Study of hydrogen migration produced during the corrosion of PWR reactors fuel cans in zircaloy 4 and zirconia

The corrosion of Zircaloy-4-claddings by water from the primary circuit of nuclear power plant goes hand in hand with the release of hydrogen which penetrates the oxide and then the metal. This work focuses on the mechanisms of hydrogen transport in oxide and in metal. Hydrogen transport in oxide is studied on the basis of corrosion tests performed in the autoclave at 360 deg C. These tests are performed on Zircaloy-4 claddings under different chemical conditions (pure water, and pure water with lithium hydroxide). The distribution of hydrogen in oxide film is measured by SIMS. Hydrogen profiles in the oxide are dependent on the oxide microstructure and vary with oxidation time. These observations are confirmed by experiments in which some samples, previously oxidized in the autoclave, are immersed in heavy water. In the oxide layer, two zones are observed: one external porous zone and one internal dense zone. Deuterium diffusion coefficients in dense oxide are determined using SIMS profiles and Fischer diffusion model. Hydrogen transport in metal is also studied by means of gas-phase permeation experiments. These are set up at different temperature (400-500 deg. C) and under different hydrogen pressures and make it possible to determine the hydrogen diffusion coefficients in a Zircaloy-4 cladding under experimental conditions. All these results lead us to discuss of hydrogen transport evolution in cladding during oxidation. A model taking into account hydrogen transport in oxide and in metal, and the hydrides precipitations is proposed. (author)