The structure of ion beam amorphised zirconolite studied by grazing angle X-ray absorption spectroscopy

Ti K edge X-ray absorption spectroscopy (XAS) was applied to determine the Ti co-ordination environment in the surface amorphised layer formed on zirconolite ceramics by 2 MeV Kr+ irradiation, to a fluence of 5 × 1015 ions cm−2. The application of XAS in a grazing angle geometry was demonstrated to be essential in order to probe only the surface damaged layer (<1000 nm thick), in isolation of the undamaged interior of the specimen. 2 MeV Kr+ irradiation induced a change in the Ti co-ordination environment from majority six fold to majority five fold in the amorphised surface layer. This finding is consistent with the formation of five fold Ti in metamict natural zirconolite, as reported previously and confirmed in this study, despite the difference in dose rate of at least 1012 between ion beam irradiated and naturally metamict materials. This study therefore opens the door to systematic investigation of composition – structure – property relations in materials designed for radioactive waste immobilisation, through the combined application of ion beam irradiation and grazing angle XAS.