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At least 199 records · Page 11

Deep glassy state dynamic data challenge glass models: Elastic models

The idea of an “ideal” glass transition temperature has persisted at least since the work from Kauzmann when it was observed that the entropy of glass-forming liquids extrapolated to below that of the crystal, thus suggesting the need for a phase transition at a finite or non-zero absolute temperature. This thermodynamic paradox was also found to be related to the observations of a diverging of the extrapolated viscosity or relaxation times at a temperature near to this ideal glass transition. Recently, however, we have carried out experiments using both an ancient amber material and an ultra-stable amorphous fluoropolymer that challenge the ideas of the divergence of the viscosity or relaxation times at this ideal glass transition. In the present manuscript we have evaluated two theories of the glass transition that are based on ideas related to elasticity of the amorphous glass-forming material. We find that the models from both J. Dyre and his group and of K.S. Schweizer and his group not only show non-diverging behavior but are also in some agreement with the new data, though still showing somewhat slower dynamics than those observed in the experiments. The work shows that the data are good enough to distinguish between theories and it is suggested that other mechanisms may be needed to fully describe the non-diverging responses of the ultra-stable glasses.

36 MATERIALS SCIENCE↗

LionGlass™: A low‐melting, carbonate‐free alternative to soda lime silicate glass

LionGlass™ is Penn State University's patent-pending alumino-silicophosphate glass compositional family that offers, for the first time, a viable low-melting, carbonate-free alternative to soda lime silicate glass by (a) lowering the melting temperature by up to 400°C compared to soda lime silicate glass and (b) eliminating the use of carbonate batch materials. The viscosity curve of LionGlass is shifted downward in temperature compared to soda lime silicate glass, enabling melting at much lower temperatures. LionGlass also has significantly improved resistance to crack initiation compared to soda lime silicate glass. Other properties, such as thermal expansion coefficient and optical dispersion curve, are comparable to those of traditional soda lime silicate glass.

Lion-Glass↗

Ultrafast Laser Welding and Terahertz Time-domain Spectroscopy of Soda Lime Silicate Glass

Joining and welding techniques of similar and dissimilar materials have reached their limits due to the inflexibility of adapting dielectric materials, e.g., glasses and ceramics, reproducibility for transparent materials, and cycle process time. The ability to join pieces of glasses using laser irradiation allows rapid processing of vacuum insulating glass (VIG) for a widening range of commercial energy-efficient applications. We have used a 1064-nm laser wavelength with 15 picoseconds pulse width and a 155-kHz repetition rate to weld commercial plate glass pieces. The welded samples were characterized via x-ray fluorescence (XRF), time-of-flight secondary ion mass spectrometry (TOF–SIMS), polarimetry, and terahertz time-domain spectroscopy (THz-TDS) to determine the integrity of the weld and chemical changes in the welded areas. Our data shows no significant changes in glass chemistry and structure on average over nano- to micro-scales occurred from the welding process within the limits of the characterization tools. Our results demonstrate successful welding of glass plates without significant changes in the glass chemistry, structure, or properties in the laser-modified region or strains in the bulk glass.

Matthies, Kathleen [ORNL] (ORCID:0009000213135441)↗

Effects of Composition and Oxidation States on the Structures of Chromium-Containing Sodium Silicate Glasses: Molecular Dynamics Simulations using Machine Learning Interatomic Potentials

Chromium represents a significant challenge for the vitrification of high-level nuclear waste into silicate and borosilicate glasses due to its low solubility and variable oxidation states, which can limit the waste loading due to promotion of crystallization or phase separation during processing. In this study, we modeled chromium containing silicate glasses using molecular dynamics simulations with three machine learning interatomic potentials (MLIPs), MACE, CHGNet, and PFP were employed, to gain insights on glass composition and oxidation states on the structures of these glasses. One of the goals is to evaluate their ability of these MLIPs to accurately represent the general structure of silicate glasses and chromium local environments as a function of chromium oxidation states. Density Functional Theory (DFT) based calculations and experimental data such as neutron structure factors were used to validate the structural models. It was found that the foundation models of all three MLIPs are able to reproduce general structural features of the sodium silicate glass structure consistent with experimental and DFT data, but only CHGNet and PFP can accurately capture the oxidation states and local environment of chromium: tetrahedral for Cr6+ and octahedral for Cr3+. Furthermore, we studied the effect of varying Cr3+/ Cr6+ (Cr3+/Crtotal) ratio and total chromium content using PFP. Our results show that Cr6+ enhances network polymerization by reducing non-bridging oxygens through Na? charge compensation required due to the formation of chromate (CrO42-) species, while Cr³? acts as a network modifier that disrupts connectivity. System size effects on the structural characteristics and chromium environments were also tested using the PFP potential. This work highlights the importance of careful validation on the precision, transferability, and potential of MLIPs for modeling glasses containing transition metal elements that can exist in multiple oxidation states. It is also encouraging to see the foundational models are all three MLFFs are able to reproduce the basic sodium silicate glass structures, while suggesting additional training or refining is needed to improve the description of more complex systems containing transition metals.

