Toward Understanding the Effect of Low‐Activity Waste Glass Composition on Sulfur Solubility

The concentration of sulfur in Hanford low‐activity waste (LAW) glass melter feed will be maintained below the point where the salt accumulates on the melt surface. The allowable concentrations may range from near zero to over 2.05 wt% (of SO₃ on a calcined oxide basis) depending on the composition of the melter feed and processing conditions. If the amount of sulfur exceeds the melt tolerance level, a molten salt will accumulate which may upset melter operations and potentially shorten the useful life of the melter. At the Hanford site, relatively conservative limits have traditionally been placed on sulfur loading in melter feed, which in turn significantly increases the amount of LAW glass that will be produced. Crucible‐scale sulfur solubility data and scaled melter sulfur tolerance data have been collected on simulated Hanford waste glasses over the last 15 years. These data were compiled and analyzed. An empirical model was developed to predict the solubility of SO₃ in glass based on 253 simulated Hanford LAW glass compositions. This model represents the data well, accounting for over 85% of the variation in data, and was well validated. The model was also found to accurately predict the maximum amount of sulfur in melter feed that did not form a salt layer in 13 scaled melter tests of simulated LAW glasses. The model can be used to help estimate glass volumes and make informed decisions on process options (e.g., scale of supplemental LAW treatment facility, and pretreatment facility performance requirements). The model also gives quantitative estimates of component concentration effects on sulfur solubility. The components that increase sulfur solubility most are Li₂O > V₂O₅ > CaO ≈ P₂O₅ > Na₂O ≈ B₂O₃ > K₂O. The components that decrease sulfur solubility most are Cl > Cr₂O₃ > Al₂O₃ > ZrO₂ ≈ SnO₂ > Others (i.e., the sum of minor components) ≈SiO₂. The order of component effects is similar to previous literature data, in most cases.     

Pyrochlore glass-ceramics fabricated via both sintering and hot isostatic pressing for minor actinide immobilization

Pyrochlore glass-ceramics (GCs) have been investigated with samples fabricated via both sintering and hot isostatic pressing (HIPing) of a mixed oxide precursor. It has been demonstrated that sintering at 1200°C in air is necessary to obtain well-crystallized pyrochlore crystals in a sodium aluminoborosilicate glass through a one-step controlled cooling. The crystallization, structure, and microstructure of Eu₂Ti₂O₇ pyrochlore as the major phases in residual glass were confirmed with X-ray diffraction (XRD), scanning electron microscopy-energy dispersive spectroscopy, transmission electron microscopy, and Raman spectroscopy. The structures of major Eu₂Ti₂O₇ pyrochlore and minor [Eu_4.67O(SiO₄)₃] apatite in both sintered and HIPed samples were refined using synchrotron XRD data. While the processing atmosphere did not appear to affect the cell parameter of the main pyrochlore phase, very small volume expansion (~0.3%) was observed for the minor apatite phase in the HIPed sample. In addition, static leaching of the HIPed sample confirmed that pyrochlore GCs are chemically durable. Overall, pyrochlore GCs prepared via both sintering and HIPing with the Eu partitioning factor of ~23 between ceramics and the residual glass are suitable waste forms for minor actinides with processing chemicals.     

Development of brannerite glass‐ceramics for the immobilization of actinide‐rich radioactive wastes

Brannerite‐based glass‐ceramics have been developed as potential waste forms for the immobilization of actinide‐rich radioactive wastes. For the first time, the formation of brannerite phases in glass has been demonstrated using uranium (U) and plutonium (Pu) with additions of gadolinium and hafnium as neutron absorbers. Both XRD and SEM‐EDS confirm that brannerite is the dominating phase with compositions close to Y_0.5U_0.5Ti₂O₆, Gd_0.2Pu_0.3U_0.5Ti₂O₆, and Gd_0.1Hf_0.1Pu_0.2U_0.6Ti₂O₆ internally crystallized in the glass. TEM SAED and Raman spectroscopy reveal the typical structure and vibration modes for brannerite. In addition, the presence of U⁵⁺ species as designed in the formulations has been confirmed by diffuse reflectance spectroscopy. More importantly, the U and Pu were partitioned exclusively in the ceramic phases with no detectable actinide in the glass.     

