Wide Range Of Glass Compositions Research Articles

Combined experiments and atomistic simulations for understanding the effect of ZnO on the sodium silicate and sodium borosilicate glass network

Combined experiments and molecular dynamics (MD) simulations were performed over wide range of glass compositions to understand the improved durability of borosilicate glass with ZnO addition. A significant change in glass structure was monitored from short range and intermediate range order parameters. The MD results were found to be in good agreement with the experimental data for Young's Modulus, glass transition temperature, and leaching. Both experiments and MD simulations report the enhanced chemical durability of glass with ZnO addition. Low R (Na2O/B2O3) and high K (SiO2/B2O3) of ZnO doped sodium borosilicate (Zn–NBS) glass surface compared to bare NBS represents the more stable structure of glass surface for Zn–NBS than NBS. The enhanced chemical resistivity of Zn–NBS was established from the increasing activation energy for diffusion of Na ions. The combined experiments and MD simulations disclose many interesting microstructure and dynamics due to the presence of ZnO in the glass.

Machine Learning Enabled Models to Predict Sulfur Solubility in Nuclear Waste Glasses.

The U.S. Department of Energy is considering implementing the direct feed approach for the vitrification of low-activity waste (LAW) and high-level waste (HLW) at the Hanford site in Washington state. If implemented, the nuclear waste with a higher concentration of alkali/alkaline-earth sulfates (than expected under the previously proposed vitrification scheme) will be sent to the vitrification facility. It will be difficult for the existing empirical models to predict sulfate solubility in these glasses or design glass formulations with enhanced sulfate loadings in such a scenario. Further, the existing models are unable to produce reliable predictions when applied to HLW glasses whose composition falls outside of the range encompassed by the database used to develop/calibrate the models. Accordingly, this study harnesses the power of artificial intelligence (machine learning, ML) with a goal to address the limitations of the existing models. Toward this, three ML models have been trained using a large database; comprising >1000 LAW and HLW glasses and encompassing a wide range of glass compositions and processing variables. Next, the ML model with the best prediction performance has been used to quantitatively assess and rank the influence (i.e., importance) of glasses' compositional/processing variables on the SO3 solubility in the glasses. Finally, on the premise of such understanding of influential and inconsequential variables, two closed-form analytical models─with disparate degrees of complexity (one highly parametrized and one with fewer input variables)─have been developed. Results show that both analytical models produce predictions of SO3 solubility in LAW and HLW glasses with an accuracy analogous to ML models and substantially higher than the analytical models that represent the current state-of-the-art. Overall, this study's outcomes present a roadmap─informed by data and channeled by artificial intelligence─that can be leveraged in the future to design nuclear waste glasses with unprecedented sulfur loadings.

Properties of glasses in the system BaO–B2O3–SiO2–xAl2O3 (x=0; 5; 10 mol.%)

This article shows the prospect of the system BaO–Al2O3–B2O3–SiO2 as the basis of vitreous and glass ceramic materials, which are widely used in rocket production for high-temperature protection of heat resistant alloys, in the power industry for sealing solid oxide fuel cells, and in the production of heat resistant glass ceramic materials. We examined the conditions of glass formation and properties of glasses with the following content of components (mol.%): BaO 30–70, B2O3 10–50, SiO2 20–60, and Al2O3 0–10. We established experimentally that the physical and chemical properties of glass, depending on its chemical composition, vary within the following limits: coefficient of linear thermal expansion of (71–122)10–7 К–1; glass transition temperature of 500–6500С; dilatometric softening point of 540–6700С; and density of 3.20–4.21 g cm–3. The volume resistivity of the studied glasses is within 1011–1013 Ohmcm at the temperature of 1500С. Generalization of the dependences of glass properties on their chemical composition was carried out with the use of the additive equations, for which the partial contributions of oxides to the values of the corresponding properties were determined by experimental and statistical methods. The established patterns of influence of components and conditions of glass formation on the physical and chemical characteristics of glasses allows implementing the process of designing of a wide range of glass compositions with the complex of specified properties in order to solve the tasks of their practical use.

Molecular Dynamics Simulation of Amorphous SiO2, B2O3, Na2O-SiO2, Na2O-B2O3, and Na2O-B2O3-SiO2 Glasses with Variable Compositions and with Cs2O and SrO Dopants.

