Raman Spectra and the Structure of Melts in the Na2O–P2O5–SiO2System

Raman spectra of melts in the Na₂O–P₂O₅–SiO₂system are measured at high temperatures. The differences between the Raman spectra of melts and glasses with identical compositions are considered. It is demonstrated that the structural inhomogeneity of the system slightly increases with a decrease in temperature and vitrification of the melt.     

On the Nature of Current Carriers in Glasses of the NaF–Na2O–B2O3 System

Glasses in the Na₂O–B₂O₃, NaF–Na₂O–B₂O₃, and NaF–B₂O₃ systems have been synthesized. The nature of current carriers and their transport numbers in these glasses are determined by the Hittorf and Tubandt techniques. The concentration dependences of the electrical conductivity and the transport numbers are investigated. It is demonstrated that the electricity transport in glasses in the NaF–B₂O₃ system is provided by sodium and fluorine ions. The results obtained are interpreted in terms of the microinhomogeneous glass structure.     

Thermal Expansion of Melts and Glasses in the As–Se System

The bulk thermal expansion coefficients of glasses and melts in the As–Se system are measured in the temperature range 298–1200 K. In glass-forming melts containing 40–60 mol % As, an increase in the density is found at temperatures above 1000 K, which is assumed to be associated with changes in the structure and character of the chemical bonding.     

Crystallization of Glasses in the K2O–Nb2O5–SiO2System

The changes in the structure and phase composition of glasses in the K₂O–Nb₂O₅–SiO₂system upon their heat treatment in the temperature range 700–800°C are studied by the small-angle X-ray scattering (SAXS) technique and X-ray powder diffraction. It is demonstrated that the crystallization is the primary process giving rise to microinhomogeneities in glasses due to heat treatment. Nanocrystals of an unidentified niobium-containing phase precipitate in glasses with the formation of regions with a decreased content of potassium and niobium oxides. An increase in the duration of heat treatment at the studied temperatures results in an increase in the size of nanocrystals without change in their phase composition. This is accompanied by the disappearance of diffusion zones, which leads to a decrease in the SAXS intensity in the range of small scattering angles and, correspondingly, to a decrease in the light scattering intensity.     

A Study of the Acid–Base Properties of Melts in the Na2O–B2O3–SiO2System: I. Composition Joins with a Na2O Content of Less Than 20 mol %

Three composition joins in the Na₂O–B₂O₃–SiO₂system at constant Na₂O contents of 5, 10, and 15 mol % are studied by the high-temperature method of determining oxygen ion exponents pO for oxide melts. It is found that the basicity of melts increases in going from the binary sodium borate system to the sodium silicate system. The acid–base properties of ternary melts are simulated under the assumption that their basicity is determined by the interaction in pseudobinary systems. It is shown that the basicity of the studied melts is governed, to a large extent, by the formation of the Na₂O · B₂O₃· 2SiO₂ternary compound.     

Effect of Fluorine Ion on the Electrical Properties of Glasses in the Na2O–P2O5 System

The temperature–concentration dependence of the electrical conductivity of glasses in the NaPO₃–NaF system has been investigated. The regularities revealed are interpreted from the standpoint of the structural microinhomogeneity of glasses, which is due to the formation of polar structural units of the Na⁺[O^–POO_2/2], Na₂ ⁺[O^– ₂POO_1/2], Na⁺[F^–POO_2/2], and Na⁺F^– types. It is shown that the concentration dependence of the electrical conductivity is governed by the ratio between the concentrations of these structural units.     

Glass Formation and Properties of Glasses in the PbO–ZnO–B2O3System

Glasses in the PbO–ZnO–B₂O₃system with a lead oxide content of less than 65 mol % are studied. The glass formation region for these glasses is determined. Their crystallization ability, density, and moisture resistance and the thermal, optical, and electrical properties are investigated. The composition–property curves are constructed. It is found that these dependences exhibit anomalies for glasses along the composition joins with constant boron oxide contents of 40 and 50 mol %. These anomalies can be associated with the change in the role of lead ions in the glass structure.     

