Radiation damage effects on the structure and properties of radioactive waste glasses

The performance assessment of glass matrices currently being used in different nuclear energy producing countries to contain and immobilise high-level waste (HLW) waste is crucial for safe and economic disposal. During the first ~500 years of geological disposal fission products will me the main source or radiation and they decay by beta-gamma emission. We studied different borosilicate glasses used in different countries to immobilise HLW, such as Indian glass (NaBaBSi), UK glasses (LiNaBSi), also called MW- Mixture Windscale, UK-CaZn a modified version of MW, French glass (SON68) and a glass proposed by six collaborating nations, called the International Simple Glass (ISG), to see whether / how irradiation defects are dependent on glass composition. Glasses were externally irradiated using a 60Co gamma source to study the effects of beta-gamma radiation (a gamma emitter loses it energy to atomic electrons they then further interact via coulombic interactions); and by He2+ ion implantation to study the effects of alpha particles. A multi-spectroscopic approach was used to characterise glass specimens before and after irradiation. NaBaBSi and LiNaBSi glasses were irradiated using 60Co gamma photons and we found boron-oxygen hole centres (BOHC), electrons trapped at alkali cations or ET centres and peroxy-radicals (PORs) as common defect in these glasses. In addition, E- or polaron centres which may be related to formation of elemental / metallic sodium colloids formed in NaBaBSi glass. Time-dependent thermal annealing of the irradiated glasses revealed that POR’s are the most thermally stable of the defect centres. BOHC and ET centres were common to SON68, ISG and CaZn glasses. In NaBaBSi, LiNaBSi and SON68 glasses loaded with non-active simulated HLW no sharp and intense signals indicative of radiation-induced paramagnetic defect centres was observed. In the study of NaBaBSi and LiNaBSi glasses doped with 0.19. 0.99, and 4.76 mol% Fe2O3 prepared in an oxidising melting environment, electron paramagnetic resonance (EPR) spectroscopy showed that gamma irradiation induced sharp and intense signals exist for only the 0 and 0.19 mol% Fe2O3 doped samples and disappeared for samples containing higher molar concentrations of Fe2O3. It is postulated that, upon gamma irradiation, in LiNaBSi glass Fe2+ is oxidised to Fe3+ by the capture of holes, whereas in NaBaBSi glass Fe3+ is reduced to Fe2+ due to capture of electrons. Further research is needed to understand the reasons behind these different behaviours.