Internal Friction of Ion-Exchanged Li2O.Al2O3.2SiO2 Glass

Fibers of Li₂O.Al₂O₃.2SiO₂ glass were ion-exchanged for 1 to 300 min in an NaNO₃ bath at 366°C. The internal friction and the Li and Na concentration profiles were measured. As Na progressively replaced Li, the alkali internal friction peak became smaller while a new peak (mixed-alkali peak) appeared and increased in magnitude. These changes in internal friction are similar to those that occur when a second alkali is added to glasses prepared by conventional melting. The magnitudes of both internal friction peaks in the ion-exchanged glass depended on the overall composition of the glass; that of the alkali peak depended on the composition of the unexchanged glass core, whereas that of the mixed-alkali peak depended on the composition of the exchanged layer on the glass surface. When the exchanged surface layer was dissolved, the original alkali peak was restored, and the mixed-alkali peak disappeared. Changing the alkali distribution did not affect the mixed-alkali peak much; however, it caused the alkali peak to shift to higher temperatures and become smaller. The height of the alkali peak can be used to determine the maximum depth of penetration of the second alkali.     

Internal Friction of Proton-Exchanged Li2O·Al2O3·2SiO2 Glass

Protons were introduced into the surface of an Li₂O·Al₂O₃·2SiO₂ glass fiber (0.5 mm in diameter) by ion exchange in NH₄HSO₄ at 366°C for 21 h. Infrared absorption measurements established that the protons were associated with bridging oxygen ions. After ion exchange, the magnitude of the alkali internal friction peak decreased and a new peak appeared at ∼220°C. This new peak is attributed to the interaction of alkali and hydrogen ions, independent of the presence of nonbridging oxygen ions.     

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.     

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 .     

Internal Friction of Glasses with Low Water Contents

Internal friction was measured for NaPO₃ glasses containing from 0.0004 to 0.146 wt% H₂O. In glasses containing ≤ 0.001 wt% H₂O, the only internal friction peak observed was that resulting from the Na⁺ ions, i.e. the alkali peak; it was ∼ 30% larger than in as-melted glasses. The second peak normally observed in as-melted NaPO₃ glass was completely absent when the water content was < 0.001 wt%, consistent with the interpretation that it is caused by a reorientation of proton-Na⁺ elastic dipoles. The concept that the second peak in as-melted alkali phosphate and silicate glasses results from nonbridging oxygen ions is not substantiated by these studies of NaPO₃ glasses, which contain a high percentage of these ions but do not exhibit this peak when the proton concentration is sufficiently low.     

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.     

Formation of Sm2+ lons in Sol-Gel-Derived Glasses of the System Na2 O-Al2O3-SiO2

Samarium ions (Sm²⁺) incorporated into aluminosilicate glasses by a sol-gel process showed persistent spectral hole burning at room temperature. Gels of the system Na₂O-Al₂O₃SiO₂ synthesized by the hydrolysis of Si(OC₂H₅)₄, Al(OC₄H₉)₃, CH₃ COONa, and SmCl₃·6H₂O were heated in air at 500°C, then reacted with H₂ gas to form Sm²⁺ ions. Whereas Al³⁺ ions effectively dispersed the Sm³⁺ ions in the glass structure, Na⁺ ions were not effective. The Al₂O₃-SiO₂ glasses proved appropriate for reacting the Sm³⁺ ions with H₂ gas and exhibited the intense photoluminescence of Sm²⁺ ions. The reaction of Sm³⁺ ions with H₂ in the Al₂O₂-SiO₂ glasses was determined by first-order kinetics, and the activation energy equaled 95 kJ/mol. At 800°C, the maximum photoluminescence of the Sm²⁺ ions was achieved within 20 min.     

Copper ⇌ Alkali Ion Exchange of Alkali Aluminosilicate Glasses in Copper-Containing Molten Salt: II, Divalent Copper Salts, CuCl2 and CuSO4

The ion-exchange mechanism between copper and alkali ions, when 20R₂O · 10Al₂O₃· 70SiO₂ (R = Li, Na, and K) glasses are immersed in divalent copper-containing molten salts in air and nitrogen at 550°C, has been investigated. In molten CuCl₂, the ion-exchange behavior in both air and nitrogen was very close to that in molten CuCl in air reported previously. This is explained by assuming that CuCl₂ decomposes into CuCl and Cl₂ at 550°C and the Cu⁺ ions thus formed mainly diffuse in glasses to replace alkali ions, where Cl₂ acts as an oxidizing agent just like oxygen. In the case of molten CuSO₄─₂SO₄, a small amount of Cu⁺ which is present in the molten state plays a primary role in the Cu ⇌ R⁺ ion exchange process, although the contribution of direct Cu²⁺⇌ 2R⁺ ion exchange cannot be ignored.     

