Sulfate Decomposition and Sodium Oxide Activity in Soda–Lime–Silica Glass Melts

Reaction equilibrium constants for the sulfate decomposition process, which releases oxygen and sulfur oxide gas in soda–lime–silica glass melts, have been determined. The chemical solubility of SO₂, probably in the form of sulfite ions in soda–lime–silica melts, has also been determined. The chemical solubility value of SO₂, dissolving as sulfite, ranges between 0.02 and 0.06 wt% SO ₃ ²⁻ at 1 bar SO₂ pressure in the temperature range of 1600–1800 K. Results of square-wave-voltammetry studies and measurements of the temperature-dependent sulfur retention after the fining process of commercial float glass melts and a model soda–lime–silica melt, with 74 wt% SiO₂, 16 wt% Na₂O, and 10 wt% CaO, are presented. The measured sulfur retention data and the results of the square-wave-voltammetry studies are used to determine the equilibrium constant of the sulfate decomposition reaction in the temperature range of 1600–1800 K. The thermodynamic relations and properties found for sulfate decomposition are used to derive activities of sodium oxide in soda–lime–silica melts. Literature values for sodium oxide activities in these glass melts are rare. In this study, these activities have been determined by a method, based on the measurement of sulfate decomposition equilibrium constants and the residual sulfate concentrations in glass melts, equilibrated with almost pure sodium sulfate galls.     

Effect of Lead Compounds on the Properties of Stannous Fluorophosphate Glasses

The effects of PbO or PbF₂ additions on the density, thermal-expansion behavior, and chemical durability of stannous fluorophosphate glasses have been determined. Lead compounds dramatically improve the chemical durability of these glasses in water, resulting in low-melting-temperature glasses (T_g<150°C) which have durabilities approaching those of commercial soda–lime–silica glasses. Possible causes of these effects are discussed.     

Mixed Mode I—Mode III Fracture in Ceramic Single Crystals

A recently reported method has been used to propagate stable mixed mode I-mode III cracks in thin slices of single-crystal α-quartz (low quartz, SiO₂) and single-crystal rutile (TiO₂). A bond-counting technique has been developed and used to isolate planes of weakness in the crystalline structures of both crystals. Good correlation has been obtained with observed crack planes. Mode III component (K_III) versus crack velocity (v) relations for specified mode I contributions have thus been determined for m {10 1 0} fracture in basal (0001) slabs and for {a+c} fracture in m {10 1 0} slabs of α-quartz and also for (110) fracture in basal (001) and (101) fracture in (010) slabs of rutile.     

Leaching Behavior of Sodium from Fine Particles of Soda–Lime–Silicate Glass in Acid Solution

The leaching behavior of Na from soda–lime–silicate glass was investigated by preparing glass powders with average particle diameters of 53 and 19 μm, and leaching in HNO₃ at 90°−140°C. A new theoretical equation for Na leaching from a spherical particle is proposed based on the assumption that a rate-determining process is the three-dimensional self-diffusion of Na in glass. The diffusion constant ( D ) of Na in glass was obtained by fitting the experimental data to a theoretical equation. The values of D and activation energy obtained are comparable to those obtained in other studies on larger particles.     

Thermooptic Coefficients of Soda–Lime–Silica Glasses

The thermooptic coefficients, d n /d T , of two series of soda–lime–silica glasses, 25Na₂O· x CaO·(75 – x )SiO₂ and (25 – y )Na₂O· y CaO·75SiO₂, have been measured. When CaO is substituted for SiO₂, the magnitude of d n /d T passes through a maximum negative value. When CaO is substituted for Na₂O, there is a monotonic change from negative to positive d n /d T . These effects are accounted for by the changes in relative values of the coefficient of thermal expansion and the temperature coefficient of electronic polarizability, Θ. The effect of composition on Θ is explained by the changes in density of various nonbridging and bridging oxygens in the glass.     

Dispersion of Thermooptic Coefficients of Soda–Lime–Silica Glasses

The thermooptic coefficients, i.e., the variation of refractive index with temperature (d n /d T ), are analyzed in a physically meaningful model for two series of soda–lime–silica glasses, 25Na₂O· x CaO·(75 – x )SiO₂ and (25 – x )Na₂O· x CaO·75SiO₂. This model is based on three physical parameters—the thermal expansion coefficient and excitonic and isentropic optical bands that are in the vacuum ultraviolet region—instead of on consideration of the temperature coefficient of electronic polarizability, as suggested in 1960. This model is capable of predicting and analyzing the thermooptic coefficients throughout the transmission region of the optical glasses at any operating temperature.     

