Assessment of glass dissolution kinetics, under disposal relevant temperature and pH environments, is required to credibly estimate radionuclide release rates from vitrified radioactive waste. Leaching of the International Simple Glass (ISG) under acidic to hyperalkaline conditions was examined. Forward rate measurements have been obtained using the dynamic leaching SPFT protocol and rate parameters for B, Na and Si in the basic regime; errors in rates predicted using these parameters at high pH and temperature are significant because the fitting uses logarithmic data. Longer term behaviour under hyperalkaline conditions, representative of some disposal environments, was investigated using the PCT and MCC-1 static leaching protocols with Ca(OH)2 solutions for up to 120 days (PCT) and 720 days (MCC-1). In hyperalkaline conditions dissolution was incongruent for all elements and the presence of alternating zirconia-rich and zirconia-poor alteration layers was observed on all leached monoliths, indicating the occurrence of a self-organisation phenomenon during leaching.

For energy saving and CO2 emissions reduction, in addition to extending the range of suitable raw material sources for glass manufacture, compositional reformulation, and alternative raw materials have been studied in the context of industrial container and float‐type soda‐lime‐silica (SLS) glasses. Lithium, potassium, and boron were applied to modify benchmark glass compositions. Reformulation impacts on key glass properties including the viscosity‐temperature relationship, thermal expansion, liquidus temperature, forming behavior and color. Compared to the benchmark glass, representative of commercial SLS glasses, melting temperatures (taken as temperatures corresponding to log (viscosity/dPa·s) = 2) of reformulated glasses are reduced by 11°C‐55°C. Investigation of four industrial by‐products (seashell waste, eggshell waste, biomass ash, and rice husk ash), and their potential suitability as alternative glass batch raw materials, was also conducted. Seashell waste and biomass ash were successfully introduced into representative green glass formulations.

The structure and dissolution behaviour of Na 2 O•CaO•(15-x)Al 2 O 3 •xB 2 O 3 •SiO 2 and Na 2 O•MgO•(15x)Al 2 O 3 •xB 2 O 3 •SiO 2 glasses, relevant to compositions of UK nuclear waste glass, have been investigated using nuclear magnetic resonance (NMR) spectroscopy and static dissolution experiments using the PCT protocol. Structural data from 11 B, 27 Al and 29 Si NMR analyses show that increasing the Increasing the [B 2 O 3 ]/([Al 2 O 3 ]+[B 2 O 3 ]) ratio of the alkali-alkaline-earth aluminoborosilicate glasses led to an overall decrease in the proportion of non-silicate tetrahedral species (IV Al + IV B) and a decrease in Si-OX bonds (X = B, Al). The Mg-containing glasses exhibited lower IV B fractions than their Ca-containing counterparts, which is thought to be due to the presence of IV Mg tetrahedra in the network. The measured corrosion rates were similar for both Ca and Mgcontaining glasses although unexpectedly some Ca-containing glasses exhibited higher corrosion losses than the Mg-containing ones for time periods up to 112 d. However, there was evidence of a greater tendency to rate resumption in the Mg containing than the Ca containing ones. Alteration products were found to contain Ca, Si and Al with the Ca containing glasses and Ca, Mg, Si and Al with the Mg containing glasses; Na was not detected in the alteration products although its presence cannot be ruled out based on the data obtained.

The first comprehensive assessment of the dissolution kinetics of simulant Magnox–ThORP blended UK high-level waste glass, obtained by performing a range of single-pass flow-through experiments, is reported here. Inherent forward rates of glass dissolution were determined over a temperature range of 23 to 70°C and an alkaline pH range of 8.0 to 12.0. Linear regression techniques were applied to the TST kinetic rate law to obtain fundamental parameters necessary to model the dissolution kinetics of UK high-level waste glass (the activation energy (Ea), pH power law coefficient (η) and the intrinsic rate constant (k0)), which is of importance to the post-closure safety case for the geological disposal of vitreous products. The activation energies based on B release ranged from 55 ± 3 to 83 ± 9 kJ mol–1, indicating that Magnox–THORP blend glass dissolution has a surface-controlled mechanism, similar to that of other high-level waste simulant glass compositions such as the French SON68 and LAW in the US. Forward dissolution rates, based on Si, B and Na release, suggested that the dissolution mechanism under dilute conditions, and pH and temperature ranges of this study, was not sensitive to composition as defined by HLW-incorporation rate.

Reproducible preparation of lithium tetraborate fused beads for XRF analysis of glass and mineral samples is of paramount importance for analytical repeatability. However, as with all glass melting processes, losses due to volatilisation must be taken into account and their effects are not negligible. Here the effects of fused bead melting time have been studied for four Certified Reference Materials (CRM’s: three feldspars, one silicate glass), in terms of their effects on analytical variability and volatilisation losses arising from fused bead preparation. At melting temperatures of 1065 °C, and for feldspar samples, fused bead melting times shorter than approximately 25 min generally gave rise to a greater deviation of the XRF-analysed composition from the certified composition. This variation might be due to incomplete fusion and/or fused bead inhomogeneity but further research is needed. In contrast, the shortest fused bead melting time for the silicate glass CRM gave an XRF-analysed composition closer to the certified values than longer melting times. This may suggest a faster rate of glass-in-glass dissolution and homogenization during fused bead preparation. For all samples, longer melting times gave rise to greater volatilisation losses (including sulphates and halides) during fusion. This was demonstrated by a linear relationship between SO3 mass loss and time1/2, as predicted by a simple diffusion-based model. Iodine volatilisation displays a more complex relationship, suggestive of diffusion plus additional mechanisms. This conclusion may have implications for vitrification of iodine-bearing radioactive wastes. Our research demonstrates that the nature of the sample material impacts on the most appropriate fusion times. For feldspars no less than ~25 min and no more than ~60 min of fusion at 1065 °C, using Li2B4O7 as the fusion medium and in the context of feldspar samples and the automatic fusion equipment used here, strikes an acceptable (albeit non-ideal) balance between the competing factors of fused bead quality, analytical consistency and mitigating volatilisation losses. Conversely, for the silicate glass sample, shorter fusion times of less than ~30 min under the same conditions provided more accurate analyses whilst limiting volatile losses.