Crystallization of Rhenium Salts in a Simulated Low‐Activity Waste Borosilicate Glass

This study presents the characterization of salt phases that formed on simulated low‐activity waste glass melts during a rhenium solubility study. This study with rhenium salts is also applicable to real applications involving radioactive technetium salts. In this synthesis method, oxide glass powder is mixed with the volatile species, vacuum‐sealed in a fused quartz ampoule, and then heated in a furnace. This technique restricts the volatile species to the headspace above the melt but still within the sealed ampoule, thus maximizing the concentration of these species that are in contact with the glass. Above the previously determined solubility of Re⁷⁺ in this glass, a molten salt phase segregated to the top of the melt and crystallized into a solid layer. This salt was analyzed with X‐ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, as well as wavelength dispersive spectroscopy and was found to be composed of alkali perrhenates (NaReO₄, KReO₄) and alkali sulfates. Similar crystalline inclusions were found in the bulk of some glasses as well.     

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.     

Novel Synthesis Method and Characterization of Porous Calcium Hexa‐Aluminate Ceramics

Porous calcium hexa‐aluminate (CA₆) ceramics were in‐situ synthesized by heated CaCO₃ and α‐Al₂O₃ in a NaCl‐based salt at 1400°C for 3 h, and then characterized by X‐ray diffraction (XRD), scanning electron microscopy, (SEM) and mercury porosimetry. The size and morphology of the CA₆ crystals and pores were gradually changed with the increase of NaCl addition in the raw material, indicating that the molten salt not only provided a liquid environment for synthesis of CA₆, but also generated considerable pores.     

Extended glass‐forming region in the AgCl‐Ag2S‐As2S3 ternary system

In the present work, glass formation property of the AgCl‐Ag₂S‐As₂S₃ ternary system is investigated. An extended glass‐forming region rich in the AgCl content (up to 80 mol.%) is observed. It is also found that there exists a small devitrification domain dividing the whole glass‐forming region into two parts. XRD analyses confirm that the precipitated crystals in the crystallized samples are pure AgCl, or Xanthoconite and Proustite Ag₃AsS₃, depending on the Ag₂S/As₂S₃ ratio and the AgCl content. Structural evolutions of the selected samples 15AgCl‐yAg₂S‐zAs₂S₃ are examined by high‐resolution XPS, and Raman spectroscopy. The crystallization mechanisms are studied comprehensively by SEM, DSC, and XRD measurements, and tentatively assigned to the presence of phase separation. The results reported in this article are expected to serve as a guide for the selection of suitable electrode materials for electrochemical applications.     

Crystallization and luminescence properties of Eu<Superscript>2+</Superscript> doped diopside glass ceramics

Eu²⁺ doped glass ceramics have been prepared and characterized. The crystallization and optical properties of the glass ceramics were studied by XRD, SEM, and fluorescence spectra. The precipitated crystalline phase in the glass ceramics was prismatic diopside (CaMgSi₂O₆) and plate-like cristobalite (β-SiO₂). As the heat treatment time increases, the content of crystals increases gradually. Fluorescence measurements showed that Eu²⁺ ions entered into the diopside crystalline phase and induced a much stronger emission in the glass ceramics than that in the corresponding glass. With increase of Eu²⁺ content, concentration quenching was observed.     

