Crystal structures, microtopography, morphologies, elemental compositions, and ionic conductivity have been investigated for Li5-xLa3(Nb,Ta)O12-y using X-ray diffraction (XRD), field-emission analytical scanning and transmission electron microscopies (S/TEM), and electrochemical impedance spectroscopy. Using Rietveld refinements with powder XRD patterns, we determined that the number of Li atoms in the formula is less than 5 and that Li5-xLa3(NbTa)O12-y crystallizes in the cubic garnet structure with a space group Ia-3d. Sintering at varying temperatures (750–1000 °C) for 5 h in an ambient atmosphere produced distinct outcomes. Rietveld refinements disclosed that the sample sintered at 1000 °C (Li3.43(2)La3Nb1.07(2)Ta0.93(2)O12-y, a = 12.8361(7) Å, V = 2114.96(3) Å3) exhibited the highest ionic conductivity, while the 850 °C sample had the lowest conductivity, characterized by lower Li concentration and impurity phases (Li(Nb,Ta)3O88, Li2CO3). Analyses, including XRD and electron microscopy, confirmed the 1000 °C sample as a relatively phase pure with enhanced Li content (Li/La = 1.2), larger grains (15 μm), and uniform crystallinity. The 1000 °C sample introduced additional partially filled Li3 (96h) sites, promoting Li migration, and enhancing ionic conductivity. The resulting XRD pattern at 1000 °C has been submitted to the Powder Diffraction File as a reference.

Here, the authors report a detailed method of growing LaAlGe, a nonmagnetic Weyl semimetal, thin film on silicon(100) substrates by molecular beam epitaxy and their structural and electrical characterizations. About 50-nm-thick LaAlGe films were deposited and annealed for 16 h in situ at a temperature of 793 K. As-grown high-quality films showed uniform surface topography and near ideal stoichiometry with a body-centered tetragonal crystal structure. Temperature-dependent longitudinal resistivity can be understood with dominant interband s–d electron–phonon scattering in the temperature range of 5–40 K. Hall measurements confirmed the semimetallic nature of the films with an electron-dominated charge carrier density of ~7.15 × 1021 cm−3 at 5 K.

Theoretical calculations and experimental observations show MoTe2 is a type II Weyl semimetal, along with many members of transition metal dichalcogenides family. We have grown highly crystalline large-area MoTe2 thin films on Si/SiO2 substrates by chemical vapor deposition. Very uniform, continuous, and smooth films were obtained as confirmed by scanning electron microscopy and atomic force microscopy analyses. Measurements of the temperature dependence of longitudinal resistivity and current–voltage characteristics at different temperature are discussed. Unsaturated, positive quadratic magnetoresistance of the as-grown thin films has been observed from 10 to 200 K. Hall resistivity measurements confirm the majority charge carriers are hole.

Highly crystalline core-shell FeCo-CoFe2O4 nanowires were obtained from a three step process. Initially, CoFe2O4 nanowires were grown using electrospinning and annealing at higher temperatures. Through a thermal reduction under controlled conditions, CoFe2O4 nanostructures were converted to FeCo alloy nanowires. Then by natural oxidation, a highly crystalline shell of CoFe2O4 formed over the FeCo core structure. Structural and magnetic characterizations revealed the presence of highly crystalline FeCo-Co2FeO4 core-shell structure. Magnetically, the soft FeCo phase switches at a lower magnetic field compared to the hard CoFe2O4 phase, yielding an irregular hysteresis loop with a squeezed loop in the middle. The FeCo/CoFe2O4 core-shell is stable and it retains its structure for a prolonged duration.

Technetium (Tc), found in some nuclear wastes, is of particular concern with regard to long-term storage, because of its long-lived radioactivity and high mobility in the environment. Tc and rhenium (Re), commonly used as a non-radioactive surrogate for Tc, were studied to assess their behavior in borosilicate glass under hydrothermal conditions in the Vapor Hydration Test (VHT). X-ray absorption spectroscopy (XAS) and scanning electron microscopy (SEM) measurements were made on the original Tc- and Re-containing glasses and their corresponding VHT samples, and show different behavior for Tc and Re under VHT conditions. XAS indicates that, despite starting with different Tc(IV) and Tc(VII) distributions in each glass, the VHT samples have 100% Tc(IV)O6 environments. SEM shows complete alteration of the original glass, Tc enrichment near the sample surface, and Tc depletion in the center. Perrhenate (Re(VII)O4−) is dominant in both Re-containing samples before and after the VHT, where Re is depleted near the VHT sample surface and more concentrated toward the center.