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.     

Crystallization of Li2O · Al2O3· 6SiO2 Glasses Containing Niobium Pentoxide as Nucleating Dopant

Niobium pentoxide (T form, orthorhombic system) was utilized to promote devitrification in Li₂O · Al₂O₃· 6SiO₂ glasses. Two or more mole percentage of this nucleating dopant enhanced crystallization in these glasses. Glasses containing 4.0 and 8.0 mol% T-Nb₂O₅ exhibited a high tendency to form dispersed TT-Nb₂O₅ (monoclinic system) precipitates during the glass quenching process. The crystallization process in glasses containing 2.0 or 4.0 mol% T-Nb₂O₅ occurred as microphase separation, followed by the formation of dispersed TT-Nb₂O₅ crystalline precipitates (760°C), followed by β-quartz solid-solution ( ss ) formation (850° to 900°C) heterogeneously nucleated from the precipitates. β-quartz( ss ) transformed to β-spodumene( ss ), along with a polymorphic transition from the TT-Nb₂O₅ to M-Nb₂O₅ (tetragonal system) crystalline phase.     

Studies in Germanium Oxide Systems: I, Phase Equilibria in the System Li2O—GeO2

Phase equilibrium relations in the system Li₂O-GeO₂ were determined using standard quenching techniques. In contrast to published literature five congruently melting compounds were found to exist. They are Li₂O·7GeO₂, 3Li₂O O·8GeO₂, Li₂O O·GeO₂, 3Li₂O O·2GeO₂, and 2Li₂O.-GeO₂. The melting points, respectively, are 1033°± 5°C, 953°± 5°C, 1245°± 15°C, 1125°± 15°C, and 1280°± 15°C. Simple binary eutectic relations exist among the compounds. The eutectic temperature between 1:7 and GeO₂ is 1025°± 1h0°C at about 96.8 wt% GeO₂; the eutectic temperature between the 1:7 and 3:8 compounds is 935°± 10°C at about 90.9 wt% GeO₂; the eutectic temperature between the 3:8 and 1:1 compounds is 930°± 10 °C at about 89.8 wt% GeO₂. Liquidus data for compositions richer in lithia than the 1:1 compound are only approximate because of the difficulty of quenching them; the phase relations between the 1:1 and 3:2 and between the 3:2 and 2:l compounds, however, are found to be of the simple binary eutectic type. The glass–forming region was also determined. Melts allowed to cool in air crystallized. When, however, the melts were quenched, glasses containing as much as 8 wt% GeO₂ could be prepared in 5–g quantities. Both the refractive index–composition and density–composition curves for the glasses showed maxi–mums at about 6 to 8 wt% Li₂O.     

Glass Formation and Properties of Glasses in the System Na2O-B2O3-SiO2-TiO2

An investigation was made of the effect of TiO₂ on the glassforming region and on the physical properties of glasses in the system Na₂O-B₂O₃-SiO₂TiO₂. Glasses containing up to 45 mole % TiO₂ may be formed with an alkali content of 30 mole %. At lower alkali contents (10 mole % Na₂O) glasses may be formed containing up to 22 mole % TiO₂. The way in which the coefficient of linear thermal expansion and the transformation and softening temperatures are affected by TiO₂ additions has been determined.     

Preparation and Properties of Quenched Li2O-BaO-Nb2O5 Glasses

Glasses were prepared in the wide variety of compositions in the system Li₂O-BaO-Nb₂O₅, which contains no "glass-former," by the twin-roller quenching technique. The crystallization temperature ranges from 500° to 700°C and increases as Li₂O is replaced by BaO. The dielectric constant increases steeply with temperature, reaching an anomalously large value (10⁴) in glasses which contain a large amount of Li₂O. Such a temperature dependence of dielectric constant is very similar to that of conductivity in each glass, indicating that the dielectric behavior is caused by polarization due to the ionic motion in glass. The conductivity at 500 K ranges from 10⁻¹³ to 10⁻⁵Ω⁻¹·cm⁻¹ and the activation energy for conduction from 120 to 40 kJ/mol. The concentration of Li⁺ ions mainly controls the conductivity and the addition of Ba²⁺ ions slightly lowers it.     

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.     

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.     

