This study investigated the complex settling behaviour of colloidal particles with varied surface charge and shape factors, of specific relevance to nuclear waste processing. Caesium phosphomolybdate (CPM), zirconium molybdate (ZM) and zirconium citromolybdate (ZMCA) were firstly synthesised, producing spheroidal, cubic and rectangular cuboidal morphologies respectively, and compared to agglomerated titania. While zeta-potential measurements indicated all simulant particles attained low isoelectric points, surface group leaching rendered suspensions very acidic, with CPM around its IEP, and ZM/ZMCA stable and positively charged. In sedimentation tests at various concentrations in water and 2 M HNO3, CPM and titania were found to settle with extremely high hindered settling exponents, consistent with aggregated structures. Exponents for ZM and ZMCA in water were both also well above values for spherical particles; however, this was assumed to be due to heightened drag effects from relative shape factors, rather than aggregation. ZMCA in particular showed a very high exponent of ~11.4, due to the propensity for the rod-like particles to settle in a flat conformation. For ZM in acid, double layer compression from the high electrolyte aggregated the dispersions, correlating to a significant increase in the settling exponent. An extended Stokes relationship was additionally used to understand theoretical limits of shape and aggregation on particle size prediction from hindered settling curves. Importantly, calculated sizes were consistent for the stable ZM and ZMCA in water, despite their non-sphericity and enhanced drag. The relationship failed however with agglomerated suspensions, highlighting its application as a general stability test for sedimenting dispersions.
This study investigated dispersions analogous to highly active nuclear waste, formed from the reprocessing of Spent Nuclear Fuel (SNF). Non-radioactive simulants of spheroidal caesium phosphomolybdate (CPM) and cuboidal zirconium molybdate (ZM-a) were successfully synthesised; confirmed via Scanning Electron Microscopy (SEM), powder X-ray diffraction (PXRD) and Fourier transform infrared (FTIR) spectroscopy. In addition, a supplied ZM (ZM-b) with a rod-like/wheatsheaf morphology was also analysed along with titanium dioxide (TiO2). The simulants underwent thermal gravimetric analysis (TGA) and size analysis, where CPM was found to have a D50 value of 300 nm and a chemical formula of Cs3PMo12O40·13H2O, ZM-a a D50 value of 10 μm and a chemical formula of ZrMo2O7(OH)2·3H2O and ZM-b to have a D50 value of 14 μm and a chemical formula of ZrMo2O7(OH)2·4H2O. The synthesis of CPM was tracked via Ultraviolet-visible (UV-Vis) spectroscopy at both 25 °C and 50 °C, where the reaction was found to be first order with the rate constant highly temperature dependent. The morphology change from spheroidal CPM to cuboidal ZM-a was tracked via SEM, reporting to take 10 days. For the onward processing and immobilisation of these waste dispersions, centrifugal analysis was utilised to understand their settling behaviours, in both aqueous and 2 M nitric acid environments (mimicking current storage conditions). Spheroidal CPM was present in both conditions as agglomerated clusters, with relatively high settling rates. Conversely, the ZM were found to be stable in water, where their settling rate exponents were related to the morphology. In acid, the high effective electrolyte resulted in agglomeration and faster sedimentation.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.