As a result of the development of a reference glass formulation for the immobilization of West-Valley nuclear waste, a large number of glass compositions have been tested under a variety of leaching conditions for extended durations. In this work, data from the standard PCT leaching procedure (deionized water, 90°C, S/V = 2000 m-1) are evaluated for a subset of 98 of these glasses, for which the alteration times extend up to fifteen years. Analysis of the leachate data over this extended period has led to a classification of the glass compositions according to their PCT behavior, as characterized by the boron release in solution, the decrease in the rate of alteration, or the occurrence of a resumption of alteration. Three types of behavior are associated with a normalized mass loss of boron after 100 days of around 1, 2, or 5 g m-2 respectively, and a ratio of the rate of alteration at 7 days to the rate at 1000 days of about 30. A fourth type is characterized by a much larger decrease between the rates at 7 and 1000 days with a ratio exceeding 120. Four further categories are associated with late-stage resumption of glass alteration. A statistical analysis of the data has been used to model the leachate data as a function of glass composition. The effects of seven major elements (Si, B, Al, Li, Na, K, Fe) on the long-term glass durability have been studied. As a result of this analysis, the different types of leaching behaviors can be predicted with a good reliability from the composition of the pristine glass.

The kinetics of vapor phase hydration (VHT) of high-sodium waste glasses often exhibits incubation, fast-rising, and final stages. The incubation stage is characterized by the slow and gradual appearance of transformed regions on the surface of the glass, signaling the initiation of the phase transformation. This is followed by a fast-rising stage, during which most of the transformation takes place. The final stage is characterized by the slower alteration of the remaining glass phase, which can have a duration orders of magnitude longer than those of the previous stages. While the Avrami equation provides a good representation of these features, the origin of the late-stage slow-down in the Avrami model is unrealistic for the VHT process. Computer simulations based on cell models have been used to investigate possible mechanistic origins. The models consider the formation of multiple alteration phases and simulate the complex interplay among the several microscopic mechanisms involved in the hydration process. The models assume that the transformation from the original pristine glass to the final stable altered phase occurs in two steps: from glass to a metastable phase, and then from a metastable to a stable phase. The results indicate that the late-stage slow-down can be reproduced as a result of the build-up of species that are incompatible with the stable phase or by the occlusion of the surface due to the growth of a surface phase that is less permeable to water. The simulation results are in good general agreement with the features of the experimental data.

XANES and EXAFS data were collected and analyzed to characterize vanadium in borosilicate glasses used for immobilization of sulfur-containing nuclear wastes. Earlier studies suggested that adding vanadium to the melt improves sulfur solubility. Data are presented for a variety of borosilicate glasses, some containing sulfur and some sulfur-free, that have V2O5 concentrations as high as 12 wt%, and for crystalline vanadium sulfide, silicate, and oxide standards. The data for all glasses investigated indicate that most or all vanadium has a +5 valence and is tetrahedrally coordinated by oxygen atoms. Both XANES and EXAFS also show that glasses synthesized under reducing conditions can have pentacoordinated V+4 populations up to approximately 20 to 25% of all vanadium present with the remainder being V+5O4. There is no evidence from XANES or EXAFS of V-S bonds in any of the glasses investigated.

A range of compositions of high-zirconia borosilicate glasses were formulated and their structures investigated by a combination of techniques. These compositions have potential applications for high-level nuclear waste storage in combination with advanced reprocessing methods. Raman and Zr EXAFS data were collected for a series of glasses spanning a range of zirconia concentrations. The Raman spectra indicate that Zr acts as a silicate network modifier, where the silicate tetrahedral network depolymerizes as the zirconia content increases. Zr EXAFS analysis indicates that Zr is found in octahedral sites, and to a minor extent, sevencoordinated sites. As the zirconia content increases, the fraction of seven-coordinated Zr-sites increases; this may be the cause of ZrO2 baddeleyite crystallization that was observed in some Zr-rich glasses investigated.

