The local chemistry of technetium-99 (99Tc) in oxide glasses is important for understanding the incorporation and long-term release of Tc from nuclear waste glasses, both those for legacy defense wastes and fuel reprocessing wastes. Tc preferably forms Tc(VII), Tc(IV), or Tc(0) in glass, depending on the level of reduction of the melt. Tc(VII) in oxide glasses is normally assumed to be isolated pertechnetate TcO4- anions surrounded by alkali, but can occasionally precipitate as alkali pertechnetate salts such as KTcO4 and NaTcO4 when Tc concentration is high. In these cases, Tc(VII) is 4-coordinated by oxygen. A reinvestigation of the chemistry of alkali-technetium-oxides formed under oxidizing conditions and at temperatures used to prepare nuclear waste glasses showed that higher coordinated alkali Tc(VII) oxide species had been reported, including those with the TcO5- and TcO6- anions. The chemistry of alkali Tc(VII) and other alkali-Tc-oxides is reviewed, along with relevant synthesis conditions.

Additionally, we report attempts to make 5- and 6-coordinate pertechnetate compounds of K, Na, and Li, i.e. TcO5- and TcO6-. It was found that higher coordinated species are very sensitive to water, and easily decompose into their respective pertechnetates. It was difficult to obtain pure compounds, but mixtures of the pertechnetate and other phase(s) were frequently found, as evidenced by x-ray absorption spectroscopy (XAS), neutron diffraction (ND), and Raman spectroscopy. Low temperature electron paramagnetic resonance (EPR) measurements showed the possibility of Tc(IV) and Tc(VI) in Na3TcO5 and Na5TcO6 compounds.

It was hypothesized that the smaller counter cation would result in more stable pertechnetates. To confirm the synthesis method, LiReO4 and Li5ReO6 were prepared, and their Raman spectra match those in the literature. Subsequently, the Tc versions LiTcO4 and Li5TcO6 were synthesized and characterized by ND, Raman spectroscopy, XANES, and EXAFS. The Li5TcO6 was a marginally stable compound that appears to have the same structure as that known for Li5ReO6. Implications of the experimental work on stability of alkali technetate compounds and possible role in the volatilization of Tc are discussed.

Cement has been considered as a possible material present in the Deep Geological Disposal (DGD) [1] . In order to determine the effect of cementitious waters on the oxidation of the surface of Spent Fuel (SF), a series of electrochemical experiments were performed, to study the influence of two main components of cementitious water: calcium and silicate.

Test solutions with Na2SiO3 and/or CaCl2 were prepared at pH 12 and NaCl 0.1 mol·dm-3 as ionic medium. A 3 at.% doped SIMFUEL was used to perform cyclic voltammetric (CV), potentiostatic and corrosion potential (ECORR) experiments. After potentiostatic and ECORR experiments, the SIMFUEL surface was analyzed using X-Ray Photoelecton Spectroscopy (XPS).

The results showed that the presence of silicate decreased the SIMFUEL oxidation between -100 mV and 300 mV. When Ca2+ was added, the whole oxidation process was shifted to higher potentials which indicated a protective effect of the combination of Ca2+ and SiO32- . The XPS results obtained after potentiostatic experiments at 200 mV showed that the presence of silicate partially suppressed the oxidation of SIMFUEL, as indicated by the contribution of both U(IV) and U(V) XPS to the U 4f7/2 band (∼ 38%). After the addition of calcium, the predominant uranium oxidized state contribution on the surface was U(V) (40%). After the ECORR experiments, the ECORR values were similar either with or without silicate in solution (-80 mV and -70 mV respectively). The resulting surface also exhibited a similar composition. When calcium was added to the electrolyte, the ECORR value was suppressed to -105 mV, and XPS showed that the surface was less oxidized than with the other two electrolytes.