Lithium Disilicate Glass‐Ceramics by Heat Treatment of Lithium Metasilicate Glass‐Ceramics Obtained by Hot Pressing

Lithium disilicate glass‐ceramics are widely used as dental ceramics due to their machinability and translucency. In this study, lithium disilicate glass‐ceramic was fabricated through heat treatment of lithium metasilicate glass‐ceramics obtained by hot pressing of glass powder composed of SiO₂–Li₂O–P₂O₅–ZrO₂–Al₂O₃–K₂O–CeO₂ at low temperature. The crystalline phase, microstructure, and mechanical properties were investigated. The results indicated that lithium metasilicate glass‐ceramic with a relative density of higher than 99% was obtained after hot pressing, and glass‐ceramic with interlocked rod‐like Li₂Si₂O₅ crystals and good flexural strength (338 ± 20 MPa) was successfully obtained through heat treatment. The two‐step method was believed to be feasible in tailoring the microstructure and mechanical properties of lithium disilicate glass‐ceramics.     

Effect of silicon carbide whisker reinforcement on CaO–ZrO2–SiO2 glass–ceramic system

Abstract

An industrial frit formulated in the new CaO–ZrO₂–SiO₂ glass–ceramic system was studied as a matrix for whisker reinforced composites. The frit was ball milled in acetone and wet ultrasonically mixed with 5, 10, 20, and 30 vol.-% SiC whiskers in order to overcome whisker agglomeration and obtain intimate mixing of the two phases. The samples were hot pressed at 14 MPa in graphite dies, using a N₂ atmosphere, for 2 h at 1280°C. In order to investigate the effect of whiskers as a reinforcement, flexural strength as well as crack configuration and propagation were taken into consideration. Whisker orientation perpendicular to the hot pressing direction was found by SEM observation, and no carbon layer at the whisker/matrix interface was detected by EPMA. Further characterisation of the specimens involved physical (density, elastic modulus) and microstructural properties (XRD, SEM, TEM). The result of glass devitrification was inter locked wollastonite crystals.     

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.     

Infrared to Visible Up‐Conversion Emission in Er3+/Yb3+ Codoped Fluoro–Phosphate Glass–Ceramics

Erbium Er³⁺ and ytterbium Yb³⁺ codoped fluoro‐phosphate glasses belonging to the system NaPO₃–YF₃–BaF₂–CaF₂ have been prepared by the classical melt‐quenching technique. Glasses containing up to 10 wt% of erbium and ytterbium fluorides have been obtained and characterized using differential scanning calorimetry (DSC) and UV–visible and near‐infrared spectroscopy. Transparent and homogeneous glass–ceramics have been then reproducibly synthetized by appropriate heat treatment above glass transition temperature of a selected parent glass. Structural investigations of the crystallization performed through X‐ray diffractometry (XRD) and scanning electron microscopy (SEM) have evidenced the formation of fluorite‐type cubic crystals based during the devitrification process. Finally, infrared to visible up‐conversion emission upon excitation at 975 nm has been studied on the Er³⁺ and Yb³⁺ codoped glass–ceramics as a function of thermal treatment time. A large enhancement of intensity of the up‐conversion emissions–about 150 times‐ has been observed in the glass–ceramics if compared to the parent glass one, suggesting an incorporation of the rare‐earth ions (REI) into the crystalline phase.     

Can Kosmotropic Salt/Chaotropic Ionic Liquid (Salt/Salt Aqueous Biphasic Systems) be Used to Remove Pertechnetate From Complex Salt Waste?

Abstract

Aqueous solutions of water‐structuring, kosmotropic salts (e.g., salts of PO₄ ^3?, HPO₄ ^2?, CO₃ ^2?) will salt‐out water‐destructuring chaotropic ionic liquids (ILs) (e.g., 1‐butyl‐3‐methylimidazolium chloride, ([C₄mim]Cl)) forming salt/salt aqueous biphasic systems (ABS). The chaotropic pertechnetate (TcO₄ ^?) anion will partition without the use of an extractant into the IL‐rich phase. These complex salt/salt ABS are not unlike the complex and salt‐rich Hanford tank waste, and thus have been used here as a simple model to show effectiveness in the partitioning of TcO₄ ^? from such tank waste into an IL‐rich phase.     