Puga, Christina L.↗

Ab Initio Simulation of Medium-Range Ordering in Ionic Glass Electrolytes LiSiPON and LiNaSiPON

Ionic glasses can exhibit a unique combination of optical transparency, electronic resistivity, ionic conductivity, and mechanical ductility. The origin of the relatively high ionic conductivity and ductility is poorly understood. Recently, these ionic glasses were found to have medium-range ordering (MRO) similar to that of metallic glasses. This MRO significantly impacts the properties of metallic glasses and is also expected to significantly impact the properties of ionic glasses. Here, this work used ab initio molecular dynamics (AIMD) simulations to study the effect of ionic glass composition on the MRO. The AIMD models showed that the degree of MRO increased as the temperature of the LiSiPON ionic glass decreased. The modeling also showed that the MRO is suppressed when 50% of Li is substituted with Na. This work lays the foundation for using AIMD to identify clear structure–property relationships in ionic glasses, allowing their properties to be optimized.

Osetsky, Yuri N. [Oak Ridge National Laboratory (O↗

Effect of decades of corrosion on the microstructure of altered glasses and their radiation stability

Understanding the microstructural evolution of glasses during their interaction with water and radiation is of fundamental importance in addressing the corrosion of nuclear waste forms under geological disposal conditions. Here we report the results of more than 21 years of corrosion of two borosilicate glasses showing the formation of mesoporous C–S–H gels in Ca-bearing glasses and a mainly microporous microstructure in Al-bearing glasses. These porous corroded glasses were then irradiated with heavy ions to simulate the effects of recoil nucleus damage and monitored in real time using transmission electron microscopy with in situ ion irradiation. The ballistic collisions remarkably healed the porous corroded glasses to a pore-free homogeneous microstructure. Besides providing new insights and predictions about how doped glasses and actual waste forms may evolve under corrosion and irradiation, the results highlight the non-universal nature of the existing corrosion models and the important role that the glass composition and radiation damage play in the evolution of the microstructure during corrosion.

36 MATERIALS SCIENCE↗

Looking through model medieval green glasses: From color to recipe

Abstract The colors of medieval stained glasses depend on their chemical composition. The redox interactions in glass between iron and copper and their influence on the color were investigated in two soda‐lime silicate model glasses. Both glasses have close iron and copper redox ratios and copper oxidizes iron when the iron content is smaller than the copper content. The redox speciation of iron and copper was determined using combining x‐ray and optical absorption spectroscopies in relation with the resulting color. The molar extinction coefficient of Cu 2+ was estimated from the combined analysis to be 32 mol/L/cm. The glass color change from green to blue‐green color is assigned to the decrease of the total iron content, confirming that ancient glassmakers could control the final color with the glass recipe. These results provide reference data for further spectroscopic investigations of medieval stained glasses. Comparison with ancient copper‐colored green glass compositions suggests that the higher ratio of copper to iron total contents was imposed by the more reducing melting conditions in medieval furnaces.

Hunault, Myrtille O. J. Y.↗

Viscosity of glass-forming melt at the bottom of high-level waste melter feed cold caps: Effects of temperature and incorporation of solid components

At the final stages of conversion of melter feed (glass batch) to molten glass, the transient glass-forming melt becomes a continuous liquid phase encapsulating dissolving solid particles and gas bubbles that produce primary foam at the bottom of the cold cap (the reacting melter feed in an electric glass melting furnace). The glass-forming melt viscosity plays a dominant role in primary foam formation, stability, and eventual collapse, thus affecting the rate of melting (the glass production rate per cold cap area). For several melter feeds designed for nuclear waste vitrification, we have traced the glass-forming melt viscosity during the final stages of feed-to-glass conversion as it changes in response to changing temperature and composition (resulting from dissolving solid particles). Starting with a relatively low values at the moment when the melt connects, melt viscosity reaches maximum within the primary foam layer and then decreases to its final melter-operating temperature value. We paid a particular attention to the cold-cap bottom—the boundary between the primary foam layer and the thermal boundary layer—where the melt viscosity affects the rate of melting predominantly through its effect on the temperature at which primary foam is collapsing.

