Mechanochemical Wear of Soda Lime Silica Glass in Humid Environments

The mechanochemical wear of multicomponent glasses was studied under controlled humidity conditions using a reciprocating ball‐on‐flat tribometer. For dry conditions, the surfaces were extensively damaged by scratching for all of the glasses, while for humid conditions the wear behavior varied with the glass composition suggesting a chemical effect on scratch behaviors of glass surfaces. The wear of soda lime silica (also called sodium calcium silicate) glass was suppressed with increasing humidity, while the borosilicate and barium boroaluminosilicate glasses showed an increase in wear volume with increasing humidity. The unique humidity dependence of the observed mechanochemical wear of soda lime silica glass supports the hypothesis that hydronium ion formation in the sodium‐leached sites of the soda lime glass enhances its wear resistance.     

‘Optical and FT Infrared Absorption Spectra of Soda Lime Silicate Glasses Containing nano Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> and Effects of Gamma Irradiation

The optical absorption spectra of undoped soda lime silicate glass together with two glasses doped with either (1 % nano Fe₂O₃ ) or with both (1 % Nano Fe₂O₃ + 5 % cement dust) have been measured from 200 to 2400 nm before and after gamma irradiation with a dose of 8 Mrad. The undoped glass reveals strong UV absorption with two distinct peaks which are attributed trace ferric iron ions present as impurity. Upon gamma irradiation , this base glass exhibits three peaks at 240,310 and 340 nm and the resolution of an induced broad visible band centered at 530 nm. The two doped glasses show an additional small visible band at about 440 nm and followed by a very broad band centered at 1050 nm. Upon gamma irradiation, the two doped samples reveal the decrease of the intensities of the spectrum. The two additional bands are related to ferric (Fe⁺³) ions to the band at (440 nm) while and the broad band at 1050 nm is due to ferrous iron (Fe⁺²) ions. The decrease of the intensities of the UV-visible spectrum upon irradiation can be related to of capturing freed electrons during irradiation . Infrared spectra of the glasses reveal repetitive characteristic absorption bands of silicate groups including bending modes of Si–O–Si or O–Si–O, symmetric stretching , antisymmetric stretching and some other peaks due to carbonate , molecular water , SiOH vibrations . Upon gamma irradiation, the IR spectra reveal a small change in the base spectrum while the IR spectra of the two doped glasses remain unchanged. The change of the IR spectrum of the base glass is related to suggested changes in the bond angles or bond lengths of the mid band structural units. The doped glasses show resistance to gamma irradiation because the nano Fe₂O₃ can capture released electrons and positive holes.     

银纳米颗粒在钠钙硅酸盐玻璃中的应力分析

Ag K边X射线吸收精细结构谱分析显示,包裹在钠钙硅酸盐玻璃中的银纳米颗粒的Ag-Ag原子间最近邻距离大于体材料中Ag的间距,说明此时Ag晶格膨胀.晶格膨胀程度依赖于Ag纳米颗粒掺杂玻璃的制备条件.晶格膨胀表明:包裹在钠钙硅酸盐玻璃中的银纳米颗粒处于张应力状态,这主要是由于Ag纳米颗粒与钠钙硅酸盐玻璃基质热失配造成的.     

Hydronium Ions in Soda‐lime Silicate Glass Surfaces

The presence of leachable alkali ions, or their hydrated sites in the glass, is believed to be a determining factor for the interfacial water structure at the glass surface, influencing the surface properties of glass. The interfacial water structure on soda‐lime silicate glass in humid ambience at room temperature was analyzed with sum‐frequency‐generation (SFG) vibration spectroscopy, which can probe the interfacial water layer without spectral interferences from the gas phase water. The soda‐lime glass surface exposed to water vapor shows three sharp SFG peaks at 3200, 3430, and 3670 cm^?1 in SFG, which is drastically different from the SFG spectra of the water layers on the fused quartz glass surface and the liquid water/air interface. The sharp peak at 3200 cm^?1 is believed to be associated with the hydronium ions in the Na⁺‐leached silicate glass surface. The 3200 cm^?1 peak intensity varies with the relative humidity, indicating its equilibrium with the gas phase water. It is proposed that the hydronium ions in the Na⁺‐leached sites produce compressive stress in the silicate glass surface; thus the growth of hydronium ions with increasing humidity might be responsible for the increased wear resistance of soda‐lime glass surfaces in near‐saturation humidity conditions.     

Conductive and Radiative Properties of Soda‐Lime Silicate Glassmelts with Different Iron Contents from 1100°C to 1500°C

This paper presents an inverse method for retrieving (i) the true thermal conductivity, and (ii) the two‐band absorption coefficient of soda‐lime silicate glassmelts between 1100°C and 1550°C from measured steady‐state temperature profiles. This was achieved by combining (i) a forward method solving combined conductive and radiative heat transfer accounting for temperature‐dependent thermal conductivity and spectral absorption coefficient and (ii) an inverse method based on genetic algorithm (GA) optimization. Four glassmelt compositions from ultraclear to gray glasses with iron content ranging from 0.008 to 1.1 wt% were investigated. First, it was established that the steady‐state temperature in glassmelt can be predicted accurately by averaging the spectral absorption coefficient over two bands from 0 to 2.8 μm and 2.8 to 5.0 μm. The inverse method showed that the true thermal conductivity was independent of the iron content and given by k_c(T) = 1.31 + 5.90 × 10^?4T, where T is given in °C. In addition, the band absorption coefficient between 0 and 2.8 μm strongly increased with increasing iron content, while the band absorption coefficient between 2.8–5.0 μm was independent of iron content.     

