Reduction of copper in soda-lime-silicate glass by hydrogen

The reduction of copper in soda-lime-silicate glasses by hydrogen was measured as a function of time and copper content within the temperature range 440 to 650°C. Copper is reduced to the metallic state in a surface layer whose thickness increases with time and temperature and decreases with copper content. A well developed periodical precipitation of copper particles is observed in the reduced layer. The reduction is accompanied by an alteration of the glass composition in which there is an increase of the copper content and a reduction of the calcium content. The growth kinetic of the reduced layer, followed by optical spectroscopy and measurement of the layer thickness, is analyzed with regard to the tarnishing model.     

Thermodynamics of the Cu/Cu-redox equilibrium in soda-silicate and soda-lime-silicate melts

The thermodynamics of the redox equilibrium of Cu⁺/Cu²⁺ were determined by square-wave voltammetry in glass melts with the base mol% compositions x Na₂O · (100 − x) SiO₂ (x = 15, 20, 26 and 33) and (26 − x) Na₂O · x CaO · 74 SiO₂ (x = 0, 5, 10 and 15) doped with 1 mol% CuO in the temperature range from 850 to 1150 °C. All recorded voltammograms showed two maxima attributed to the reductions of Cu²⁺ to Cu⁺ and Cu⁺ to metallic copper. Both peaks are shifted to smaller potentials with decreasing temperature. With increasing melt basicity, the [Cu⁺]/[Cu²⁺]-ratio first increases, and remains constant for optical basicities >0.56. The effect of composition on the redox equilibrium is explained by the incorporation of both Cu⁺ and Cu²⁺ in octahedral coordination into the melt structure.     

A novel process utilizing subcritical water to recycle soda-lime-silicate glass

Colored soda-lime-silicate glass was successfully converted into silica by a novel process of hydrothermal treatment in subcritical condition followed by leaching in nitric acid. This method may provide a new non-toxic and low-energy consuming process for the recycling of inorganic wastes.     

Sub-critical crack growth rate of soda-lime-silicate glass and less brittle glass as a function of fictive temperature

Sub-critical crack growth rates of soda-lime-silicate glass and less brittle glass with different fictive temperatures were compared using the DCDC method under both dry and humid atmospheres in order to investigate the origin of the unique mechanical features of the less brittle glass developed by Ito and his collaborators. In both dry and humid atmospheres, the crack velocity of the soda-lime-silicate glass was slower than that of the less brittle glass. For both glasses, the glass sample with higher fictive temperature showed a slower crack growth rate under both dry and humid atmospheres. These observations can be explained by the tendency for the plastic flow at the crack tip; the soda-lime-silicate glass is expected to show easier plastic flow under tension than the less brittle glass, and also the samples with higher fictive temperatures are expected to show easier plastic flow, leading to greater fracture toughness, K_IC, and slower crack growth rate.     

Effect of stirring on striae in glass melts

Chemical striae have often negative effect on the glass properties, and hence, elimination of striae has been a key issue in glass science and technology. To produce highly homogeneous glasses, it is necessary to stir melts during the melting process. To explore the physical origin of the stria elimination during stirring, and to optimise the homogenisation process, both simulations of striation and homogenisation experiments are performed. The results show that stirring broadens the stria size distribution in the melt through conversion of larger striae into smaller ones. Only the striae with a size below half the diffusion length in the melt can be eliminated during the melting process. Stirring itself does not homogenise the melt, but enhances the stria elimination rate by generating small striae.     

Inward cationic diffusion in glass

We report that inward diffusion of network-modifying divalent cations can occur in iron-containing silicate glasses when they are treated in a reducing atmosphere near the glass transition temperature. As a result of the inward diffusion, a silica-rich nanolayer forms on the glass surface, which increases the hardness and chemical durability. The thickness of the layer can be controlled by varying the heat-treatment conditions. We clarify the mechanism of the inward diffusion and calculate the diffusion coefficient for the network-modifying divalent cations. We demonstrate that the diffusion of these ions is the rate-limiting factor for the reduction process.     

The optimal parameters of bubble centrifuging in glass melts

The mathematical model of a multicomponent bubble in a glass melt under the influence of gravitational and centrifugal fields has been applied in the model TV glass. The optimal fining conditions have been examined in a rotating cylinder with the aim of determining their general features. All of the dependences between the bubble-removal time and the rotational velocity showed the region of bubble removal by centrifuging at low cylinder rotational velocities and the region of complete bubble dissolution when the rotation was intensive. The low rotational velocities, characterised by the minimal bubble-centrifuging time, appeared to be suitable for industrial application. Consequently, the influence of temperature, pressure and glass-layer thickness on the value of the optimal rotational velocity and optimal fining time of small-critical bubbles has been investigated in detail in a glass melt containing fining agent. The significant role of temperature and minor role of pressure have been proved and the identical features of bubble removal have been identified in cylinders with different radii and filling by glass but with the same average thickness of the glass layer on the cylinder walls.     