Vitrification has become the international method of choice for the immobilization of highlevel nuclear wastes (HLW) from both commercial and defense fuel reprocessing activities. However, there are clear economic incentives for "next-generation" melters that might achieve increased waste loadings and higher throughput rates. In addition, BNFL is investigating potential immobilization processes for projected high-zirconium waste streams that would be generated from advanced nuclear fuel reprocessing processes. One approach towards addressing both of these challenges is waste vitrification at temperatures above the limits that are imposed on all currently operating HLW melters (around 1100 -1200°C). A unique high-temperature joule-heated melter that has been operating at the Vitreous State Laboratory for several years was used to conduct a matrix of tests designed to address these issues. The tests used simulants of two reprocessing waste streams: (i) A blend of "Magnox" and "Oxide" wastes, similar to those currently being vitrified at BNFL's Sellafield site; and (ii) The projected high-zirconium wastes. Each type of waste was investigated both as a wet slurry feed using chemical additives and as a dry calcined waste feed mixed with glass frit. Three target glass compositions were designed for these tests in order to permit processing over a wide range of temperatures. Data were collected on processing rates, off-gas composition, glass product composition and product quality, as well as on general processing behavior. In all cases, glass production rates increased rapidly with processing temperature, typically doubling for every 100°C, and decreased with increasing water content of the feed. The glass production rates per unit melt surface area were significantly higher than those typically observed for hot-wall induction melters operating under comparable conditions. Interestingly, off-gas emissions were much greater for the slurry feeds than for the comparable solid feeds. The resulting glass products were characterized for melt viscosity and electrical conductivity, leachability by both soxhlet and PCT procedures, glass transition temperature, and the amounts and types of any secondary phases that were present.

Vitrification studies of actual Savannah River M-Area mixed wastes have shown that the limiting factor for high waste loading of this waste stream is its chemical durability as defined by the toxicity characteristics leaching procedure (TCLP). As part of the optimization study of Savannah River M-Area wastes, a number of additives were examined including Na2O, Li2O, B2O3, ZrO2, and TiO2. This paper reports on the effect of varying the boron to total alkali ratio and on the effect of substitutions such as ZrO2 for waste and TiO2 for SiO2 on the chemical durability and processability of M-Area waste glasses.

In many vitrification processes, refractory materials are used to contain the waste glass melt. The corrosive nature of the high-temperature melt consumes the waste feed materials but also limits refractory life. As vitrification is applied to more diverse waste streams, and particularly in higher-temperature applications, increasingly severe demands are placed on the refractory materials. A variety of potential refractory materials including Fused-cast AZS, Monofrax K3, Monofrax E, and the Corhart refractories ER1195, ER2161, C1215, C1215Z, Rechrome, and TI 186, were subjected to corrosion testing at 1450°C using the ASTM C-621 procedure. A series of simulated waste glasses was used which included F, Cl, S, Cu, Zn, Pb; these minor components were found to cause significant, and in some cases drastic, increases in corrosion rates. The corrosion tests were conducted over a range of time intervals extending to 144 hrs in order to investigate the kinetics of the corrosion processes. The change of the concentrations of constituents in the glass was monitored by compositional analysis of glass samples and correlated to the observed extent of corrosion; typically, components of the material under test increase with time while key minor components, such as Cu and Pb, decrease. The rate of corrosion of high-zirconia refractories was slowed considerably by adding zirconia to the waste glass composition; this has the added benefit of improving the aqueous leach resistance of the waste form that is produced.