Shrinkage Behavior of Knoop Indentations in Silica and Soda–Lime–Silica Glasses

The annealing characteristics of Knoop-indented silica and soda–lime–silica glasses were investigated. These glasses were indented using a Knoop indenter in water, and they were annealed at various temperatures below the glass transition temperature. The major diagonal length of the Knoop indentation was measured before and after annealing, and the change of the diagonal length was determined. The change of diagonal length in silica glass was much larger than that in soda–lime–silica glass. This was attributed to the occurrence of more densification around the Knoop indentation in the silica glass. The activation energy of the shrinkage of the Knoop indentation in the silica glass, estimated from the temperature dependence of the relaxation time, was 46 kJ/mol, which was much less than that of viscous flow in silica glass. This suggested that the shrinkage of the Knoop indentation was caused by the structural relaxation of densified glass around the Knoop indentation.     

Chemical Durability of Lead-Oxide-Based, Thick-Film Binder Glasses

Lead-oxide-bearing glasses are incompatible with aluminum nitride metallizations, and federal legislation is recommending their replacement in thick-film electronics and labeling. To evaluate alternatives, the benchmark chemical durabilities of the lead borosilicate and lead aluminate thick-film binder glasses have been determined. Aluminum oxide (Al₂O₃) benefits water durability moderately, acid durability substantially, and basic durability indistinguishably. The rate of attack in water is approximately two orders of magnitude greater than for soda–lime glass. The thermal contractions of the glasses are compatible. An apparent, spontaneous phase separation in the Al₂O₃-free glass is suppressed by Al₂O₃ that is included as a batch component.     

Recycle of Waste Glass into "Glass–Ceramic Stoneware"

The reuse of soda–lime–silica scrap or waste glasses as additives for traditional ceramics has been investigated extensively in the literature. Although interesting, this solution does not generally allow large quantities of glass to be recycled. This study reports a novel high glass recycle approach that replaces, in the formulation of porcelain stoneware, the feldspar flux with finely powdered glass derived from the melting of different waste products, e.g. lime from fume abatement systems, feldspar mining residues, and scrap soda–lime glass. At an optimized glass/clay ratio, the "glass–ceramic stoneware" samples sinter at 1000°C. The "glass–ceramic stoneware" has a bending strength approaching 90 MPa and a fracture toughness exceeding 2.0 MPa·m^0.5, similar to those of conventional porcelain stoneware, which requires sintering at higher temperatures. The high strength and fracture toughness are attributed to the interaction between the glass and clay residues upon sintering, which allows the development of several different crystalline phases.     

Sodium Coordination Environments in Silica Films

The local structure centered on sodium after diffusion in silica (Na-SiO₂ samples) has been determined by means of extended X-ray absorption fine structure (EXAFS) studies. The Na-SiO₂ samples are of particular interest because (i) their sodium content can be varied over a wide range of concentration and (ii) their local structure is representative of that of soda–silica glass. EXAFS analyses reveal the existence of a well-defined local structure involving oxygen, sodium, and silicon neighbors. The Na-O, Na-Na, and Na-Si bonds lengths, which amount to 0.23, 0.30, and 0.38 nm, respectively, do not depend on sodium concentration. This environment closely resembles that found in soda–silica glass. Moreover, it is compatible with the "target site" and "the site memory effect" suggested by recent theories of the ionic conductivity in oxide glasses.     

Surface-Energy Determinations of Tin Oxide-Coated Soda–Lime–Silica Glass

The dispersive and polar surface-energy components, as well as the total surface energy, of tin oxide coatings on soda–lime–silica glass were determined by the Owens–Wendt method. The total surface energy of tin oxide is greater than soda–lime–silica glass and, more importantly, exhibits significantly more-dispersive and less-polar character. These results indicate that tin oxide is significantly more covalent than soda–lime–silica glass. It is postulated that the more-covalent tin oxide coatings increase the bond strength of organic coatings to soda–lime–silica glass. These effects improve the friction-damage resistance of glass surfaces coated with metal oxides and organics, compared with glass surfaces coated with organics only.     