Selection of suitable glass composition for vitrification of high-level radioactive wastes (HLWs) is one of the major challenges in nuclear waste reprocessing. Atomic and molecular level understanding of various structural, thermodynamical, and dynamical properties of a glass matrix can help in preliminary screening and thus reduce the dependency to some extent on tedious experimental procedures. In that context, extensive molecular dynamics (MD) simulations have been performed to calculate various microscopic properties of the glass matrix. The present article demonstrates that the "Buckingham potential-included long-ranged Coulomb interaction" can be utilized to simulate the glasses of varied compositions. The proposed simulation model has been validated for a wide range of glass compositions: pure glass matrix-SiO2 and B2O3; binary glass mixtures-SiO2-B2O3, Na2O-SiO2, and Na2O-B2O3; ternary glass-Na2O-SiO2-B2O3; and also the Cs2O- and SrO-doped matrix of sodium borosilicate. Most importantly, the MD results have been validated with those of in-house synthesized glasses. The effect of alkali addition on the density and network connectivity of the glass matrix has been explored. The results capture well the boron anomalies for varied concentrations of network formers and network modifiers. The intermediate structural ordering in glasses has been explored by calculating the partial and total structure factors. Further, the characteristic vibration density of states of constituent atoms in the glass matrix is determined. In addition, the glass structures with the addition of dopant oxides Cs2O and SrO have been examined as they are known to be prime heat-generating agents in HLWs. The results establish the structure and dynamics of the doped glass matrix to be a complex nature of the dopant's mass, concentration, charge, and ionic radius. The present MD results might be of great academic and technological significance for further studies in the field of vitrification and prediction of effects associated with the dopant's nature and concentration.

Hardness of oxynitride glasses: topological origin.

Oxynitride glasses are mixed-anion systems, in which the 2-fold coordinated oxygen atoms have been partially substituted by 3-fold coordinated nitrogen atoms. This so-called nitridation process introduces additional bonds and thereby constrains and compacts the glass network and consequently alters the glass hardness. To explore how and why hardness varies with the degree of nitridation, we have derived a topological model of oxynitride glass hardness using temperature-dependent constraint theory, by which the scaling of glass hardness with nitrogen content can be predicted. A linear model has been derived based on the assumption that the substitution of oxygen atoms with nitrogen atoms is responsible for the hardness increase due to the increase in the number (n) of bond-bending and bond-angular constraints. It turns out that the model agrees with the experimental observation, i.e., an approximate positive linear trend of the hardness change with nitrogen content is observed for a wide range of glass compositions. The topological model may thus be useful for designing new oxynitride glass compositions with targeted hardness values.

Peralkaline magma evolution and the tephra record in the Ethiopian Rift

The 3.119 ± 0.010 Ma Chefe Donsa phreatomagmatic deposits on the shoulder of the Ethiopian Rift mark the northern termination of the Silti-Debre Zeyit Fault Zone, a linear zone of focused extension within the modern Ethiopian Rift. These peralkaline pumice fragments and glass shards span a wide range of glass compositions but have a restricted phenocryst assemblage dominated by unzoned sanidine. Glass shards found within the ash occupy a far more limited compositional range (75–76 wt% SiO2) in comparison with the pumice (64–75 wt% SiO2), which is rarely mingled. Thermodynamic modeling shows that liquids broadly similar to the least evolved glass composition can be achieved with 50–60 % fractionation of moderately crustally contaminated basalt. Inconsistencies between modeled solutions and the observed values of CaO and P2O5 highlight the important role of fluorine in stabilizing fluor-apatite and the limitations of current thermodynamic models largely resulting from the scarce experimental data available for the role of fluorine in igneous phase stability. On the basis of limited feldspar heterogeneity and crystal content of pumice at Chefe Donsa, and the difficulties of extracting small volumes of Si-rich melt in classical fractional crystallization models, we suggest a two-step polybaric process: (1) basaltic magma ponds at mid-upper-crustal depths and fractionates to form a crystal/magma mush. Once this mush has reached 50–60 % crystallinity, the interstitial liquid may be extracted from the rigid crystal framework. The trachytic magma extracted at this step is equivalent to the most primitive pumice analyzed at Chefe Donsa. (2) The extracted trachytic liquid will rise and continue to crystallize, generating a second mush zone from which rhyolite liquids may be extracted. Some of the compositional range observed in the Chefe Donsa deposits may result from the fresh intrusion of trachyte magma, which may also provide an eruption trigger. This model may have wider application in understanding the origin of the Daly Gap in Ethiopian magmas—intermediate liquids may not be extracted from crystal-liquid mushes due to insufficient crystallization to yield a rigid framework. The wide range of glass compositions characteristic of the proximal Chefe Donsa deposits is not recorded in temporally equivalent tephra deposits located in regional depocenters. Our results show that glass shards, which represent the material most likely transported to distal depocenters, occupy a limited compositional range at high SiO2 values and overlap some distal tephra deposits. These results suggest that distal tephra deposits may not faithfully record the potentially wide range in magma compositions present in a magmatic system just prior to eruption and that robust distal–proximal tephra correlations must include a careful analysis of the full range of materials in the proximal deposit.