Liquid Immiscibility Phenomena in Melts of the ZrO2–FeO–Fe2O3 System

The ZrO₂–FeO _x melts prepared by induction melting in a cold crucible in air are investigated experimentally. It is found that the immiscibility region exists in the liquid phase. The theoretical fusibility curves (calculated according to the authors' DIATRIS 1.2 program) for the ZrO₂–FeO–Fe₂O₃ system are compared with the experimental temperatures of the formation of the secondary phase, liquidus and solidus lines, and X-ray microprobe spectroscopic and X-ray powder diffraction data for quenched and slowly cooled samples. It is demonstrated that the immiscibility region in the liquid phase in an air atmosphere is observed in the temperature range 1870–2230°C and the concentration range 34–82 wt % ZrO₂.     

A Study of the Acid–Base Properties of Melts in the Na2O–B2O3–SiO2 System: II. Composition Joins with Sodium Oxide Contents of 25, 30, and 35 mol %

The exponent of oxygen ion activity pO = for melts in the Na₂O–B₂O₃–SiO₂ system along the composition joins with constant sodium oxide contents of 25, 30, and 35 mol % is studied by an electromotive force (emf) technique at 950°C. Measurements are performed using two variants of the technique of determining pO, namely, in high-temperature salt solutions of oxide systems in KF and with a salt bridge between two oxide melts. It is shown that the basicity of melts increases with an increase in the Na₂O content at a constant concentration ratio of glass-forming oxides. The acid–base properties of sodium borosilicate melts are simulated under the assumption of acid–base interaction between the components. It is found that the basicity of the studied melts along the composition joins with constant sodium oxide contents of 30 and 35 mol % is governed primarily by the acid–base interaction in Na₂O–B₂O₃ and Na₂O–SiO₂ binary systems and, to a lesser extent as compared to low-alkali composition joins (below 20 mol % Na₂O), by the formation of Na₂O · B₂O₃ · 2SiO₂ and Na₂O · B₂O₃ · 6SiO₂ ternary compounds.     

Volatilization of fluorine in a CaO–SiO2–CaF2-based system with the substitution of Na2O with K2O

Cuspidine-based systems are used to control the crystallization in mold fluxes, which is enabled by CaF₂ additions. However, excess CaF₂ increases the corrosion of casting machines. Therefore, Na₂O and K₂O are added to the mold flux system to ensure an optimized crystallization and lubrication ability of the flux with the CaF₂ content. This study investigated the effect of substituting Na₂O with K₂O on the volatilization of fluorine in a CaO–SiO₂–CaF₂-based slag system at high temperatures. The substitution of Na₂O with K₂O was performed at 5 mol% intervals. The volatilization was observed by thermogravimetric analysis under several isothermal conditions. The mass loss was measured at a heating rate of 5, 10, and 20 K/min. As the temperature increased, the volatilization of the mixed samples increased. The activation energy was calculated using the Flynn–Wall–Ozawa and Kissinger–Akahira–Sunose methods. A kinetic analysis of the volatilization of fluorine was conducted using the calculated parameters and several known kinetic models. Consequently, the volatilization of the Na-rich sample was controlled by chemical reactions and that of the K-rich sample was identified to be controlled by a phase-boundary-controlled reaction. These results suggest that the addition of mixed alkali oxide promote the volatilization during the early stages of the reaction. From the post-experimental composition analyses, the remaining Na and K in the samples suggested a different mechanism for the Na and K volatilization. The volatilization of Na increased with time, whereas K volatilized easily during the beginning of the reaction.     

Glass Formation in the MgO–B2O3–SiO2 System

Silicon - The glass formation region in the MgO–B2O3–SiO2 system was determined by the conventional melt-quenching technique at 1450 °C. The homogeneous transparent...     

The Impact of Cr2O3 on the Mechanical,Physical, and Radiation Shielding Characteristics of Na2B4O7–CaO–SiO2 Glasses

Silicon - The rapid-quenching route was used to prepare Na2B4O7–CaO–SiO2 glass formulations with various Cr2O3 concentrations. XRD analyses were used to determine the amorphous states...     

Calculation of the Viscosity of Glass-Forming Melts: VI. The R2O–B2O3–SiO2and RO–B2O3–SiO2Ternary Borosilicate Systems

A method for calculating the viscosity from composition and temperature for melts in the R _m O _n –B₂O₃–SiO₂systems is proposed. The change in the concentrations of structural groups depending on the melt composition is taken into account in calculations. The results of calculations are compared with the experimental data available in the literature on the viscosity of 1200 melts with the use of the SciGlass information system. The root-mean-square deviation between the experimental and calculated characteristic temperatures varies from 30 K (for the glass transition temperature and the Littleton point) to 50 K (for a viscosity of 10⁴P).     

