DOE OSTI2018
Caesium phosphomolybdate (Cs{sub 3}PMo{sub 12}O{sub 40}.xH{sub 2}O, CPM) and zirconium molybdate (ZrMo{sub 2}O{sub 7}(OH){sub 2}.xH{sub 2}O, ZM) are two known fission products that precipitate out within the Highly Active Storage Tanks (HASTs) at Sellafield, potentially causing 'hot-spots' and blocking pipes. Currently, there is not enough behavioural understanding of these compounds present in the Highly Active Liquor (HAL) for effective Post Operational Clean Out (POCO) strategic planning. As the HASTs do not have an in situ monitoring system the behaviour of the HAL cannot be directly observed. Therefore, as with this research, non-radioactive simulants can be utilised to aid behavioural understanding to assist with the planning of future waste management programs. CPM, along with two different morphologies of ZM were characterised and compared to the common oxide particle material titanium dioxide (TiO{sub 2}). The study provides a detailed physical characterisation of the simulants including: particle shape, particle size, water content and crystal structure, along with zeta particle potential, suspension settling and compressive yield stress. CPM was found to be spheroidal in nature with a particle size of 275 nm and an x value of 13 H{sub 2}O which crystallises as a cubic lattice with space group Pn-3m. ZM was found to have a range of morphologies from cuboidal to wheat-sheaf, varying in size from 10 μm to 20 μm, with an x value of between 3 and 4 H{sub 2}O, which crystallise as a body-centred tetragonal lattice with space group I4{sub 1cd}. TiO{sub 2} used as a comparison simulant was found to be spheroidal in shape with particle size of 725 nm. The isoelectric points (IEPs) of the two ZM samples (ZM-A and ZM-B) with different morphologies were found to be pH 2.5, while for TiO{sub 2} it was pH 3.2. For CPM it could not be confidently identified due to its instability within the acidic environment. The settling rates and compressive yield stress of all simulants were tested in both water and 2 M nitric acid, conditions that replicate the HASTs. TiO{sub 2}, ZM-A and ZM-B all found settled faster in acid than in water. For CPM, slightly faster settling in acid was measured. For all samples it was found that as the particle concentration increased the settling rate decreased, which is a result of hindered settling. For compressive yield stress, similar trends were observed for CPM with little variation in its behaviour in acid and water, suggesting that the particles are highly aggregated in both fluids. For ZM samples little change in equilibrium volume fraction was measured with an increase in pressure (both acid and water). However, overall the sediment bed was denser in water, a result of the rapid settling in acid not allowing the non-spherical particles to pack in an ordered manner. It has been highlighted that both CPM and ZM within the acidic conditions of the HASTs, result in unstable and aggregated compounds, which settle quickly to form large open networks. (authors)
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