Development of empirical potentials for sodium borosilicate glass systems

New parameter values are proposed for the empirical potentials used to describe SiO2–B2O3–Na2O alkali borosilicate glass systems. They are based on Buckingham potentials, but include dependence between the fitting parameters and the glass chemical composition to improve the representation of the complex environment around the boron atoms. In particular, the boron anomaly (observed when the [Na2O]/[B2O3] ratio varies) is correctly reproduced. The structural and mechanical properties of a wide range of glass compositions and of reedmergnerite crystals are correctly simulated: bond distances, mean angles, densities, elastic moduli. The deviations from the experimental values are small.

Glasses and their crystallization in the (1 − х)KNbO 3· хSiO 2 system at low glass-forming oxide contents, 0 ⩽ х ⩽ 0.35

Glasses based on the K 2O–Nb 2O 5–SiO 2 system have been a subject of numerous studies thanks to promising electro-optical and non-linear optical properties. Most of the studies of Nb-containing glasses deal with compositions including not less than 40 mol% of SiO 2 or B 2O 3. In the present work, we studied glass-forming and crystallization properties of (1 − х)KNbO 3· xSiO 2 glasses with x varying from 0 to 35 mol% by melt quenching between steel plates or by exposure to air or nitrogen flow. Thin transparent glassy plates can be obtained by quenching via pressing between metal plates for glasses with x ⩾ 0.12, and transparent glass-ceramics allowing a remarkable second harmonic generation (SHG) response can be formed by heat-treatment near the first exothermic differential thermal analysis (DTA) peak over a wide range of glass compositions. It is shown that in these glasses, the crystalline K 4Nb 6O 17 phase and a small amount of ferroelectric KNbO 3, along with ceolite-like, cristobalite and α-quartz SiO 2 phases precipitate at low temperatures in the range between the glass transition point, T g, and the first exothermic peak on DTA curve, whereas ferroelectric KNbO 3 precipitates at temperatures above 800 °C. Ferroelectric crystals which precipitate in the glass bulk are shown to produce high SHG activity.

Extraordinary Laser-Induced Swelling of Oxide Glasses

We describe a novel process of laser-assisted fabrication of surface structures on doped oxide glasses with heights reaching 10 - 13% of the glass thickness. This effect manifests itself as a swelling of the irradiated portion of the glass, which occurs in a wide range of glass compositions. The extent of such swelling depends on the glass base composition. Doping with Fe, Ti, Co, Ce, and other transition metals allows for adjusting the absorption of the glass and maximizing the feature size. In the case of bumps grown on borosilicate glasses, we observe reversible glass swelling and the bump height can increase or decrease depending on whether the consecutive laser pulse has higher or lower energy compared with the previous one. The hypothetical mechanism includes laser heating of glass, glass melting, and directional flow. We review several potential applications of such glass swelling.

Survey of Potential Glass Compositions for the Immobilisation of the UK's Separated Plutonium Stocks

AbstractThe Nuclear Decommissioning Authority (NDA) has taken over ownership of the majority of the UK's separated civil plutonium stocks, which are expected to exceed 100 metric tons by 2010. Studies to technically underpin options development for the disposition of these stocks, for example by immobilization or re-use as fuel, are being carried out by Nexia Solutions on behalf of NDA. Three classes of immobilization matrices have been selected for investigation by means of previous studies and stakeholder dialogue: ceramic or crystalline wasteforms, storage MOx, and vitreous or glass-based wasteforms. This paper describes the preliminary inactive experimental program for the vitrification option, with results from a wide range of glass compositions along with conclusions on their potential use for plutonium immobilization.Following review, four glass systems were selected for preliminary investigation: borosilicate, lanthanide borosilicate, aluminosilicate and phosphate glasses. A broad survey of glass properties was completed in order to allow meaningful evaluation, e.g. glass formulation, waste loading, chemical durability, thermal properties, and viscosity. The program was divided into two parts, with silicate and phosphate glasses being investigated by Nexia Solutions and the Immobilisation Science Laboratory (ISL) at the University of Sheffield respectively.