Lee, Seung Min↗

Derivation of the Structural Integrity of Residual (SIR) glass model for the enhancement of waste loading

A new model based on glass structure to allow for enhanced waste loading in nuclear waste glass while maintaining chemical durability is proposed. The model is derived by splitting the molar concentrations of the targeted starting glass composition into theoretical crystalline phases anticipated to be observed during devitrification and a residual glass. An empirically derived relationship based on maintaining the residual glass structure, determined from a calculated non-bridging oxygen content, was demonstrated to successfully screen glasses for acceptable durability. The proposed model can successfully identify durable glass compositions containing 20–35 wt% Al 2 O 3 , a concentration that would significantly increase the projected waste loading in glasses processed at the Hanford Tank Waste Treatment and Immobilization Plant.

36 MATERIALS SCIENCE↗

Vibrational spectroscopy analysis of silica and silicate glass networks

Vibrational spectroscopy has been widely used to investigate various structural aspects of the glass network, and there are a plethora of papers reporting subtle but consistent changes in infrared and Raman spectral features of glass upon alterations of glass compositions, thermal histories, mechanical stresses, or surface treatments. However, interpretations of such spectral features are still obscured due to the lack of well-established physical principles accurately describing vibrational modes of the non-crystalline glass network. Due to the non-equilibrium nature of the glass network, three-dimensionally connected without any long-range orders, vibrational spectral features of glass cannot be interpreted using the analogy with those of isolated molecular moieties or crystalline counterparts. Here, this feature article explains why such comparisons are outdated and describes the recent advances made from theoretical calculations of vibrational spectral features of amorphous networks or comparisons of computational results with experimental data. For the interpretation of vibrational spectral features of silica and silicate glasses, the following empirical relationships are suggested: (i) the intensity-weighted peak position of the Si-O-Si stretch mode negatively correlates with the weighted average of the Si-O bond length distribution, and (ii) the broad band of the Si-O-Si bending mode negatively correlates with the Si-O-Si bond angle distribution. Selected examples of vibrational spectroscopic imaging of surface defects are discussed to deliberate the implication of these findings in the structure-property relationship of silica and silicate glass materials. Unanswered questions and continuing research challenges are identified.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Glass Crystallization Constraints for WTP LAW Operations: Assessment of Isothermal Treatments on Crystal Formation

Much work has been done to expand the glass composition region available for operation of the Hanford Tank Waste Treatment and Immobilization Plant. This includes the development of updated glass property-composition models as well as constraints. This report supports this effort by suggesting constraints for avoiding excessive, and likely detrimental, crystallization during melter operation while processing advanced low-activity glasses. The constraints target Cassiterite and ZrO 2 -containing phases (ZCP, e.g., Baddeleyite and Zircon) that can form when melter temperatures drop below 1100 °C. These types of crystals were found to be potentially detrimental during processing as they are denser than low-activity waste glass melts; with densities of 6.95 g/cm 3 for Cassiterite and 5.68 g/cm 3 for Baddeleyite (the most prevalent ZCP). Compared to melt densities of approximately 2.65 g/cm 3 . Thus, they have the potential to form during melter idling and settle to the bottom of the melter or inside the melter. If the crystals are present in appreciable amounts, they can result in blockages of the pour-spout riser, which impacts glass pouring and melter operation. Additionally, SnO 2 and ZrO 2 are added to glass formulations to improve glass durability. Their precipitation from the melt may reduce overall glass durability. Using previously acquired results and results from testing during this effort, the following constraints (Table S.1) were determined and are recommended to reduce the risk of forming crystals of the types and concentrations that are likely detrimental to melter operation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Product Consistency Test Results for the LAW ML1 Glasses