Hot corrosion of glass coating on nickel base superalloy

Hot corrosion behaviour of BaO–MgO–SiO₂ based glass coating on nickel base superalloy was studied using 80 wt.% Na₂SO₄ + 20 wt.% NaCl salt mixture, which melts at about 700 °C. In one set of experiments the glass coated superalloy substrates were immersed in the molten salt wherein in the other samples were suspended in the salt vapour at 1000 °C. During the test, mass loss per unit surface area was observed to be higher for specimens suspended in the salt vapour. The phase composition and microstructure of the corroded coating were investigated by X-ray diffraction (XRD), optical microscopy and scanning electron microscopy (SEM) in association with energy dispersive X-ray (EDX) analysis.     

Characterization of New Categories of Bioactive Based Tellurite and Silicate Glasses

New types of tellurite glass ceramics were prepared and studied from the viewpoint of bioactivity. The obtained results were compared with those of silicate glass ceramics. The crystallization behaviors of both silicate and tellurite glass ceramics with equal ratio of CaO/P₂O₅ were investigated. The silicate glass samples were transformed to glass ceramics by a thermal treatment process. While the tellurite glass ceramics were directly obtained without any thermal treatment. The microstructure of these materials was characterized by X-ray diffraction (XRD), Fourier transform infrared absorption spectroscopy (FTIR) and a scanning electron microscope (SEM) equipped with an energy dispersive spectrometer (SEM/EDX). The results revealed clear proof that TeO₂ promoted the nucleation and crystallization processes which led to the formation of different crystalline bio-phases. While the silicate glasses showed a much lower degree of crystallinity than that presented by the tellurite glass ceramics. The crystals of tellurite containing glass were needle- like morphology, which is attributed to the one-dimensional rapid growth of the apatite-tellurite phase. On the other hand, a particle-like morphology is shown in the silicate glass matrix. Bioactivity of the glasses in simulated body fluids (SBF) was investigated. Tellurite containing glass ceramics showed a better bioactivity during the in vitro test than that of the silicate one. This was attributed to a great analogous between the morphology of crystals of tellurite glass and the morphology of hydroxyapatite in human bone, since both possess a needle-like morphology.     

Recrystallization of Er3+:CaF2 in Transparent Fluorophosphate Glass‐Ceramics with the Co‐Firing Method

Transparent glass‐ceramics containing Er³⁺:CaF₂ crystallites were prepared with the co‐firing method. The formation process of the glass‐ceramics was investigated by means of SEM, XRD, and DSC. The results reveal that the Er³⁺:CaF₂ nanocrystals do not dissolve into the fluorophosphates (FP) glassmelt until the co‐firing temperature increase higher than about 920°C. Below this temperature, Er³⁺:CaF₂ survives the co‐firing process and the nanocrystals just grow to spherical crystals of micrometers in size. Co‐firing temperature higher than this temperature leads to the dissolution of Er³⁺:CaF₂ and the dissolved Er³⁺:CaF₂ recrystallized during quenching process and takes the shape of dendrite.     

Melting treatment of waste asbestos using mixture of hydrogen and oxygen produced from water electrolysis

In this study, we melted four types of waste asbestos containing material such as spread asbestos, plasterboard asbestos, slate asbestos and asbestos 99 wt%, in a melting furnace at 1,450–1,550 that uses a mixture of hydrogen and oxygen (Brown’s gas) as a fuel. More volatile components (CaO, K₂O) are enriched in spread asbestos, plasterboard asbestos, and slate asbestos, while less volatile compounds (SiO₂, Fe₂O₃, MgO) remain in asbestos 99%. Through basicity of raw materials, spread asbestos, plasterboard asbestos, and slate asbestos were found to have more alkalinity, and asbestos 99% was found more acidic. SEM and EDX results revealed that all raw materials had various kinds of asbestos fiber. Spread asbestos, plasterboard asbestos, and slate asbestos were considered as tremolite asbestos, whereas asbestos 99% was considered as chrysotile asbestos. It was further confirmed by SEM and XRD studies that all waste materials contained some crystalline structures which transformed into amorphous glassy structure on melting. Also, in case of added glass cullet during the melting of spread asbestos, it transformed the raw material into a perfect vitrified product having more glassy surface and amorphous in nature     

