Oxide characteristics and their relationship to hydrogen uptake in zirconium alloys

This paper reports on secondary ion mass spectrometry (SIMS) and transmission electron microscopy (TEM) that have been used to investigate composition and structure of oxides on pure zirconium and Zr-2.5Nb following both in and out-reactor exposures in aqueous and gaseous environments. Thin oxides formed in steam at 400 degrees C on Zr-2.5Nb act as excellent hydrogen permeation barriers for CANadian Deuterium Uranium (CANDU) pressure tubes. Following up to 4350 effective full power days (EFPD) exposure in-reactor in the annulus gas, and out-reactor elevated exposures to deuterium gas, these oxides generally continue to show diffusional-type through-thickness deuterium concentration profiles, with negligible deuterium contents at the metal/oxide interface. Diffusion coefficients inferred from these profiles are as low as ∼2 x 10-22 m2/s at 300 degrees C. The structure of these thin oxides on Zr-2.5Nb consists of columnar grains with amorphous regions at grain boundaries and at the metal/oxide interface, and non-interconnected porosity, which implies that deuterium permeation is likely controlled by solid state diffusion through the bulk oxide. At regions containing relatively high deuterium contents in the bulk metal of removed pressure tubes, outside surface oxides showed several regions with flat deuterium concentration profiles with higher deuterium concentrations at the metal/oxide interface