This report summarizes the chemical analysis of Product Consistency Test (PCT) leachates received from Pacific Northwest National Laboratory (PNNL). The leachates are from a series of quenched simulated nuclear waste glasses designated Low-Activity Waste Machine Learning (LAW ML1) glasses that were designed and fabricated at PNNL. The reported data will be used in the development, validation, and implementation of enhanced property/composition models for waste glass vitrification at Hanford. The elemental release for the study glasses is reported as normalized concentration NCi. NCi of several elements was computed for both the target and measured glass compositions, which were similar, resulting in no significant differences. Several of the glasses exhibited NC B , NC Na , and/or NC Si values that were greater than the Waste Treatment Plant (WTP) low-activity waste constraint of 4 g/L. All reference glasses included with the study glasses had measurements that fell within the expected ranges.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Product Consistency Test Results for the HLW HAlG Glasses

This report summarizes the chemical analysis of Product Consistency Test leachates received from Pacific Northwest National Laboratory (PNNL). The leachates are from a series of quenched simulated nuclear waste glasses designated High-Level Waste High Aluminum Glass that were designed and fabricated at PNNL. The reported data is provided to be used in the development, validation, and implementation of enhanced property/composition models for waste glass vitrification at Hanford. The elemental release for the study glasses is reported as normalized concentration NCi. NCi of several elements was computed for both the target and measured glass compositions. Several of the glasses exhibited NC B , NC Li , and/or NC Na values that were greater than the Environmental Assessment (EA) benchmark values. Several of the leachates from approved reference material (ARM) glasses included with the study glasses had elemental concentrations greater than the expected ranges. Two water blanks contained measurable amounts of Si; measurements confirmed by rerun samples. One water blank also contained a measurable amount of Na.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

LAW Glass Formulation to Support Melter Runs with Simulants

The major objective of this work was to prepare and characterize glass formulations in order to develop and select formulations that are compliant with contractual and processing requirements to support melter tests with each of the LAW Sub-Envelopes. Glasses that cover composition ranges of interest were prepared and characterized to ensure that selected glass compositions can tolerate expected composition variations resulting from process errors without adversely affecting processing characteristics or product quality. Glass compositions that are expected to result during transitions from one waste stream to another were also prepared and characterized. Other objectives of the work included preparation and characterization of glasses with respect to the properties of interest, optimization of sulfate loading in the glasses, evaluation of ability to achieve waste loading limits, testing to demonstrate compatibility of glass melts with melter materials of construction, and identification of glass formulation issues with respect to contract specifications and processing requirements.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Enhanced HLW glass property-composition models - phase 3

During the present phase (Phase 3) of work to enhance and expand the HLW glass property-composition models, test data for 137 glasses were collected and incorporated into the combined WTP/ORP database. The new data include those collected on glasses from two statistically designed matrices to augment the moderate alumina region (the HLW16-MA matrix covering the region of 9 wt% < Al2O3 < 12 wt% with 16 glasses) and the ultra-high alumina region (the HLW16-UHA matrix covering the region of 26 wt% < Al2O3 < 29 wt% with 29 glasses). The addition of ORP glasses over the different phases of testing has significantly expanded the combined WTP/ORP database. The compiled data include glass compositions, PCT (B, Li and Na) releases, spinel T1%, electrical conductivity, viscosity, TCLP-Cd releases, and nepheline formation upon CCC. With the exception of the CCC spinel formation data – the CCC data will be used to support the further development of nepheline models for Hanford HLW glasses.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Glass-bonded ceramic waste forms for immobilization of radioiodine from caustic scrubber wastes

Glass-bonded sodalite composite waste forms have been developed for the immobilization of liquid radioactive wastes resulting from off-gas treatment during aqueous reprocessing of used nuclear fuel, with a particular focus on 129I. The proposed composite waste form is comprised of aluminosilicate ceramic phases containing volatile radionuclides bonded with a glassy matrix. In this work, a suite of ten candidate low-temperature glass binders (ZnO-Bi2O3-based glasses and a Na2O-B2O3-SiO2 glass) were examined. Six glasses were mixed with caustic scrubber waste simulant previously converted into a sodalite-rich material (to provide glass fractions of 10 and 20 wt.%), uniaxially pressed into pellets, and sintered at 350 °C or 550 °C for 8 h in air. Iodine retention after heat treatment was assessed by neutron activation analysis, showing retention of 67-100 % of expected iodine. The aqueous durabilities of the resulting materials were then determined, following the ASTM C1308 standard test, showing iodine releases of 1 to 23 g m-2 after 4 d. The cumulative iodine release for the best performing system (a zinc-bismuth-borate glass binder) was <1 g m-2, and its iodine retention from processing was 67 %. The iodine releases compared favorably with other waste forms. In parallel, this best-performing composition was also consolidated via hot isostatic pressing (HIP) in a stainless-steel canister at 550 °C for 2 h under 100 MPa pressure. The HIPed sample was produced at the ~20 g scale and showed improved densification and minimal reaction with the canister.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Insights on the structure and properties of sodium iron phosphate glasses from molecular dynamics simulations