Submixture model to predict nepheline precipitation in waste glasses

High-alumina high-level waste (HLW) glasses are prone to nepheline precipitation during canister-centerline cooling (CCC). If sufficient nepheline forms, the chemical durability of the glass will be significantly impacted. Overly conservative constraints have been developed and used to avoid the deleterious effects of nepheline formation in U.S. HLW glasses. The constraints used have been shown to significantly limit the loading of waste in glass at Hanford and therefore the cost and schedule of cleanup. A 90-glass study was performed to develop an improved understanding of the impacts of glass composition on the formation of nepheline during CCC. The CCC crystallinity data from these glasses were combined with 657 glasses found in the literature. The trends showed significant effects of Na₂O, Al₂O₃, SiO₂, B₂O₃, CaO, Li₂O, and potentially K₂O on the propensity for nepheline formation. A pseudo-ternary submixture model was proposed to identify the glass composition region prone to nepheline precipitation. This pseudo-ternary with axes of SiO₂ + 1.98B₂O₃, Na₂O + 0.653Li₂O + 0.158CaO, and Al₂O₃ was found to divide glasses that precipitate nepheline during CCC from those that do not. Application of this constraint is anticipated to increase the loading of Hanford high-alumina HLWs in glass by roughly one-third.     

Synthesis and Toluene Adsorption/Desorption Property of Beta Zeolite Coated on Cordierite Honeycomb by an In Situ Crystallization Method

The beta zeolite on cordierite ceramic monolith was synthesized by an in situ crystallization method and characterized by XRD, N₂ adsorption/desorption, SEM and NH₃‐TPD techniques. Toluene adsorption/desorption was used as probe test for the control of cold‐start emissions and treatment of volatile organic compounds. The presence of beta on the supports was confirmed by XRD, SEM, and N₂ adsorption/desorption measurements. The zeolite crystals grow both into the cordierite macropores and on the surface of the monolith channels, which form an integrated network ensuring a strong adherence. The highly dispersed beta on supports, demonstrated by larger surface area and adsorption capacity of N₂, resulted in a significant increase of the total acidity, and thus a greater adsorption capacity for toluene. Furthermore, it could trap larger amounts of toluene to higher temperature and show considerable activity for toluene cracking and oxidation. These are attributed to the greater acidity and stronger acid sites of in situ synthesized beta.     

Heterogeneous Ziegler–Natta catalysts with various sizes of MgCl<Subscript>2</Subscript> crystallites: synthesis and characterization

A MgCl₂-based Ziegler–Natta catalyst was characterized using X-ray diffraction (XRD) patterns, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) and IR spectra. We focused on the XRD reflection at 2θ = 50° to determine the thickness of MgCl₂ crystals, and validated these results with TEM pictures. SEM pictures were taken in order to measure the size of the nanoparticles formed by the MgCl₂ crystals. Several compounds were synthesized for comparison and to aid interpretation of the infrared (IR) spectra. The catalysts were prepared by precipitating MgCl₂, which was used as support material and subsequently treated with TiCl₄. The thickness of the catalyst crystals was calculated from the XRD reflection at 2θ = 50°. Changing the precipitation temperature within a range from 40 to 90 °C altered the thickness of the MgCl₂ crystal plates. The maximum thickness of 7 nm was achieved at a precipitation temperature of 60 °C. The SEM pictures showed that the nanoparticles had a diameter of ~200 nm. A crystal base unit had a volume that corresponded to that of a sphere of 3.5 nm radius. Thus, we estimated that a typical catalyst particle with a diameter of 20 μm contained about one million nanoparticles, each of which consisted of about 25,000 MgCl₂ crystal units.