Raman Study of Glasses of Ba2TiSi2O8 and Ba2TiGe2O8

Raman spectra are reported for fresnoite (Ba₂Ti(Si,Ge)₂O₈ glasses, and comparison is made between the Raman spectra of the corresponding crystalline powders and glasses of Ba₂TiSi₂O₈ and Ba₂TiGe₂O₈. The Ba₂TiGe₂O₈ glass spectra show correspondence with the Ba₂TiGe₂O₈ crystalline Raman spectra; the v _s(Ge–O–Ge) mode occurs at 518 cm⁻¹ in the glass and at 521 cm⁻¹ in the crystalline material. Five-fold coordinated titanium is the majority species present in the Ba₂TiGe₂O₈ glass as revealed by a strong band at 824 cm⁻¹ in the I glass spectrum. The Ba₂TiSi₂O₈ glass spectra are similar to the Ba₂TiSi₂O₈ crystalline spectrum; the strongest band is found at 836 cm⁻¹ in the I glass spectrum. Through comparison with the previous Raman data of other titania silicate glasses, we conclude that the Ba₂TiSi₂O₈ glass has a structure similar to the crystalline phase.     

Dissolution Rates of Silicate Glasses in Water at pH 7

Dissolution rates of different glasses in buffered solutions of constant pH of 7 were measured by weight change, profilometry, and ion implantation with Rutherford backscattering. Rates with different techniques agreed within experimental error. Natural obsidian glass dissolved most slowly, at a rate comparable with those of quartz and crystalline aluminosilicate minerals. Commercial soda–lime glass containing alumina dissolved slowly, at about the same rate as vitreous silica; soda–lime silicate glasses both commercial and laboratory without alumina dissolved much more rapidly. Pyrex borosilicate glass dissolved at a rate intermediate between those of soda–lime silicate glasses with and without alumina; at room temperature Pyrex borosilicate glass dissolved about 100 times faster than a commercial soda–lime glass containing alumina. We suggest that surface structure is the main factor determining the relative dissolution rates of silicate glasses. Glasses with transformed surface layers caused by hydration dissolve most rapidly; phase separation and openness of the glass structure are also important factors.     

Formation and Properties of Calcia-Calcium Fluoride-Alumina Glasses

The glass formation region has been determined for the CaO-CaF₂-Al₂O₃ ternary system. The glass transformation temperature of these glasses decreases as the CaF₂ concentration increases, whereas the thermal expansion coefficient and electrical conductivity increase. MAS-NMR (magic-angle-spinning nuclear magnetic resonance) indicates that the aluminum ions in these glasses are in tetrahedral coordination. The structures of these glasses are proposed to be analogous to those of similar silicate glasses, with aluminum ions replacing silicon ions and fluorine acting as a nonbridging anion.     

Microstructural Evolution on Firing Soda–Lime–Silica Glass Fluxed Whitewares

Density and microstructural evolution of porcelains containing 0–25 wt% soda–lime–silica (SLS) waste glass fired over a range of temperatures from 600° to 1400°C have been investigated. After firing 3 h at 1100°C, batches containing 6.25 wt% SLS glass and 18.75 wt% nepheline syenite flux system attained open-pore closure and a bulk density of 2.40 g/cm³, comparable to results from commercial porcelain after firing at 1200°C. SLS glass softens and melts, conferring early densification and overfiring on porcelains fired at normal commercial firing temperatures. The microstructural evolution examined using XRD, SEM/energy dispersive spectroscopy (EDS), and TEM/EDS revealed formation of a variable composition plagioclase, rounded wollastonite particles, sodium silicates, and tridymite in batches containing SLS glass, in addition to primary and secondary mullites, partially dissolved quartz, and a glassy matrix as found in the waste-free batch. Ca²⁺ and Na⁺ from the SLS glass migrate to regions containing the products of clay decomposition to form plagioclase, limiting the extent of mullite crystallization. The presence of a solution rim surrounding quartz and different glass compositions around wollastonite crystals indicate that the system is not in equilibrium, although phases predicted by the Na₂O–CaO–SiO₂ equilibrium diagram were formed.     