Redox behavior and diffusion of copper in soda-lime-silica melts

Glasses with the base mol% composition xNa₂O · 10CaO · (90 ? x)SiO₂ with x = 10, 16, 20 and 26 were investigated at high temperatures using square-wave voltammetry. The recorded voltammograms exhibit two peaks. That at less negative or (depending on temperature and glass composition) even positive potential is attributed to the reduction of Cu²⁺ to Cu⁺, while that observed at more negative potential is caused by the reduction of Cu⁺ to metallic copper. For both redox steps, the peak potentials decrease linearly with temperature. Those of the composition with 10 mol% Na₂O show the most negative values. The diffusion coefficients can be fitted to Arrhenius equation. If referenced to the same viscosity, the diffusion coefficients decrease with increasing Na₂O-concentration. The effect of composition on the thermodynamics as well as on diffusivities is explained by the incorporation of the copper ions into the melt structure.     

Quantitative model studies of stirrers for laboratory glass melts

The stirrers widely used in practice are investigated and compared in the present work using the method of quantitative assessment of homogeneity.     

Water and the glass transition temperature of silicate melts

Literature data on the effect of water on the glass transition in silicate melts are gathered for a broad range of total water content c_w from 3 × 10⁻⁴ to 27 wt%. In terms of a reduced glass transition temperature T_g^*=T_g/T_g^GN, where T_g^GN is T_g of the melt containing c_w≈0.02 wt% total water, a uniform dependence of T_g^* on total water content (c_w) is evident for silicate melts. T_g^* decreases steadily with increasing water content, most strongly at the lowest water content where H₂O is dominantly dissolved as OH. For water-rich melts, the variation of T_g^* is less pronounced, but it does not vanish even at the largest water contents reported (≈27 wt%). T_g^* vs. c_w is fitted by a three-component model. This approach accounts for different transition temperatures of the dry glass, hydroxyl and molecular water predicting T_g^* as a weighted linear combination of these temperatures. The required but mostly unknown water speciation in the glasses was estimated using IR-spectroscopy data for hydrous sodium trisilicate and rhyolite.     

Diffusion of the S isotope in soda-lime-silica and sodium trisilicate glass melts

The diffusivity of sulphur in nominal 10 Na₂O-16 CaO-74 SiO₂ (NCS) and 26 Na₂O-74 SiO₂ (NS3) melts was investigated in the temperature range 1273-1473 K using the ³⁵S radioactive isotope in a sandwich setup. Samples were sealed in platinum capsules and run with vertical alignment at 100 MPa confining pressure in an internally heated gas pressure vessel. Using the lowest diffusion coefficient D (m² s^− 1) for each temperature the Arrhenian relations logD = −(4.6 ± 0.3) − (216 ± 7) kJ mol^− 1/RT for NCS and logD = −(6.3 ± 0.6) − (167 ± 17) kJ mol^− 1/RT for NS3 were determined. Viscosity of the melts was used to test the applicability of the Stokes-Einstein (SE) and the Eyring (EY) equations to sulphur diffusion. The SE equation yields unrealistically low radii of the diffusing particles, a consequent of the non-molecular structure of the silicate melts. On the other hand, the Eyring relation yields reasonable jump distances of 550 pm (NCS) and 750 pm (NS3) by fitting the diffusion data to the EY equation. These large values imply that sulphate ions (ionic diameter = 290 pm) migrate as large entities through the silicate network.     

Oxygen and silver diffusion into float glass

In the float glass process, molten glass is floated on a molten metallic tin bath, such that tin penetrates the glass surface. Consequently, the glass has distinctly two different faces; the tin-penetrated face (bottom face) and the opposite face (top face). In this paper, the effects of tin on oxygen and silver diffusion into the top and bottom faces of a soda–lime–silica float glass are reported. It was revealed that oxygen diffusion from the atmosphere into the bottom face at temperatures above glass transition temperature was extremely suppressed near the surface region of the glass. This was not observed for the top face. This effect was ascribed to chemical reactions between the diffused oxygen and Sn²⁺ near the surface of the glass. Silver diffusion was also influenced by the tin due to chemical reactions of Ag⁺ ions with Sn²⁺, leading to the precipitation of nanometer-sized Ag crystals. As a result, the coloration due to the surface plasmon resonance of the Ag crystals was significantly different between the top and bottom faces because of differences in the nucleation and growth processes associated with the Ag crystals.     