Network connectivity in aluminoborosilicate glasses: A high-resolution 11B, 27Al and 17O NMR study

O-17 enriched calcium and potassium aluminoborosilicate glasses with compositions similar (or analogous) to commercial E-glass were made and studied by 11B, 27Al and 17O NMR in order to explore the network speciation and mixing. Fractions of non-bridging oxygens associated with silicon and boron can be obtained simply from 17O magic angle spinning (MAS) NMR, while bridging oxygen populations result from complete peak assignment of high-resolution 17O triple quantum magic angle spinning (3QMAS) NMR spectra. Dramatic differences between the two samples in boron and oxygen speciation demonstrate a large effect of the charge of the modifier cation on mixing behavior and on the stabilization of non-bridging oxygens. The observed oxygen speciation is compared with that calculated from two models: random mixing of Si, B, and Al, and mixing with avoidance of linkages between tetrahedral aluminum and tetrahedral boron groups. Mixing of B and Al in the K-containing glass tends to follow the latter, while the network speciation in the Ca-containing glass is closer to the random model. The effects of Al and Si on boron speciation are discussed, and indicate that the maximum fractions of four-coordinated boron observed in a wide range of glass compositions are closely related to tetrahedral B and Al ‘avoidance’. A modified ‘Dell and Bray’ model is proposed which seems to accurately approximate boron speciation in many alkali aluminoborosilicate glasses. The higher field strength modifier cation (Ca2+ vs. K+) promotes the formation of non-bridging oxygen, trigonal over tetrahedral boron, and at least minor amounts of five-coordinated aluminum.

Use of local raw materials

The Krasnyi Luch Glass Factory (Pskov Region) is one of the oldest glass factories in the North-West of Russia. It produces a wide range of illumination and signal glass fittings for railways and automobiles. This production is characterized by a wide range of glass compositions and small production lots.

Optimisation of borophosphosilicate glass compositionsfor silica-on-siliconintegrated optical circuits fabricated by the sol-gel process

Silica-on-silicon channel guide devices fabricated in sol-gel borophosphosilicate glass deposited by repetitive spin-coating and rapid thermal annealing (SC-RTA) are described. Process parameters for a wide range of glass compositions are given. The optimum performance is obtained using a borosilicate buffer layer, a phosphosilicate core and a borophosphosilicate cladding with a low melting point. Low-loss thermo-optic interferometric modulators fabricated by this process are described.

Observations on the fabrication of useful superconductors in the Bi-Sr-Ca-Cu-O system via the glass route

A study of the devitrification of glasses in the system Bi2O3-SrO-CaO-CuO has been carried out to assess the feasibility of producing useful superconducting material particularly in wire form. A wide range of glass compositions in this system has been devised, prepared and devitrified to produce glass-ceramics. DTA, XRD, EDS and density measurements have been made. The results of the study show that materials produced in this way are of low strength and contain voids, characteristic of glass-ceramics with low nucleation density. These defects must be overcome for useful materials to be produced.

Differential pulse voltammetric determination of arsenic(III, V) and antimony (III, V) in glasses

Analytical methods based on differential pulse voltammetry (DPV) have been described for the determination of total As, As(III), As(V), total Sb and Sb(III) as trace to minor constituents in complex glasses. For total As, the sample is decomposed with HF-H2SO4-KMnO4. The As(V) is chemically reduced to As (III) by hypophosphite and a DPV scan is carried out at the dropping mercury electrode from −0.2 to −0.7 Vvs. SCE (Ep−0.41V). As(V) is determined by decomposing the sample in HF-H2SO4 and volatilizing the As(III) as AsF3. The chemical reduction of As(V) and the DPV scan are then applied. If the glass can be decomposed with cold HF, the As(III) present in the glass can be determined by applying the DPV scan after cold sample-dissolution. For Sb(III), the sample is decomposed with HF-H2SO4, diluted, and adjusted to 1M in HCl. A DPV scan is conducted from −0.03 to −0.5 V (Ep −0.15 V). Sb(V) is not reduced in the 1M HCl supporting electrolyte. Total Sb is determined by using an aliquot of the sample solution adjusted to 6M in HCl. The DPV sweep is carried out from −0.5 to −0.1 V [Ep for Sb(V) and Sb(III) is −0.30 V]. The methods have been applied to a wide range of glass compositions and the results compared with values obtained by spectrophotometry and coulometric titration.