Glass Transition and Infrared Spectra of Low-Alkali, Anhydrous Lithium Phosphate Glasses

Anhydrous glasses in the series x Li₂O + (1 - x )P₂O₅ have been prepared and characterized in the range 0 ≤ x ≤ 0.5. FT-IR spectroscopy and glass transition temperature measurements have been used to explore the structure and a key physical property of the low-alkali phosphate glasses. The structure of v -P₂O₅ is proposed to consist of a 3-D network of trigonally connected tetrahedra decorated with a P=O unit. Contrary to what has long been proposed for these glasses, the addition of alkali degrades the 3-D network through the generation of nonbridging oxygens rather than strengthen the network through the proposed alkali ion bridging. The T _g of v -P₂O₅ is ∼653 K and decreases some 130 K with the addition of 10 mol% Li₂O. T _g then reaches a minimum value at 20 mol% Li₂O and increases with further Li₂O additions. The increase in T _g, even though the fraction of nonbridging oxygens is still increasing, is interpreted in terms of an increasing entanglement of long-chain PO₂ groups in the glass. Such a structural transition from a 3-D network of interconnected PO₄ groups for P₂O₅ to a 1-D chain structure for LiPO₃ is one of the first examples of the importance of intermediate-range order in governing the properties of glass.     

Compositional Dependence of Judd-Ofelt Parameters in Silicate, Borate, and Phosphate Glasses

Judd-Ofelt parameters Ω _t with t = 2,4, 6 for the rare-earth ions Pr³⁺, Nd³⁺, Sm³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Er³⁺, and Tm³⁺ in alkali and/or alkaline-earth silicate, borate, and phosphate glasses have been determined. The variations of Ω _t with the number of 4 f electrons of the rare-earth ions are demonstrated, and factors affecting the Judd-Ofelt parameter Ω₆are discussed. The intensity parameter Ω₆ depends on the ionic packing ratio of the glass host by changing modifier type in silicate and borate glasses, and it is independent of that in a series of borate glasses as a function of modifier content and phosphate glasses. The peak wavenumbers of the transitions whose intensities are determined mainly by the Ω₆<| U ⁽⁶⁾|>² term—where <| U ⁽⁶⁾|> is one of the reduced matrix elements—shift systematically with the values of Ω₆ for all the rare-earth ions.     

Effect of Fluorides on Infrared Transmittance of Certain Silicate Glasses

Relatively large amounts of fluorides can be incorporated into silicate glasses without producing opalescence or turbidity if certain oxides, such as La₂O₃ or Ta₂O₅, are included in the glass composition. In most cases, the fluorides reduce the absorption at the 2.75-μ water band, thus improving the glasses for use as infrared material. The fluorides also decrease the refractive index values of the glasses. Striae are produced in the glasses when the fluoride content is more than about 4 mole %.     

Stannous-Stannic Equilibrium in Molten Binary Alkali Silicate and Ternary Silicate Glasses

The stannous-stannic equilibrium in binary alkali silicate and ternary silicate glasses was studied by equilibrating glassmelts with air at 1400°C. The Sn²⁺-Sn⁴⁺ equilibrium shifts more toward the oxidized state with increasing ionic radii of the alkali ions or with increasing concentration of the alkali ions in the same series of glasses. The slope of the straight lines obtained on plotting log (Sn⁴⁺)/(Sn²⁺)( pO₂ )^n/2 vs mol% R₂O increased in the order Li→Na→K. In ternary silicate glasses having the base glass composition 20Na₂O·10RO·70SiO₂, the Sn²⁺-Sn⁴⁺ equilibrium shifts more toward the reduced state, with increasing bond strength between the divalent cations and the nonbridging oxygens. With increasing temperature, the equilibrium shifts more toward the reduced state.     

Alkali Magnesium/Zinc Silicate Glasses with Low Rayleigh Scattering

The Rayleigh scattering of silicate glasses (M₂O-RO-SiO₂, M: Na and K, R: Mg, Ca, and Zn) was measured. Soda magnesium silicate (NMS) glasses exhibited the smallest scattering intensity. It is comparable with that of soda aluminosilicate (NAS) glass, one of the candidates for use in fabricating ultralow-loss fibers. The scattering intensity decreased with decreasing SiO₂ content, and NMS glasses with 60 mol% of SiO₂ are still stable against crystallization. It is concluded that NMS is a new candidate for ultralowloss fiber use.