Crystallization of aluminosilicates during the conversion of Hanford high-level waste (HLW) to glass is a function of the composition of the glass-forming melt. In high-sodium, high-aluminum waste streams, the crystallization of nepheline (NaAlSiO4) removes chemically durable glass-formers from the melt, leaving behind a residual melt that is enriched in less durable components, such as sodium and boron. We seek to further understand the effect of lithium, boron, and iron addition on the crystallization of model silicate glasses as analogues for the complex waste glass. Boron and iron behave as glass intermediates which allow for crystallization when present in low additions but frustrate crystallization in high additions. In this work, we seek to compare the average structures of quenched and heat treated glasses through Raman spectroscopy, X-ray diffraction, vibrating sample magnetometry, and X-ray pair distribution function analysis. The endmembers of this study are feldspathoid-like (LiAlSiO4, NaAlSiO4, NaBSiO4, and NaFeSiO4), pyroxene-like (LiAlSi2O6, NaAlSi2O6, NaBSi2O6, and NaFeSi2O6), and feldspar-like (LiAlSi3O8, NaAlSi3O8, NaBSi3O8, and NaFeSi3O8). Such a comparison will provide further insight on the complex relationship between the average chemical ordering and topology of glass on crystallization.

Due to their high actinide content MOX residues require immobilization within a robust host matrix. Although it is possible to immobilize actinides in vitreous wasteforms; ceramic phases, such as brannerite (UTi2O6), are attractive due to their high waste loading capacity and relative insolubility. Brannerites Gd0.1U0.9Ti2O6, Ce0.1U0.9Ti2O6 and Gd0.1U0.81Ce0.09Ti2O6 were prepared using an oxide route. Charge compensation of trivalent cations was expected to occur via the oxidation of U (IV) to higher valence states (U (V) or U (VI)). Gd was added to act as a neutron absorber in the final Pu bearing wasteform and Ce was used as a structural surrogate for Pu. X-ray absorption spectroscopy showed that Ce (IV) was reduced to Ce (III) in all cases. X-ray powder diffraction of synthesized specimens found that the final phase assemblage was strongly affected by processing atmosphere (air or argon). Prototypical brannerite was formed in all compositions, secondary phases observed were found to vary according to processing atmosphere and stoichiometry. Microstructural analysis (SEM) of the sintered samples confirmed the results of the X-ray powder diffraction.

In the context of management of the wastes arising from the reprocessing of spent nuclear fuel, studies have been conducted into the solvent extraction kinetics of lanthanide fission products by TODGA and the effects of solvent phase acidity on the effectiveness of this organic extractant molecule. In this study we observe an increase in organic phase viscosity increasing acidity and, potentially by consequence, that the rate of cerium extraction is summarily decreased.

Glassy materials for HLW immobilization were produced from HLW surrogate, quartz sand, datolite (CaBSiO4OH), and bentonite clay at a temperature of up to 1200 °C. Waste loading (WL) ranged between 20 and 40 wt.%. The glasses were characterized by X-ray diffraction, scanning electron microscopy and Fourier-Transform infrared spectroscopy. Glasses with waste loading of up to 35 wt.% obtained by melt pouring onto a metal plate were found to be rather homogeneous but contained minor noble metal oxides and britholite (at high waste loadings) while those annealed in turned-off furnace were partly devitrified. Average chemical composition of britholite corresponded to formula Na1.00Ca4.02Y0.33Ce0.05Nd3.64Gd0.17Si6.79O24.39. The glass network is built from SiO4 units with one or two bridging oxygens and complex borate groups with primarily ternary coordinated boron. Increase of waste loading resulted in shift of band’s maxima to lower wavenumbers exhibiting increasing the fraction of SiO4 unit with lower number of bridging oxygen ions and thus reduction of glass network connectedness. Glasses with up to 30 wt.% waste loading kept their high hydrolytic durability making them suitable for HLW immobilization.

Monitoring and understanding of corrosion on nuclear sites is key to safe asset management (predicting plant life, assessing efficacy of corrosion inhibitors for plant lifetime extension) and supporting informed choice of decontamination methods for steels due for decommissioning. Recent advances in Quartz Crystal Nanobalance (QCN) technology offer a means to monitor corrosion in-situ in radiologically harsh environments, in real time and with high sensitivity.

Oxalic acid has been widely used in nuclear facilities as a corrosion inhibitor for carbon steels and as a decontamination cleaning agent due to its ability to remove rust from the surface of ferritic metals and alloys. As an exemplar system for decontamination, the corrosion behavior of pure iron samples in 1 wt% oxalic acid solution has, for the first time, been measured in simulated radioactive environments in real time, in situ using the QCN. Results show that the QCN is a promising tool for studying the efficacy of oxalic acid decontamination agent formulations with the sensor providing useful mechanistic information regarding decontaminating agent mode-of-action derived from the mass change (gain or loss) in real time when a quartz crystal is immersed in oxalic acid solution in simulated and non–simulated radioactive environments.