Self-diffusivity of iron in alkali–lime–alumosilicate glass melts

Self-diffusion coefficients of iron were measured in glass melts with the basic mol% composition of 16 R₂O, 10 CaO, x Al₂O₃ and (74 − x) SiO₂ with x=0, 5, 10, 15 and R=Li, Na, K and Cs in the temperature range of 900–1300°C using square-wave voltammetry. All diffusion coefficients had an Arrhenian dependence which depended on the type of alkali present and the Al₂O₃-concentration. Larger alkali cations, e.g. Cs⁺, as well as an increase in the Al₂O₃-content led to a decrease in the diffusion coefficients and also to an increase in viscosity. Within one glass composition, the Stokes–Einstein equation is fulfilled with respect to the dependence of the diffusivity upon viscosity. At constant viscosity, however, increasing size of the alkali cation and increasing Al₂O₃-content led to larger iron diffusion coefficients.     

Compositional dependence of fragility and glass forming ability of calcium aluminosilicate melts

The compositional dependence of glass forming ability (GFA) of two series of calcium aluminosilicate melts is studied by measuring their viscous behavior and crystallization tendency. The first series consists of five compositions on the joining line between the eutectic point of anorthite–wollastonite–tridymite and that of anorthite–wollastonite–gehlenite. The series includes the eutectic compositions as end members. The second series consists of five compositions on a line parallel to the joining line on the alumina rich side. In the present work, GFA is described in terms of glass stability. The Hrubÿ parameter (K_H) [A. Hrubÿ, Czech. J. Phys. B 22 (1972) 1187] obtained from calorimetric data is used as a measure of glass stability. From the viscous behavior of the undercooled melts studied by viscometry the fragility (m) is derived. The results show that m is inversely proportional to K_H for the two series of melts, proposing m as an indirect measure of GFA. However, this proportionality is only valid for comparison of the glasses in the series of systematic substitutions of components. In general, the melts on the joining line between the two eutectic compositions are found to have superior GFA. Within each series GFA increases as a function of the network polymerization.     

Voltammetric approach to redox behavior of various elements in cathode ray tube glass melts

The redox behavior of various elements (Fe, Sb, Ce, Ti, Zn) was investigated in alkali–alkaline earth-silica CRT (Cathode ray tube: TV panel) model glass melts using the square-wave voltammetry (SWV). The current–potential curve, so called voltammogram, was produced at temperature range of 1000–1400 °C under the scanned potential between 0 and –800 mV at 100 Hz. The Fe, Ti and Zn doped melts exhibited one peak due to reduction reaction. In the case of the Sb doped melts, two traces doubted as peak were found in the voltammogram at low temperature while only one peak existed at high temperature. The peak potential was shifted to the negative direction with decrease of temperature, however, its temperature dependence showed linearity. On the other hand, no peak was found in voltammogram of the melts doped with Ce. Based on the temperature dependence of the peak potential, standard enthalpy (ΔH⁰) and standard entropy (ΔS⁰) for the reduction of Fe³⁺ to Fe²⁺, Sb³⁺ to Sb⁰ and Zn²⁺ to Zn⁰ in CRT model glass melts were calculated.     

Water diffusion into a silica glass optical fiber

The diffusion coefficient and solubility of water in silica glass optical fiber cladding were measured in the temperature range of 600-800 °C and were compared with the corresponding values of bulk silica glasses. It was found that the diffusion coefficient was slightly lower and the solubility was appreciably higher in optical fiber, especially at low temperatures, compared with those in bulk silica glasses. The observed trend was consistent with the expected effect of fictive temperature.     

Ac conductivity and dielectric relaxation in ionically conducting soda-lime-silicate glasses

The frequency dependent conductivity and dielectric relaxation of alkali ions in some soda-lime-silicate (Na₂O-CaO-SiO₂) glasses are investigated over a frequency range from 50 Hz to 1 MHz and in a temperature range from room temperature to 603 K by using alternating current impedance spectroscopy. The conductivity isotherms show a transition from frequency independent dc region to dispersive region where the conductivity continuously increases with increasing frequency. The electric modulus representation has been used to provide comparative analysis of the ion transport properties in these glasses. The scaling behavior of imaginary part of electric modulus indicates that all dynamical processes occurring at different frequencies give the same activation energy.     

Composition dependence of the optical absorption spectra of cupric ion in sodium borosilicate glass melts

Optical absorption spectra of Cu²⁺ d–d transition peak in sodium borosilicate glasses and their melts were measured from room temperature to 1100 K. In the case of borate glass free from silicon, increase of the temperature above T_g shifts the peak position to the low energy side and decreases the peak height. Peak width is gradually increased with the increase in temperature. On the other hand, in the case of silicate glass free from boron, peak width is decreased with the increase in temperature from room temperature to liquidus temperature. In addition, peak height is slightly decreased with the temperature increase in this temperature range. Further increase of the temperature makes the peak width large. In borosilicate glasses, temperature dependence of the optical absorption spectra is different both from borate and from silicate, and the temperature dependences of the peak position and of the peak height are very small. Temperature dependence of the peak width depends on the boron/silicon ratio.