Volume Relations in Na2O·B2O3 and Na2O·SiO2 B2O3, Melts at 1300·C

Density (and some viscosity) data are presented for binary sodium borate melts containing as much as 60 mole % Na₂O and for ternary sodium silicoborate melts with B/Si <2.0 between 1000°C and 1300°C. The high-temperature partial molar volume analysis of the binary sodium borate melts reveals about 50% BO₄ tetrahedra at the 40 mole % Na₂O composition, in agreement with recent NMR estimates for the binary glasses. No "boron anomaly" was found near 18 mole % Na₂O at high temperature. The synthetic partial molar volume model that agrees best with experiment for all ternary melts studied involves the presence of some BO₄ tetrahedra, the percentage of which varies with composition. This ternary model involves a high degree of internal consistency. No tendency toward extensive micro-immiscibility was observed for ternary melts near the SiO₂·B₂O₃ binary.     

Heats of Solution, Density, and Refractive Index Changes in Sodium Borate Glasses Subjected to High Pressure

The densification produced in sodium borate glasses by pressures to 40 kbars at 25° and 250°C was measured. At a constant temperature and pressure, the densification decreased with increasing alkali content. For specimens pressed at 40 kbars and 250°C, the densification ranged from 14.2% for B₂O₃ to 6.3% for the 33.3 mole % Na₂O composition. Under the same conditions, the refractive index increase ranged from 4.8 to 1.1%, and the decrease of the molar refraction of the oxygen ions ranged from 2.5 to 1.5%. The heats of solution of the pressed glasses were more negative than those of the corresponding unpressed glasses. The heats of solution of both the pressed and unpressed glasses pass through a minimum near 20 mole % Na₂O. A decrease in density was observed at room temperature for all pressed specimens. Electron micrographs were made of two of the pressed specimens. The results could be explained on the basis of a repacking of structural units.     

Preparation of Inorganic Compounds at Near Room Temperature by the Direct Conversion of Borate Glass in Solutions of the Corresponding Anions

The preparation of alkaline-earth chromate, selenite, and stannate compounds at near room temperature by the direct conversion of borate glass in aqueous solutions of the corresponding anions was investigated. Borate glass particles (150–300 μm) with the composition 20Na₂O·20CaO·60B₂O₃ or 20Na₂O·20BaO·60B₂O₃ (mol%) were prepared by conventional methods and immersed in dilute solutions of K₂CrO₄, K₂SeO₃, or K₂SnO₃ at 37°C. The conversion of the glasses was monitored using weight loss and pH measurements, while X-ray diffraction (XRD), X-ray fluorescence, and scanning electron microscopy were used to characterize the structure and composition of the products. After a reaction for 140–320 h, porous crystalline products identified by XRD as CaSeO₃.H₂O, CaSnO₃.3H₂O, BaCrO₄, and BaSeO₃ were obtained. The conversion of fibers (0.5–1.0 mm in diameter) of the Na₂O–BaO–B₂O₃ glass in K₂CrO₄ solution was pseudomorphic. The kinetics and mechanisms of the conversion process, as well as the structure of the products, are discussed.     

Effect of Water Content on Transport in Na2O·3SiO2 Glass

Na₂O·₃SiO₂ glasses of high water content were prepared under high-pressure, hydrothermal conditions. The sodium diffusion coefficient, DNa , in these glasses measured at 100°C depended strongly on H₂O content. With increasing H₂O content, DNa . at 100°C decreased initially to a minimum at 3∼4 wt% H,O and then increased. This behavior of DNa . Was similar to that of dc conductivity.     

Energy Relations in Binary Alkali Borates

The heats of solution of glasses and devitrified alkali borates in the systems Li₂O–B₂O₃, Na₂O—B₂O₃, and K₂O–B₂O₃ were measured in 2 N nitric acid with a simple vacuum-bottle calorimeter. The standard deviation was 0.35 cal. per gm. for approximately 130 determinations. From these data, together with available thermodynamic data, heats of formation were calculated for alkali borate glasses and devitrified alkali borates from two combinations of possible reactants. All the curves for the heats of solution of glasses showed minima at 20 mole % alkali oxide, but similar curves for devitrified alkali borates showed minima at 20 mole % for potassium and sodium borates only. The curve for devitrified lithium borates showed a minimum at 25 mole % alkali. The conclusion was drawn that there is probably no congruently melting Li₂O.4B₂O₃ compound.     

