Influence of restart conditions of nuclear power reactor on release of corrosion products and oxidation on alloy 690 steam generator tubes

Steam generator tubes in pressurized water reactors are made of nickel-based alloys. The exchange surface of these tubes represents nearly 75% of the primary circuit. Due to oxidation in primary environment, corrosion products are released into the circuit. The phenomenon of release of corrosion products and their activations in the core of reactor, after neutron flux exposure, are mainly responsible for radioactive contamination of the primary circuit. The limitation of this phenomenon represents one of the major industrial issues to reduce the radiation exposure of maintenance personnel during shutdown. The controlling and modelling of such phenomenon requires a detailed understanding of release kinetics and oxide layers formed. The release and the oxide film formation, on the internal surface of 690 alloy tubes, are strongly impacted by the materials parameters of the tube, as well as by the physico-chemical conditions of the primary water. The objective of this work is to study the impact of thermal and chemical conditions during transient phases of the reactor restart after the replacement of steam generator on the release and on the formation of oxides/hydroxides. Usually, tubes are tested under conditions of nominal primary chemistry at constant high temperature. To be as representative as possible of industrial conditions, this study is carried out on an industrial tube under the conditions characteristic of a reactor restart in an experimental test loop. Fine characterizations of the internal surface of the tube are performed before and after oxidation using several techniques as profilometry, Raman, SEM-EDS, SEM-EBSD, SEM-FIB, TEM, ToF-SIMS. The native oxide layer is formed of a very thin layer (1-2 nm) of oxidized matrix, without specific enrichment. During the restart, the most critical step for the release phenomenon is revealed from 170 deg. C to 297 deg. C. In fact, the majority of the metal is released into the fluid during this step. In addition, isothermal tests, between 25 deg. C and 325 deg. C, have shown that the most significant release is around 250 deg. C. Up to 170 deg. C, a thin layer of amorphous chromium oxide is formed by selective dissolution of iron and nickel. When the temperature rises, this chromium oxide layer is not stable enough to be protective and the diffusion phenomena are activated. At 325 deg. C, the oxide does not exhibit any particular enrichment and corresponds to oxidized metal layer, an equilibrium is established and the rate of release reaches a pseudo-stationary regime. (author)