Phase Equilibria in the System Na2O – Nb2O5

Phase equilibria data, obtained both by differential thermal analysis and by quenching, are presented for the system Na₂O-Nb₂O₅. Five compounds corresponding to the formulas 3Na₂O.1Nb₂0₆, lNa₂O. 1Nb₂O₅, lNa₂O 4Nb₂O₆, lNa_zO.7Nb₂O₅, and lNa₂O. 10Nb₂O₆ have been found. The compound 3Na_z0.lNb₂O₅ melts congruently at 992°C. The compounds 1Na₂O. 4Nb₂O₆, lNa₂O.7Nb₂O, and 1Na₂O. 1Onb₂O₅ melt incongruently at 1265°, 1275°, and 1290°C., respectively. The well-known perovskite structure phase NaNbO₃ was found to melt congruently at 1412°C. The transition temperatures in NaNbO₅ were checked by thermal analysis and only the major structural changes at 368° and 640°C. could be detected. A new disordered form of NaNbO₃ could be preserved to room temperature by very rapid quenching.     

Effect of P2O5 on the Crystallization of Lead Silicate Glasses

The effect of P₂O_S on the devitrification of binary lead silicate glasses containing 64 and 59 mol% PbO was studied. Glasses underwent isothermal crystallization treatments at 400°, 450°, 500°, and 550°C. A polymorph of 3PbO₂SiO₂ was the major product of crystallization for all compositions of glasses. Secondary products of crystallization were found to be a polymorph of PbOSiO₂ in the 59 mol% and a low-temperature polymorph of 2PbOSiO₂ in the 64 mol% PbO glasses. Dominant mode of crystallization in both binary glasses was surface devitrification at all temperatures studied. Addition of P₂O₅ promoted internal crystallization in the form of spherulites. 400°C was found to be the most effective temperature for nucleating spherulitic growth. Crystallization at 400°C led to high concentrations of spherulites in all glasses containing at least 0.5 mol% P₂O₅. Concentrations of 0.5 mol% P₂O₅ were needed to produce detectable levels of spherulitic nucleation at r<400°C.     

Chemical Durability of Sodium Silicate Glasses Containing AI2O3 and ZrO2

A sodium silicate glass and ternary glasses derived from it by substituting AI₂O₃ and ZrO₂ for SiO₂ were exposed to water and aqueous solutions of pH 1.4 to 12.7; the kinetics of the reactions were studied. Diffusion of alkali ions and leaching of alkali and SiO₂ from the glasses were influenced by the occupancy of surface sites by alkali ions above a critical pH; however, the activation energies of the processes varied linearly with the logarithm of mole fraction of surface sites occupied by H^plus;. Identical slopes were obtained for all glasses for a given process. The results are explained on the basis that transport of alkali ions is retarded as a result of increased boundary concentration and that suitable sites for reaction are lacking.     

Reaction Between K2O and Al2O3-SiO2 Refractories as Related to Blast-Furnace Linings

An examination was conducted to determine the mechanism of peeling of fire-clay brick in the low-temperature region of a blast furnace where 3 to 10% K₂O is the principal contaminant. In laboratory tests, as-received high-duty and superduty fire-clay brick and 70% alumina brick treated with KCl-K₂CO₃ mixtures showed no peeling at a temperature of 1600°F. Cracks were found in high-duty brick that were treated with KCN at 1500°F. under partially reducing conditions. X-ray diffraction studies of mixtures of crushed brick and K₂CO₃ indicated the formation of leucite (K₂O.Al₂O₃.4SiO₂) and kaliophilite (K₂O.-Al₂O₃.2SiO₂) at temperatures below 1700°F. These latter data, confirmed by specimens from used blast-furnace linings, showed that silica is the first constituent attacked by alkali. Since the formation of leucite and kaliophilite in fire-clay brick is the probable cause of peeling, the increased reaction of silica, in a dense Al₂O₃.SiO₂ refractory of higher silica content than fire-clay brick, should confine the alkali attack to the surface of the brick in low-temperature applications.     

Internal Friction of Progressively Crystallized Glasses

The internal friction of partly crystallized Li₂O.-2.75 SiO₂ glass fibers, containing a maximum of 78% lithium disilicate crystals, was measured by the torsion pendulum technique. The following changes in the internal friction were observed with increasing crystallization: (1) The low-temperature peak, generally attributed to the stress-induced diffusion of alkali ions, decreased continuously in height and shifted to higher temperatures at the higher crystal contents, (2) the intermediate-temperature peak decreased continuously in height, and (3) a new relaxation, which first appeared as an inflection in the background of the glasses which had been nucleated at 500° C. without any crystallization, became a well-defined peak in the partly crystallized fibers. It is suggested that this new relaxation may be an indication of the early stages of nucleation. Possible explanations are given for the high-temperature relaxation observed in the partly crystallized glasses.