Abstract
The synthesis of a palladium-containing iodovanadinite derivative, hypothetically "PdPb(9)(VO(4))(6)I(2)", was attempted using PdI(2) as a source of iodine in searching for a novel waste form for radioiodine. Stoichiometric amounts of Pb(3)(VO(4))(2) and PdI(2) were batched and reacted at elevated temperatures in sealed vessels. Batched material was also subjected to high-energy ball-milling (HEBM) in order to reduce reaction time and the potential for iodine volatilization during subsequent reaction at 200-500 °C. The resulting products were characterized using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, IR spectroscopy, thermal analysis and Pd K XANES. Results showed that PdI(2) can function as a sacrificial iodine source for the formation of iodovanadinite, prototypically Pb(10)(VO(4))(6)I(2), however, the incorporation of Pd into this phase was not definitively observed. The sacrificial reaction mechanism involved the decomposition of PdI(2) to Pd metal and nascent I(2), with the latter incorporated into the iodovanadinite Pb(10)(VO(4))(6)I(2) phase. In comparison to processing using standard solid state reaction techniques, the use of HEBM prior to high temperature reaction generates a more homogeneous end-product with better iodine retention for this system. Overall, the key novelty and importance of this work is in demonstrating a method for direct immobilisation of undissolved PdI(2) from nuclear fuel reprocessing, in a composite wasteform in which I-129 is immobilised within a durable iodovandinite ceramic, encapsulating Pd metal.