Synthesis and characterization of iodovanadinite using PdI2, an iodine source for the immobilisation of radioiodine

Abstract

The synthesis of a palladium-containing iodovanadinite derivative, hypothetically “PdPb₉(VO₄)₆I₂”, was attempted using PdI₂ as a source of iodine in searching for a novel waste form for radioiodine. Stoichiometric amounts of Pb₃(VO₄)₂ and PdI₂ 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 PdI₂ can function as a sacrificial iodine source for the formation of iodovanadinite, prototypically Pb₁₀(VO₄)₆I₂, however, the incorporation of Pd into this phase was not definitively observed. The sacrificial reaction mechanism involved the decomposition of PdI₂ to Pd metal and nascent I₂, with the latter incorporated into the iodovanadinite Pb₁₀(VO₄)₆I₂ 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 PdI₂ from nuclear fuel reprocessing, in a composite wasteform in which I-129 is immobilised within a durable iodovandinite ceramic, encapsulating Pd metal.