Transmission Electron Microscopy Examinations of Metal-Oxide Interface of Zirconium-Based Alloys Irradiated in Halden Reactor-IFA-638

This paper provides the results of investigations by transmission electron microscopy (TEM) on the selected materials from in-reactor oxidation tests in the Halden test reactor (Reference No. IFA-638) from 1998 to 2006. The objective of the IFA-638 test was to study the corrosion behavior of modern zirconium-based claddings to high burnup in pressurized water reactor water chemistry and thermal hydraulic conditions. The aim of this paper is to report on the microstructure of selected materials (ZIRLO (R), E635, and Alloy A) after the irradiation to different burnup levels to determine the modifications induced by irradiation and to correlate results to their oxidation behavior. The TEM examinations revealed the nature of secondary phase particles (SPPs) and their modification under irradiation. Four types of SPPs were observed, namely beta-niobium precipitates, Zr0.5Nb0.3Fe0.(2) (mainly in the ZIRLO alloy), Zr(Fe,Nb)(2) (in E635), and (Cr,Fe)(2)Zr,Nb with varying niobium content (present in Alloy A: Zr-0.58Sn-0.31Nb-0.36Fe-0.26Cr). TEM observations showed that all three materials contained still several precipitates after irradiation and in the case of the ZIRLO alloy even after high burnups. Furthermore, the analysis of the metal side of the interface and its comparison with the oxide side led to the conclusion that all types of precipitates dissolved to some extent under irradiation and that their alloying element content decreased. The dissolution was intensified in the oxide. However, a more detailed examination showed that the beta-niobium precipitates dissolved at a slower rate, or knowing that their composition was much richer in niobium, the time needed for the precipitates to become fully depleted from niobium was longer. Regarding the amorphization under irradiation, the beta-niobium- and chromium-containing precipitates did not amorphize in the metal part of the interface. This was not the case for the other types of precipitates. Furthermore, these two types of SPP both showed delayed oxidation and due to this behavior the typical crack above the SPP in the oxide was also observed. These results are discussed to gain an improved understanding of the oxidation behavior of materials studied as a function of irradiation and residence time.