States of Sulfur in Alkali Borate Glasses

Simple binary alkali borate glasses of differing alkali content (alkali = Li, Na, or K) containing sulfur were prepared and their absorption spectra were measured in the range of 200 to 700 nm. The absorption bands obtained were used to determine the stable states of sulfur in these glasses by directly comparing them with published data. The following states of sulfur were identified and their ranges of stability were determined: the S₂ molecule in glasses containing at least 15 mol% alkali oxide, the S₃⁻ and S₂⁻ in glasses containing 20 to 30 mol% Na₂O or K₂O, and the polysulfide ion (S x ²⁻) in glasses of 30 to 35 mol% Na₂O or K₂O.     

Studies in Germanium Oxide Systems: IV, Phase Equilibria in the System K,O-GeO,

Phase relations in the binary system K₂O-GeO₂ were determined by conventional quenching techniques. Three compounds, K₂O.2GeO₂, 3K₂O.11GeO₂, and K₂O.7GeO₂, exist in the composition range 65 to 100% GeOn. The compound 3K₂O.1lGeO₂ melts congruently at 1055°C, whereas K₂O.2GeO₂ and K₂O.7GeO₂ melt incongruently at 761° and 950°C, respectively. Thermal expansion data for the crystalline compounds are presented. The structure of potassium germanate glasses is discussed.     

Viscosity and Thermal Expansion of Alkali Germanate Glasses

Transformation-range viscosities are reported for Na₂O-, K₂O-, Rb₂O-, and Cs₂O-GeO₂ glasses. A minimum in viscosity occurs between 1 and 5 mol% alkali oxide and a maximum between 17 and 22 mol% alkali oxide. The thermal-expansion coefficients of the Na₂O-GeO₂ glasses also exhibit a minimum at < 5 mol% Na₂O. The accepted structural model for alkali germanate glasses does not predict the minimum at low R₂O concentrations. A modification of this model is suggested to explain these data.     

Visible Spectroscopy of Irradiated High-Alkali Borate and Mixed-Alkali Phosphate Glasses

Expectations of increased stability for trapped electrons in high-alkali glasses, based on extrapolations from observations on low-alkali borate glasses, are not borne out. In 69Na₂O-31B₂O₃ glass, electron centers have approximately the same thermal stability as in Na₂O·2B₂O₃ glass. In Na₂Oplus;P₂O₅ glasses the lifetimes, 3 · 0.5 μS, of transiently trapped electrons as well as their absorption spectra prove to be independent of increase of Na₂O content from 50 to 60 mol%. The same composition change destabilizes "permanent" hole centers. Exchange of Na₂O with K₂O in the metaphosphate glass also has no effect on the trapped electron lifetime. Small linear shifts in the trapped-hole absorption peak wavelengths are observed in the latter case. The most important positive finding in the phosphate glasses is a pronounced mixed-alkali effect on the yield of transiently trapped electrons and holes and of permanently trapped holes. The yield is a minimum at Na:K=1:1, due either to the elimination of trap sites or to the reduction of alkali ion mobilities which play a role in trap formation.     

Mixed-Alkali Effect in Low-Alkali Germanate Glasses

Direct-current conductivities of mixed-alkali Na₂O-K₂O-GeO₂ glasses with ∼0.02 mol% total alkali were investigated. No minima in conductivity isotherms were indicated as K₂O is substituted for Na₂O. However, a conductivity-suppressing effect with the-addition of K₂O to Na₂0-GeO₂ glass was demonstrated, from the comparison with the conductivity ofNa₂O-GeO₂ glasses of varied sodium content (0.0079∼0.30 mol% Na₂O.     

