Radiation Effects on the Performance of Advanced Sulfur Monochloride Chlorination Processes

Abstract

Advanced sulfur chloride-based chlorination technologies are being developed to enable efficient recycling of aluminum and zirconium-based materials used in the nuclear industry. However, the impacts of ionizing radiation on the performance of these sulfur chloride compounds are not well established, despite this being critical knowledge for assessing their feasibility and longevity under envisioned process conditions. In the present article, we report on the effects of cobalt-60 gamma irradiation (≤5 MGy) on the aluminum alloy 6061 (AA6061-T6) chlorination yield in sulfur monochloride (S₂Cl₂). Our findings indicate that, compared to nonirradiated solvent, radiation-induced changes in the chemical composition of S₂Cl₂─identified using Raman spectroscopy─afford an additional, dose-dependent exothermic process prior to the chlorination reaction’s typical thermodynamic behavior. We attribute this new process to reactions involving aluminum species (metal, oxide, or [oxy]hydroxides) and sulfur dichloride (SCl₂), an S₂Cl₂ radiolysis product that accumulates with absorbed gamma dose, but is absent following an AA6061-T6 chlorination study. Despite the exothermicity of this new process, the overall yield of chlorination decreased with increasing preirradiation dose. Consequently, the chemical reactivity, specificity (aluminum metal vs aluminum passivation and corrosion layer constituents), and byproducts of SCl₂ must be more thoroughly evaluated to support the continued development of advanced S₂Cl₂ chlorination technologies.