Thermal Stability and Crystallization Kinetics of MgO–Al2O3–B2O3–SiO2 Glasses

To support commercialization of the MgO–Al₂O₃–B₂O–SiO₂-based low-dielectric glass fibers, crystallization characteristics of the relevant glasses was investigated under various heat-treatment conditions. The study focused on the effects of iron on the related thermal properties and crystallization kinetics. Both air-cooled and nucleation-treated samples were characterized by using the differential thermal analysis/differential scanning calorimeter method between room temperature and 1200°C. A collected set of properties covers glass transition temperature (T_g), maximum crystallization temperature (T_p), specific heat (ΔC_p), enthalpy of crystallization (ΔH_cryst), and thermal stability (ΔT=T_p—T_g). Using the Kinssiger method, the activation energy of crystallization was determined. Crystalline phases in the samples having various thermal histories were determined using powder X-ray diffraction (XRD) and/or in situ high-temperature XRD method. Selective scanning electron microscope/energy-dispersive spectroscopy analysis provided evidence that crystal density in the glass is affected by the iron concentration. Glass network structures, for air-cooled and heat-treated samples, were examined using a midinfrared spectroscopic method. Combining all of the results from our study, iron in glass is believed to function as a nucleation agent enhancing crystal population density in the melt without altering a primary phase field. By comparing the XRD data of the glasses in two forms (bulk versus powder), the following conclusions can be reached. The low-dielectric glass melt in commercial operation should be resistant to crystallization above 1100°C. Microscopic amorphous phase separation, possibly a borate-enriched phase separating from the silicate-enriched continuous phase can occur only if the melt is held at temperatures below 1100°C, that is, below the glass immiscibility temperature. The study concludes that neither crystallization nor amorphous phase separation will be expected for drawing fibers between 1200°C and 1300°C in a commercial operation.     

Chemical Stability of ZnO–Na2O–SO3–P2O5 Glasses

We report on chemical stability and corrosion behavior of highly depolymerized sulfophosphate glasses from the system ZnO–Na₂O–SO₃–P₂O₅ in aqueous solution, providing data on weight loss, ion release rates, and modifications of surface topology as a function of time, temperature and pH value. Observations seem consistent with the previously developed structural model of chemical heterogeneity, where cations Na⁺ and Zn²⁺ cluster selectively in the vicinity of sulfate and phosphate anions, respectively.     

Electrical Properties and the Structure of Glasses in the xNa2O–(1 – x)2PbO · B2O3 System

The temperature–concentration dependences of the electrical conductivity and the activation energy for electrical conduction of glasses in the Na₂O–B₂O₃ and Na₂O–2PbO · B₂O₃ systems are studied. The investigation into the nature of the electrical conduction in these glasses reveals that the contribution from the electronic component (10^–3%) of the conductivity is within the sensitivity of the Liang–Wagner technique. A considerable alkali conductivity is observed upon introduction of more than 12 mol % Na₂O. The true transport number of sodium _Na is as large as unity at [Na₂O] 15 mol %. It is shown that the observed temperature–concentration dependences of the electrical and transport properties are governed by the ratio between the concentrations of polar and nonpolar structural–chemical units of the Na⁺[BO_4/2]^–, Na⁺[O^–BO_2/2] Na⁺[O^–BO_2/2], Pb²⁺ _1/2[BO_4/2]^–, Pb²⁺ _1/2[O^–BO_2/2], and [BO_3/2] types.     

Thermal expansion and characteristic points of –Na2O–SiO2 glass with added oxides

A differential method with an optical lever system was used to determine the thermal expansion of the glasses based on Na₂O–SiO₂ and containing the following oxides: Al₂O₃, CaO, TiO₂, ZnO, Al₂O₃–TiO₂, CaO–TiO₂, or ZnO–TiO₂. The determination was carried out on both as-drawn and annealed rods. The influence of the thermal history as well as of the added oxide(s) on the thermal expansion of glasses is dealt with in this paper. The experimental results for the thermal expansion of annealed rods show that the addition of CaO–TiO₂ in the glass has the lowest value while the addition of CaO in the glass has the highest value for the coefficient of linear expansion. At the same time, the characteristic points of the annealed glasses, determined from the expansion-temperature curves, show that the addition of ZnO in the glass has the lowest values while the addition of TiO₂ in the glass has the highest values.