Effect of H2O Vapor on the Internal Friction of Binary Alkali Silicate Glasses

Internal friction and shear modulus of Na, K, and Li disiticate glasses were measured by a torsional pendulum as a function of H₂O vapor treatment at T=300°C. H₂O produced changes in the acoustic spectra (between—100° and 400°C and f=0.5 Hz) similar to the mixed-alkali effect which appears upon introduction of a second alkali to a single-alkali glass. An Na₂O·2SiO₂ glass free from the common nonbridging oxygen relaxation was produced .     

Optical Absorption Characteristics of Ni2+ in Mixed-Alkali Borate Glasses

Nickel-containing mixed-alkali borate glasses were prepared and their spectral absorption in the visible and near-ir were measured and used to determine the ligand field strength, Racah parameter, and state of coordination of Ni²⁺ ions. The change in these parameters with alkali content is discussed in terms of mixed-alkali effect. Nickel ions were found to occupy octahedral sites in the 20 mol% (Li₂O+Na₂O) glasses, whereas in the 30 mol% (Na₂O+K₂O) glasses Ni^Z+ ions are believed to occupy both octahedral and tetrahedral sites. In most cases slight deviations were observed which increased with increasing alkali content. The results obtained suggest that the substitution of one alkali for another in alkali borate glasses did not produce gross alterations of the glass network sufficient to induce deviations from linearity in property-composition relations.     

Relative Activity of Oxygen Ions in Molten Sodium Phosphate as Determined from the Solubility of Sulfur Trioxide

The solubility of sulfur trioxide in sodium phosphate melts with Na₂O/P₂O₅ ratios from 1.0 to 1.4 was investigated at 653° to 1021°C. The oxygen-ion activity estimated from the solubility of SO₃ increased exponentially as the Na₂O/P₂O₅ ratio increased. This compositional dependence of the activity is discussed on the basis of a polymer model.     

Conversion of Quartz to Tridymite

The conditions under which tridymite becomes a stable phase have been reinvestigated. When quartz was heated with 2% alkali oxide, tridymite formed directly at 872° to 898°C. with Na₂O, at 883° to 902°C. with K₂O, and above 1005°C. with Li₂O. Cristobalite occurred as an intermediate phase above 893°C. with Li₂O, above 898°C. with Na₂O, and above 902°C. with K₂O. When quartz plus sodium chloride was heated in vacuum, tridymite did not form but cristobalite started to appear at 1050°C. The results showed that the formation of tridymite can be strictly a solid-state process. New schematic tentative diagrams for the high-silica region of binary systems are suggested. Quartz and cristobalite are regarded as the only stable crystalline phases of pure silica. Tridymite is pictured as a binary incongruently melting phase.     

Studies in Germanium Oxide Systems: II, Phase Equilibria in the System Na2O—GeO2

Phase equilibrium relations in the system Na₂O-GeO₂ have been determined using standard quenching techniques supplemented by differential thermal analysis. Two congruently melting compounds, Na₂O·GeO₂ and 2Na₂O·9GeO₂, exist; the melting points are 1103°± 15°C and 1073°± 3°C, respectively. The eutectic temperature between GeO₂ and 2Na₂O·9GeO₂ is 950°±f 10°C at 94.5 wt GeO₂. The eutectic temperature between 2Na₂O · 9GeO₂ and Na₂O·GeO₂ is 790° f 10°C at about 75 wt% GeO₂. Both the refractive index and the density of glasses in the system Na₂O-GeO₂ exhibit maximum values at about 16 to 18 mole % Na₂O. The Ge-O-Ge absorption band at 890 cm⁻¹ shifts toward lower wave numbers with the addition of Na₂O.     