In our previous studies on the optimization of glass compositions for high-level nuclear waste vitrification it was found that, over certain composition ranges, PCT leachate concentrations increased dramatically with very small changes in glass composition. The large differences that are observed between the leachate pH values for the “durable” and the “less-durable” glasses is one possible cause for this strongly non-linear glass composition effect; conversely, the pH difference may be merely another symptom. In this study, four simulated nuclear waste glasses (two of the less-durable and two of the durable types), were leached in both zwitterionic and inorganic buffer solutions, at fixed pH-values in the ranges of 7 to 12. The very different leaching behaviors of the two types of glasses persisted and, furthermore, different pH-dependence was found despite their very similar glass composition. This study suggests that the leachate pH difference observed between the less-durable and the durable glasses under uncontrolled pH conditions is not the major cause of the large difference of leaching behavior between those glasses. The normalized release ratios of soluble components (B, Li, Na) to Si show significant differences for the two types of glasses.

Explanation of the striking non-linear effect of glass composition on the aqueous dissolution represents an important challenge to existing dissolution mechanisms. Surface layers that are formed during glass dissolution may play an important role in this effect. One chemically reactive and one less-reactive nuclear waste glass (leachate concentrations differ by about a factor of 10) were reacted in deionized water. Two types of glass powders were used: Type A powders were pristine glass powders; Type B powders were the glass powders which had been reacted for 120 days to develop the surface layers. Both the solution concentrations and the surface layers were investigated. The experimental observations indicate that: (i) There is a range of glass compositions over which small differences in composition lead to large changes in both reaction rates and surface layer thickness; and (ii) The reaction rate is strongly affected by the formation of the surface layer (the layer appears to be protective) and cannot be explained in terms of saturation effects alone. The findings are contrary to the conclusion of a previous study and serve to highlight the inadequacy of existing dissolution models predicated on an overly simplistic mechanism, especially with regard to glass composition effects.

A glass-based waste form used for the immobilization of high-level nuclear wastes should exhibit good resistance to aqueous corrosion since typically this is the primary process by which radionucleides could be released into the environment upon failure of other barriers. In the USA, the Waste Acceptance Product Specifications (WAPS) provides a set of requirements to ensure the consistency of the waste forms produced and specifies the Product Consistency Test (PCT) as a measure of relative chemical durability. While the PCT procedure permits usage of both Teflon and stainless steel vessels for testing of simulated development glasses, Teflon is not permitted for testing of production glasses due to radiative degradation. The results presented in this paper indicate that there are very significant differences between tests conducted in the two types of vessels due to the well-known permeability of Teflon to atmospheric carbon dioxide which results in lowering of the solution pH and a consequent reduction in the leach rate of silicate glasses. A wide range of nuclear waste glass compositions was subjected to the PCT procedure using both Teflon and stainless steel vessels. The magnitude of the effect (up to a factor of four for B, Na, Li concentrations) depends strongly on glass composition, therefore the isolated checks performed previously were inconclusive. The permeability to CO2 of two types of Teflon vessels specified in the PCT procedure was directly measured using buffer solutions: ingress of CO2 is linear in time, strongly pH-dependent, and was as high as 100 ppm after 7 days. In actual PCT tests in Teflon vessels, the total CO2 content was 560 ppm after 87 days and 1930 ppm after one year.

Results are presented from treatability studies on the vitrification of hazardous and low-level radioactive soils and sludges from the Fernald site. The majority of the contaminants of concern are contained in large volumes of sludges accumulated from uranium and thorium production operations that are presently stored in pits at Fernald. These sludges present particular challenges to the vitrification process in that they contain significant amounts of fluorides (mostly magnesium and calcium). In this study, glass formulations used sludges, soils and a minimum amount of additives resulting in waste loadings as high as 94%. Several of these formulations were evaluated by continuous feeding of slurries into a joule-heated vitrification system. Melter off-gases were treated in a two-stage NaOH scrubbing system. HF acid fumes were neutralized, resulting in the formation of a NaF solid precipitate which is removed from the scrubber and recycled to subsequent melter feeds. Elemental and isotope compositions of the glasses, scrubber solutions, NaF precipitate and off-gases show that greater than 99.7% of uranium and thorium, 95% of Pb, Cd, Ni, Sb, Cr, and Hg were retained in the glass. Fluoride and other gaseous emissions from the scrubber system were below regulatory limits, even before HEPA filtration.