Iron phosphate glasses are promising nuclear waste forms while more detailed understanding of their structures and structure-property relations are still needed to better design waste glass compositions. In this work we report studies of three series of sodium iron phosphate (NFP) glasses: 60P 2 O 5 -(40-x)Fe 2 O 3 -xNa 2 O (x = 0→40), (100–2x)P 2 O 5 -xFe 2 O 3 -xNa 2 O (x = 5→17.5) and one with different iron redox ratio, to understand the composition as well as the iron redox effects on the structure and properties of these glasses using molecular dynamics simulations with effective two-body and three-body potentials. Structural analyses, including pair distribution function, bond angle distribution, Q n distribution, and polyhedral connectivity, were performed to obtain in-depth information on short-range and medium-range structural features. The P-O pair distributions showed a first peak splitting with phosphorus-bridging and non-bridging oxygen contributions. This and the average P-O and other cation-oxygen bond distances are in excellent agreement with experiments. The coordination number of P 5+ remained four while that of Fe 3+ increased from 4.30 to 4.72 with decreasing Fe/Na ratio. Polyhedral linkage analysis showed [PO 4 ] units linked with [PO 4 ] and [FeO x ] through corner-sharing while the [PO 4 ]-[FeO x ] linkages become dominant for compositions with Fe 2 O 3 larger than 15 mol%. The effect of iron redox ratio on the structure of NFP glasses was also studied and it was found that bond lengths and coordination numbers were not strongly affected, while the reduction of iron introduced higher network distortions, as evident by O-P-O bond angle and Q n distribution. The glass transition temperature (T g ) showed a monotonic increase with Fe 2 O 3 in the first series, in good agreement with experiments, while those of the second series showed a maximum at P 2 O 5 = 82 mol%. Here, calculated elastic moduli were found to increase with Fe 2 O 3 in the first glass series, which was be explained by the increase of network connectivity, while those of the second series decrease with Fe 2 O 3 due to decrease of P 2 O 5 .

36 MATERIALS SCIENCE↗

The Global LAnd Surface Satellite (GLASS) evapotranspiration product Version 5.0: Algorithm development and preliminary validation

An accurate estimation of spatially and temporally continuous global terrestrial evapotranspiration (ET) is essential in the assessment of surface energy, water and carbon cycles. The Global LAnd Surface Satellite (GLASS) ET product Version 4.0 (v4.0) based on the Bayesian model averaging (BMA) method was generated to estimate global terrestrial ET. However, certain uncertainty for the GLASS ET product v4.0 limits its application. In this study, we introduced the deep neural networks (DNN) merging framework to improve terrestrial ET estimation for GLASS ET product Version 5.0 (v5.0) generation by integrating five satellite-derived ET products [Moderate Resolution Imaging Spectroradiometer (MODIS) ET product (MOD16), Shuttleworth–Wallace dual-source ET product (SW), Priestley–Taylor-based ET product (PT-JPL), modified satellite-based Priestley–Taylor ET product (MS-PT) and simple hybrid ET product (SIM)]. We compared the performance of DNN method against other merging methods, including GLASS ET algorithm v4.0 (BMA), the gradient boosting regression tree (GBRT) method and the random forest (RF) method, based on 195 global eddy covariance (EC) flux towers covering observations from 2000 through 2015. Validations indicated that the DNN had the highest accuracy among four merging methods across different land cover types, yielding the highest average determination coefficients (R 2 , 0.62), root-mean-squared-error (RMSE, 24.1 W/m 2 ) and Kling–Gupta efficiency (KGE, 0.77) with a of 99% confidence interval. Compared with GLASS ET algorithm v4.0, the DNN improved on the R 2 by approximately 7% (p < 0.01) and the KGE by 10%. Based on the DNN, we then generated 8-day GLASS ET product v5.0 globally with a 1 km spatial resolution from 2001 to 2015 driven by GLASS vegetation and surface net radiation (R n ) datasets and Modern-Era Retrospective Analysis for Research and Applications, Version 2 (MERRA2) datasets. Finally, this global terrestrial ET product provides a valuable dataset for monitoring regional and global water resources and environmental changes.

54 ENVIRONMENTAL SCIENCES↗