Thermodynamic assessment of the pseudoternary Na2O–Al2O3–SiO2 system

Vitrified high‐level radioactive waste that contains high concentrations of Na₂O and Al₂O₃, such as the waste stored at the Hanford site, can cause nepheline to precipitate in the glass upon cooling in the canisters. Nepheline formation removes oxides such as Al₂O₃ and SiO₂ from the host glass, which can reduce its chemical durability. Uncertainty in the extent of precipitated nepheline necessitates operating at an enhanced waste loading margin, which increases operational costs by extending the vitrification mission as well as increasing waste storage requirements. A thermodynamic evaluation of the Na₂O–Al₂O₃–SiO₂ system that forms nepheline was conducted by utilizing the compound energy formalism and ionic liquid model to represent the solid solution and liquid phases, respectively. These were optimized with experimental data and used to extrapolate phase boundaries into regions of temperature and composition where measurements are unavailable. The intent is to import the determined Gibbs energies into a phase field model to more accurately predict nepheline phase formation and morphology evolution in waste glasses to allow for the design of formulations with maximum loading.     

Corrosion of Borosilicate Glasses Subjected to Aggressive Test Conditions: Structural Investigations

Sodium borosilicate (NBS) and barium sodium borosilicate (BBS) glasses, used for immobilization of high‐level nuclear waste with compositions (SiO₂)_0.477(B₂O₃)_0.239(Na₂O)_0.170(TiO₂)_0.023(CaO)_0.068(Al₂O₃)_0.023 and (SiO₂)_0.482(B₂O₃)_0.244(Na₂O)_0.220(BaO)_0.054 were subjected leaching experiments under hydrothermal conditions in an autoclave at 200°C for different time durations. Morphological and structural transformations associated with leaching, have been monitored with techniques like XRD, SEM, solid‐state nuclear magnetic resonance. XRD and SEM along with NMR studies have confirmed that, upon leaching, formation of an aluminosilicate phase, Zeolite‐P (Na₆Al₆Si₁₀O₃₂·12H₂O), occurs with NBS glass. BBS glass upon subjecting to the same conditions leads to formation of multiple amorphous phases having Q⁴ (silica rich phase) and Q³ structural units of Silicon along with structurally modified residual glass. Upon leaching BO₃ structural units preferentially get released from BBS glass. Comparison of results with international simple glass confirmed that, for the latter, mass loss rates are one order of magnitude lower.     

Borate melt structure: Temperature‐dependent B–O bond lengths and coordination numbers from high‐energy X‐ray diffraction

Borate melts containing <20 mol% Na₂O have been studied using high‐energy synchrotron X‐ray diffraction. Temperature dependencies of the mean B–O bond lengths are shown to vary strongly with soda content, by comparison to previous measurements on liquid B₂O₃ and Na₂B₄O₇. Whereas in liquid B₂O₃ linear thermal expansion of the BØ₃ units is observed, with coefficient α_BO = 3.7(2) × 10^?6 K^?1, this expansion is apparently slightly suppressed in melts containing <20 mol% Na₂O, and is dramatically reversed at the diborate composition. These effects are interpreted in terms of changes in the mean B–O coordination number, where the reaction BØ₄^? + BØ₃ ? BØ₃ + BØ₂O^? shifts to the right with increasing temperature. The empirical bond‐valence relationship is used to convert measured bond lengths, r_BO, to coordination numbers, n_BO, including a correction for the expected thermal expansion. This method is more accurate and precise than direct determination of n_BO from peak areas in the radial distribution functions. Gradients of Δn_BO/ΔT = ?3.4(3) × 10^?4 K^?1 close to the diborate composition, and Δn_BO/ΔT = ?0.3(1) × 10^?4 K^?1 for a 13(3) mol% Na₂O melt are observed, in reasonable agreement with Raman spectroscopic observations and thermodynamic modeling, with some quantitative differences. These observations go toward explaining isothermal viscosity maxima and changes in fragility across the sodium borate system.     

Formation of Technetium Salts in Hanford Low‐Activity Waste Glass

The distribution and physical form of technetium in a Hanford low‐activity waste (LAW) glass was examined with scanning electron microscopy (SEM) and X‐ray diffraction (XRD). A simulated Hanford LAW glass was spiked with varying amounts of potassium pertechnetate and melted at 1000°C. The glass was melted in a sealed quartz ampoule with the air pumped out, so that volatile material could leave the glass but would not be lost from the system. Previous studies have shown that technetium remains in the glass up to about 2000 ppm, but rises to the top of the melt as a separate salt phase above this concentration. Examination by SEM shows that crystals of technetium compounds appear to grow out of the hot glass, which implies that the hot glass was supersaturated in technetium salts. Some of the technetium compound crystals had apparently melted, but other crystals had obviously not melted and must have formed after the glass had partially cooled. The technetium compounds in the salt layer are KTcO₄ and NaTcO₄, according to SEM and XRD. No TcO₂ was found in the salt phase, even though Tc(IV) has been previously reported in the glass.     