Synthesis of Titanate Derivatives Using Ion-Exchange Reaction

Two types of titanate derivatives, layered hydrous titanium dioxide (H₂Ti₄O₉· n H₂O) and potassium octatitanate (K₂Ti₈O₁₇) with a tunnellike structure, were synthesized using an ion-exchange reaction. Fibrous potassium tetratitanate (K₂Ti₄O₉· n H₂O) was prepared by calcination of a mixture of K₂CO₃ and TiO₂ with a molar ratio of 2.8 at 1050°C for 3 h, followed by boiling-water treatment of the calcined products for 10 h. The material then was transformed to layered H₂Ti₄O₉· n H₂O through an exchange of K⁺ ions with H⁺ ions using HCl. K₂Ti₈O₁₇ was formed by a thermal treatment of KHTi₄O₉· n H₂O. Pure KHTi₄O₉· n H₂O phase was effectively produced by a treatment of K₂Ti₄O₉ with 0.005 M HCl solution for 30 min. Thermal treatment at 250°–500°C for 3 h resulted in formation of only K₂Ti₈O₁₇.     

Sodium Transport in the Na2O-H2O-SiO2 Glass System

The variation with water content of dc conductivity and Na diffusion coefficient for the Na₂O · 4siO₂ and Na₂O · 2SiO₂ glass systems was found to be similar to that of the Na₂O.3SiO₂ series reported earlier. The conductivity was estimated for the ternary system Na₂O-H₂O-SiO₂ by combining the present results with the previous data on the Na₂O · 3SiO₂ system. When the conductivity of those glasses with a constant [Na₂O] + [H₂O] content was plotted against water content, a pronounced mixed "alkali" effect was demonstrated. The Haven ratio, calculated by comparison of the dc conductivity to the Na diffusion coefficient at 100°C for each of the three glass systems, was found to increase toward unity with increasing water content. This suggests that the addition of water reduces the number of sodium charge carriers. The subsequent increase in conductivity beyond the minimum with the introduction of larger amounts of water is, probably, due to an increase in the mobility of the Na⁺ ions.     

Structure of Glasses and Melts in the Na2O·GeO2·B2O3 System

Density and viscosity results are presented for ternary Na₂O·GeO₂·B₂O₃ melts (∼600° to 1300°C) and glasses containing as much as 35 mole % Na₂O. Synthetic partial molar volume models indicate a fairly broad stability region for BO₄ tetrahedra in the B₂O₃-rich melts. Similar models for GeO₂-rich melts reveal a more limited stability region for GeO₆ octahedra. The expansion coefficient contours and viscosity isotherms confirm the volume-based conclusions for the liquid state. The high-temperature volume models were used to develop glass volume models that agree to within several percent of experiment. It has been concluded that the melts and glasses possess similar structures. The relatively greater compositional stability of GeO₆ octahedra in the presence of B₂O₃ (compared to Al₂O₃) can be related to the smaller average number of oxygens around boron (III), at a fixed O/Ge ratio, compared to aluminum (III). Evidence is presented for a slight decrease of the thermal stability of GeO₆ octahedra in the GeO₂-rich melts above about 1000°C.     

Preparation and Properties of Nitrogen-Containing Na2O-B2O3 Glasses

Up to 3.3 wt% nitrogen can be incorporated into Na₂O-B₂O₃ glass melts. The melting procedure is described, and structure models are given. In contrast to N-containing silicate glasses, the borate glasses were transparent; however, micrographs of their fracture surfaces showed some crystallinity. Properties were determined as a function of the N and Na₂O contents of the glasses. Compared with N-containing silicate glasses, the properties of borate glasses are much less changed by the nitrogen introduced.     

Effect of Na2O/K2O Ratio on Chemical Durability of Alkali-Lime-Silica Glasses

The chemical resistance of mixed-alkali glasses to water was measured by determining the sodium, potassium, calcium, and silicon ions extracted instead of evaluating it from the alkalinity of the mixed-alkali extracts. In glasses of the composition K₂O and Na₂O 18, CaO 10, and SiO₂ 72% the minimum extraction of alkali (maximum durability) occurred for a K₂O/-Na₂O ratio of 2.6/1.0 (by weight). Based on an ionic-composition analysis of the results, an empirical index is suggested for determining the relative degree of ion-exchange and network-breakdown modes of reactions that occur when such mixed-alkali glasses are attacked by water.