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Title: Structure and durability of UK simulated high level nuclear waste glasses
Author: Cassingham, Nathan
ISNI:       0000 0004 2744 6176
Awarding Body: University of Sheffield
Current Institution: University of Sheffield
Date of Award: 2013
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The understanding of dissolution of the British nuclear waste glass, as compared to other nuclear waste glasses, is limited. The few studies that have been performed were generally done in static leach tests with the exception of the single pass flow through test performed by Abratis during his PhD, producing a number of papers (Abraitis, P.K., Univ. Manchester, 1999; Abraitis, P.K. et. al., Applied Geochemistry 15 (2000) 1399; Abraitis, P.K. et. al., Mat. Res. Soc. Sym. Pro. 556 (1999) 401). In order to gain further insight to the British nuclear waste glasses X-ray absorption spectroscopy was used along with dissolution studies of British simulated nuclear waste glasses to determine the role of Zn and to ascertain the mechanisms of corrosion. Both baseline glasses along with a Blend simulated nuclear waste glass were studied to give better comparisons with previous results by other authors. The Blend waste glass is composed of a mixture of Magnox reactor waste and thorium oxide reprocessing (ThORP) waste at a wt% of 25wt% Magnox waste and 75 wt% ThORP. Zn K edge X-ray absorption spectroscopy was applied to determine the Zn coordination environment in model inactive UK high level waste (HLW) glasses. Quantitative analysis of the X-ray absorption fine structure (EXAFS) data provided conclusive evidence for the presence of ZnO4 species participating in network formation, linking, on average, to 2 ± 1 SiO4 units via bridging oxygen atoms. Excellent quantitative agreement was observed between the Zn-O contact distance and coordination number determined from EXAFS and previous Molecular Dynamics simulations of glasses with the same nominal composition. Analysis also provided evidence in support of the network forming role of Zn as predicted from Molecular Dynamics simulation, but it was not possible to confirm the predicted clustering of Zn species at high Zn concentration in simple soda lime silica glasses. The single pass flow through (SPFT) work in this study has shown that the steady state dissolution of a base glass with 25 wt% waste loading (MW+25wt%) and a base glass with 30 wt% waste loading (MW+30wt%) of Blend simulated nuclear waste glasses is similar to that of previous studies. The SPFT flow per surface area (Q/S) results are consistent with previous studies. The dissolution rate dependency on temperature and pH of was also consistent with similar glasses. The NRi with respect to B, Si, Na and Al, of the glasses in this study increased with an increase in solution pH. The average activation energy with respect to Si was consistent for a surface controlled reaction with these glasses as was shown in previous studies on MW+Magnox, a similar glass. One of the current designs for a geological repository of HLW is a co-located repository with intermediate level waste (ILW). At long times, there is the possibility of hyper alkaline solution from the ILW repository interacting with the vitrified HLW glass wasteforms. Dissolution studies were performed to understand the mechanisms by which the UK HLW glasses will corrode under hyper alkaline solutions. The addition of an alkali buffer to high purity H2O resulted in a decrease of the dissolution rate for the MW Blend glasses during the product consistency type tests. The concentration of Si in solution for all of the samples suggests that Ca and Si are co-precipitating as was evident from the decrease in Ca concentrations at short times. It is suggested that the presence of Ca in solution forms a passive reactive interface (PRI) which decreases the rate of formation of a hydrated surface layer decreasing the overall dissolution rate. The results from the geochemical modelling of the product consistency type tests showed that Ca and Si are co-precipitating at short times decreasing the normalised mass loss. This is evident from the Ca and Si phases which are most probable to precipitate out of solution as suggested by the geochemical modelling results from PhREEQC In order to understand the mechanisms of alteration layer formation of the UK HLW glasses, vapour hydration tests (VHT) were performed. Results from the time dependant VHT experiments have shown changes in the mechanisms of alteration layer formation with the addition of the simulated Blend waste to the base glasses. It was also shown that iron may be a suppressor to zinc dissolution. Both a Ca and Zn doped Blend waste glass and a base glass doped with Fe Zn and Zr did not show significant layers of zinc in the alteration layer as shown in the Ca and Zn doped base glass in both the reproducibility or time-dependant VHT experiments. Giesler et al. have similar results to the VHT results in this study, which correlate to an interface-coupled dissolution-reprecipitation mechanism when simulated Blend waste is added to the base glasses (Giesler, T. et. al., J. Non-Cryst. Solids 356 (2010) 1458). However, further work needs to be performed in order to prove this second mechanism of waste glasses.
Supervisor: Neil, Hyatt ; Paul, Bingham Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available