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.     

On the Possibility of Forming Complexes with the Participation of O2– Ions in Melts and Glasses of the Na2O–SiO2–Cu2O System

The structural role of copper ions in melts (glasses) of the Na₂O–SiO₂–Cu₂O–CuO system is analyzed in the framework of the acid–base concept with due regard for the geometric (the radius ratio for Cu²⁽¹⁾⁺ and O^2– ions) and energy (the mean enthalpies of the Cu²⁽¹⁾⁺–O bonds) factors. It is demonstrated that copper ions in the structure fulfill the function of modifier cations. In these melts, the Cu¹⁺–Cu²⁺ redox equilibrium can be described without regard for the formation of [Cu²⁽¹⁾⁺O_4/2]^2(3)– ionic complexes (which could be incorporated into the structure of silicon–oxygen anions) and [Cu²⁺O _b/k ]^{2 – b/k} polyhedra providing the interaction between Cu²⁺ ions and anions. The influence of the formation of these polyhedra on the redox equilibrium is considered within the formalism of chemical thermodynamics. The composition dependence of the oxygen ion exponent pO is measured by an electromotive force (emf) technique. The ratio between the numbers of copper atoms with different valences is determined by chemical analysis. The experimental data obtained are in agreement with the theoretical inferences.     

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.     

Effect of Tungsten Oxide on the Crystallization Properties of Glasses of the B2O3–La2O3–Nb2O5 System

Glass Physics and Chemistry - The effect of tungsten oxide on the crystallization properties of glasses of the 37.5B2O3 22.5La2O3 (40 – x)Nb2O5 xWO3 (where x = 10, 15, 20, 30, 40 mol %)...     

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.     

Dielectric Relaxation in CaO–Bi2O3–B2O3 Glasses

Glasses in the system CaO–Bi₂O₃–B₂O₃ (in molar ratio) have been prepared using melt-quenching route. Ion transport characteristics were investigated for this glass using electric modulus, ac conductivity and impedance measurements. The ac conductivity was rationalized using Almond–West power law. Dielectric relaxation has been analyzed based on the behavior of electric modulus behavior. The activation energy associated with the electrical relaxation determined from the electric modulus spectra was found to be 1.76 eV, close to that the activation energy for dc conductivity (1.71 eV) indicating that the same species took part in both the processes. The stretched exponent β (0.5–0.6) is invariant with temperature for the present glasses.     

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.     

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...     

Comparative studies on the bioactivity of some borate glasses and glass–ceramics from the two systems: Na2O–CaO–B2O3 and NaF–CaF2–B2O3

Combined FTIR spectroscopy and X-ray diffraction analysis have been employed to investigate the bone-bonding ability or bioactivity of some prepared borate glasses and their glass–ceramic derivatives from the two systems (Na₂O–CaO–B₂O₃) and (NaF–CaF₂–B₂O₃). The present study includes the mentioned FTIR spectral and X-ray analytical techniques before and after immersion of the glasses and glass–ceramics for 2 weeks in 0.025 M sodium phosphate (Na₂HPO₄) solution. Also, the work extends to evaluate the corrosion behavior for specified grains of the studied samples (0.3–0.6 mm) after immersion in phosphate solution for 2 weeks at 37 °C. The FTIR spectra of the two glass systems after immersion show some changes in the vibrational bands than before immersion. The generation of the characteristic peaks at about 580 and 680 cm⁻¹ after immersion confirms the bone bonding ability by the formation of hydroxyapatite phase. The X-ray diffraction studies show the separation of (CaF₂) which is known to be an efficient nucleator. Weight loss data show a difference in solubility in the sodium phosphate solution between fluoride and oxide glass systems due to the strong action of the leaching solution and ease of solubility of fluoride glasses than corresponding oxide glasses in this solution. SEM data indicate the formation of small rounded or nodular shape crystals which are characteristics for the formation of hydroxyapatite layer and complete agreement with X-ray data.     

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.     