Generalized Titanate Ceramic Waste Form for Advanced Purex Reprocessing

Alternative dissolution processes for spent nuclear fuel lead to highly active waste streams rich in zirconium, iron, chromium, and nickel at levels that vary with fuel assembly design. A titanate ceramic phase assemblage has been developed with the flexibility to accommodate these variations in waste stream composition. Waste loadings range from 42 to 50 wt%. Leach rates are comparable to those from Synroc C.     

Thermodynamic Solubility Constant of Ca(OH)2 in Simulated Radioactive Sulfate Liquid Waste

The thermodynamic solubility product constant ( K _sp) of Ca(OH)₂ in simulated radioactive sulfate liquid waste was experimentally determined at temperatures of 25° and 40°C. Synthetic solutions were prepared with pH ranging from 12.6 to >14 and ionic strength ranging from 0.25 M to 3.7 M . All the solutions were saturated in CaO and contained Na₂SO₄ to simulate the salts accompanying radioactive liquid waste. The Bromley model was applied to estimate the global ionic activity coefficients, and the K _sp value was compared with those found in the literature. The stability ranges of the different compounds formed as a function of pH were determined by X-ray diffractometry analysis, and their quantification was conducted by thermal analysis.     

Foam Fractionation and Precipitate Flotation of Zinc(II)

Abstract

The hydrolytic behavior of a metal can be related to its removal by foaming. In this study the effect of pH and ionic strength on the foam separation of 0.1 mM zinc (II) was investigated using different concentrations of sodium lauryl sulfate as the collector. At low pH Zn²⁺ ion was removed by foam fractionation while above pH 8 Zn(OH)²(s) was removed by precipitate flotation. The results demonstrate that precipitate flotation is a more efficient removal process than the foam separation of soluble metal species.     

Processing Impurities as Phase Assemblage Modifiers in Titanate Nuclear Waste Ceramics

The tolerance of titanate nuclear waste ceramics to fluctuations in the concentrations of processing contaminants was monitored using X-ray diffraction, electron microscopy, secondary ion mass spectrometry, and analysis of dissolution liquors. Several waste forms were fabricated, all of which contained idealized Purex waste simulant and, in addition, varying quantities of the common waste stream impurities P₂O₅, MgO, Fe₂O₃, Na₂O, and SiO₂. Incorporation of the oxides individually stabilized new phases including monazite (P₂O₅), pseudobrookite (MgO), loveringite (Fe₂O₃), freudenbergite (Na₂O), and pollucite (SiO₂)—only the latter phase deleteriously affected waste form performance by promoting cesium dissolution. However, when the processing contaminants were added simultaneously, a number of synergetic effects, particularly the stabilization of a soluble glassy phase, resulted in elemental losses which were an order of magnitude greater for some matrix and radwaste species. It was found that up to 25 wt% of the idealized Purex waste could be incorporated in the waste without diminution of its properties.     

Patent abstracts

This paper gives an overview of the feasibility of the application of biotechnology to nuclear waste treatment. The contents are based on a report which PA Technology carried out for the Department of the Environment (DoE Reference: DoE/RW/88.008 Sector No 2.3). Many living and dead organisms accumulate heavy metals and radionuclides. The controlled use of this phenomenon forms the basis for the application of biotechnology to the removal of radionuclides from nuclear waste streams. Indeed, biotechnology offers a series of new opportunities for removal of radionuclides from dilute aqueous process effluents. Such technology is already used for heavy metal removal on a commercial basis and could be optimised for radionuclide removal. An overview of biotechnology areas, namely the use of biopolymers and biosorption using biomass applicable to the removal of radionuclides from industrial nuclear effluents is given. The potential of biomagnetic separation technology, genetic engineering and monoclonal antibody technology is also to be examined. The most appropriate technologies to develop for radionuclide removal in the short term appear to be those based on biosorption of radionuclides by biomass and the use of modified and unmodified biopolymers in the medium term.     

Interdependence of Phase Chemistry, Microstructure, and Oxygen Fugacity in Titanate Nuclear Waste Ceramics

Titanate ceramic waste forms were prepared using several combinations of calcination atmosphere (N₂, N₂-3.5% H₂, H₂) and metallic redox buffers (Ni, Fe, Ti, Al) to examine the dependence of microstructure and durability upon oxygen activity. It was found that the microstructures and phase assemblages were mostly insensitive to the fabrication method, although in detail systematic changes were recognized. The correlation of aqueous durability with oxygen fugacity was not straightforward, because of density variations in the hot-pressed ceramics. These fluctuations in density dominated the dissolution characteristics of the waste forms and sometimes obscured the more subtle changes associated with redox potential. It is concluded that although the best durability is achieved at lower fugacities (i.e., Ti metal buffer and H₂ calcination atmosphere), a satisfactory product can be produced using any of the preparative routes examined, provided the material is completely densified.