Properties of thin anodic oxide films on zirconium alloys

Abstract

Thin (0.1–0.2 μm) anodic oxide films were formed on zirconium, Zircaloy-2 and Zr-2.5 wt% Nb alloy specimens and examined by AC impedance spectroscopy (using both metal and aqueous electrolyte contacts), UV/VIS interferometry, and scanning electron microscopy (SEM). The SEM studies showed that the extent of oxide cracking was a function of the particular alloy and the electrolyte in which the oxide was formed. AC impedance spectroscopy showed that with metallic contacts a Young impedance behaviour was observed as a result of local conduction paths in the oxide film, probably resulting from second phase particles. The extent of cracking in the oxide was identified best from SEM and AC impedance measurements in aqueous electrolytes, and did not appear to contribute to the results obtained with metallic contacts. Large discrepancies between the apparent oxide thicknesses measured from AC impedance data obtained from measurements with aqueous electrolyte and liquid metal contacts, respectively, were shown to result from surface roughness and inadequate wetting by the liquid metals. These discrepancies could be eliminated by using evaporated platinum contacts, which also showed evidence for local conduction in the oxides. UV/VIS interferometry results for the oxide refractive indices and oxide thicknesses gave much scatter because of the small number of fringes available for the analysis and the difficulties in establishing the positions of interference minima with the same accuracy as was possible for interference maxima. The use of this combination of techniques still appears to be the best method for investigating the presence of conducting paths in thick porous oxide films on these alloys. Preference should be given to using evaporated rather than liquid metal contacts when studying such oxides. The advantages of easy removal for the liquid metal contacts often, however, outweigh the errors introduced by surface roughness when using them for repetitive measurements on the same area.