A Study of Ionic Conductivity of Glasses in the PbCl2–PbO · B2O3 and PbCl2–2PbO · B2O3 Systems

The steady-state electrical conductivity of oxychloride glasses in the PbCl₂–PbO · B₂O₃ and PbCl₂–2PbO · B₂O₃ systems is investigated. In the temperature range from 190 to 380°C, the dependence of log on the reciprocal of the temperature exhibits a linear behavior. The nature of charge carriers is studied using the Hittorf technique. It is demonstrated that protons and chlorine ions are charge carriers in solid glasses. The concentration dependence of the transport numbers of chlorine ions is examined by the Tubandt method. The contribution of the electronic component to the total electrical conductivity is estimated with the use of the Liang–Wagner technique. The concentration dependences of the electrical conductivity and the transport numbers of chlorine ions are interpreted in terms of the microinhomogeneous glass structure associated with the selective interaction of components during synthesis of glasses.     

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.     

Glass Formation in the ZrF4–LaF3–BaF2–NaF System

The glass formation in the ternary ZrF₄–LaF₃–BaF₂and quaternary ZrF₄–LaF₃–BaF₂–NaF systems at a zirconium fluoride content of 50–60 mol % is investigated. The glass formation region in the ternary system has the shape of a petal and lies along the LaF₃–BaZr₂F₁₀join. The glass formation regions in the quaternary system are either localized or continuous depending on the zirconium fluoride content. The glass transition temperatures T_gfall in the range 180–290°C, and the temperatures of the onset of crystallization lie in the range 250–340°C. Glasses crystallize in one, two, or three stages. The melting temperature varies in the range from 390 to 650°C. The microhardness of glasses is measured. The compositions of the most stable glasses are determined.     

Near Constant Loss Dielectric Response in 2Bi2O3–B2O3 Glasses

Electrical conduction and relaxation phenomena in bismuth borate glasses in the composition 2Bi₂O₃–B₂O₃ (Bi₄B₂O₉) were investigated. Dielectric studies carried out on these glasses revealed near constant loss response in the 1 kHz–1 MHz frequency range at moderately high temperatures (300–450 K) associated with relatively low loss (tan δ = 0.006) and high dielectric constant (ε_r′ = 37) at 1 kHz, 300 K. The variation in AC conductivity with temperature at different frequencies showed a cross over from near constant loss response characterized by local ion vibration within the potential well to universal Jonscher's power law dependence triggered by ion hopping between potential wells or cages. Thermal activation energy for single potential well was found to be 0.48 ± 0.05 eV from cross over points. Ionic conduction and relaxation processes were rationalized by modulus formalism. The promising dielectric properties (relatively high ε_r′ and low tan δ) of the present glasses were attributed to high density (93% of its crystalline counterpart), high polarizability, and low mobility associated with heavy metal cations, Bi³⁺.     

Calculation of the Structural Linear Expansion Coefficient from the Chemical Composition of Glasses in the R2O(RO)–Al2O3–B2O3 (R = Li, Na, Ca, and Ba) System

The regularities of the influence of the glass composition on the structural linear expansion coefficient in the glass transition range are analyzed using the published data obtained in systematic experimental investigations of glasses in the R ₂O(RO)–Al₂O₃–B₂O₃ (R = Li, Na, Ca, and Ba) system. A method is proposed for calculating the structural linear expansion coefficients of these glasses from the chemical composition with a mean relative error of 10%. The possibilities of extending the composition range covered by the calculation are considered.     

Glass Formation and Luminescence of Glasses in the Ga2S3–GeS2–Nd2S3System

The results of spectral measurements and the differential thermal analysis (DTA) data for glasses in the Ga₂S₃–GeS₂–Nd₂S₃system are presented. The boundaries of the glass formation region in the Ga₂S₃–GeS₂–Nd₂S₃system are determined. It is shown that the luminescence efficiency increases with an increase in the gallium sulfide content due to the displacement of the concentration quenching boundary of Nd³⁺luminescence with a change in the glass matrix composition.     

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.