 and M5Framatome are trademarks or registered trademarks of Framatome or its affiliates, in the USA or other countries. and Optimized ZIRLO™22Optimized ZIRLO is a trademark or registered trademark of Westinghouse Electric Company LLC, its affiliates and/or its subsidiaries in the United States and may be registered in other countries throughout the world. All rights reserved. Unauthorized use is strictly prohibited. Other names may be trademarks of their respective owners., have been studied using Thermo-Gravimetric Analysis (TGA) technique in the temperature range of 900–1200 °C. A specific test procedure allowing the use of a high steam flow rate and good steam supply to the whole specimen surface, as well as fast heating of the specimen, has been developed. Clean kinetic data, not affected by steam starvation, were obtained on the bare, as-received alloys. For as-received claddings, oxidation kinetics are comparable and close to parabolic for the three alloys at 1100 °C and above. Below 1100 °C, a significant deviation from the parabolic kinetic regime was observed, and M5 Framatome oxidizes slower than Zircaloy-4 and Optimized ZIRLO. Thanks to the fast-heating protocol, the influence of pre-oxidation, simulating corrosion in normal reactor operation, could be investigated, avoiding evolution of the pre-oxidation scale during a slow, long heating phase. Pre-oxidized Zircaloy-4 and M5 Framatome were investigated. A strong protective effect is observed below 1200 °C, while at 1200 °C, the pre-oxidation layer appears to be much less protective, possibly due to the monoclinic to tetragonal zirconia phase transformation.