Luminescence of modified nonbridging oxygen hole centers in silica and alkali silicate glasses

This paper reports on the results of the investigation of the cathodoluminescence spectra of silica and alkali silicate glasses upon excitation with a pulsed electron beam (energy, 180 keV; current density, 700 A/cm²; pulse duration, 2 ns). The luminescence band observed in the energy range 2.4–2.6 eV is assigned to modified structural defects of the ≡Si-O·/Me ⁺ type. These defects are revealed under high-density electronic excitation and, unlike the known L centers in alkali silicate glasses, are interpreted as a variety of nonbridging oxygen hole centers (defects of the dangling bond type) subjected to a disturbing action of the nearest neighbor alkali metal cations. The cathodoluminescence of similar centers is observed in neutron-irradiated silica glasses with lithium impurities; alkali silicate glasses with Li, Na, and K cations; and glasses in the two-alkali Na-K systems. It is established that the energy of the radiative transition of a modified nonbridging oxygen hole center, namely, ≡Si-O·/Me ⁺, depends on the alkali cation type.     

Coupling of diffusion and chemical stress: The case of ion exchange in glass

The chemical strengthening of glass results from an ion exchange process in which smaller alkali ions in a glass are replaced with larger alkali ions from a molten salt bath. This interdiffusion process leads to a buildup of chemical stress in the glass. However, traditional modeling of the ion exchange process has not fully accounted for interaction effects between mass diffusion and the chemical stress developed during the process. In this study, we develop the general theory of coupling between diffusion and stress, resulting in a single flux equation with a concentration- and stress-dependent interdiffusion coefficient. We apply the theory to the specific cases of chemically strengthened soda lime silicate and aluminosilicate glasses, demonstrating the impact of interaction terms on concentration profiles and interdiffusion coefficient. Following a phenomenological approach, this study demonstrates the effect of the interdiffusion on stress generation and vice versa to account for deviations from the simple expressions published hitherto in the literature.     

Aluminum‐enhanced alkali diffusion from float glass to PVD‐sputtered silica thin films

Interdiffusion processes between aluminum enriched PVD‐sputtered silica thin films and industrial float soda‐lime silicate glass substrates are quantitatively studied using SIMS analysis. Heat treatments are performed at temperatures close or above the glass transition temperature of the float glass. Aluminum doping of the film is shown to strongly increase the migration of alkali from the glass substrate to the silica thin film. In particular the final alkali content in the film exhibits a linear scaling with the aluminum concentration. An interdiffusion process is evidenced between bulk alkali ions and protons originating from a significant water content in the as‐deposited silica film. Experimental measurements of sodium concentration are shown to be consistent with a simple thermodynamic model based on the equilibration of the activity of sodium between the film and the glass substrate.     

Molecular dynamics study of correlations between IR peak position and bond parameters of silica and silicate glasses: Effects of temperature and stress

In the IR spectra of the silica and silicate glasses, the shifts of the maximum intensity position of the ν_{Si–O–Si,as} band upon heating or applying mechanical stress could be attributed to changes in the distribution of bond parameters such as bond length and bond angle. Upon heating, isotropic expansion occurs and the density changes; upon applying mechanical stress, anisotropic strain is induced and a significant change in the Si–O–Si bond angle is observed. From molecular dynamics simulations of a silica glass, we show that the peak position shift correlates better with the asymmetric change in the Si–O bond length distribution, rather than the Si–O–Si bridge angle, the O–Si–O tetrahedral angle, or the density change. This new finding provides an insight into how and why the ν_{Si–O–Si,as} IR peak of soda lime silica (SLS) glass shifts upon chemical strengthening via ion exchange and thermal tempering.     

Thermodynamic insight into the evolution of medieval glassworking properties

We present differential scanning calorimetry (DSC) analyses of seven French stained glasses from the 13th to 16th centuries. These glasses illustrate the dramatic compositional change from the antique soda‐rich glasses to potash‐ and lime‐rich compositions, resulting in drastic temperature and viscosity increases. We investigate the influence of chemical composition on glass thermal properties: glass‐transition (T_g), crystallization, and melting temperatures. We find that T_g varies from 533°C (soda type) to 638°C±17°C (potash type) to 685°C±5°C (lime type). The viscous slowdown of the melt as a function of the temperature, close to T_g, was modeled using the Vogel‐Tammann‐Fulcher equation. This enables temperature‐viscosity profile calculations, and suggests that recipes have been empirically optimized to reach similar thermoelastic properties suitable for glassmaking despite changing the nature of raw materials.     

Specific Features of Changes in the Properties of One- and Two-Alkali Borate Glasses Containing Water: I. Viscosity, Thermal Expansion, and Kinetics of Structural Relaxation in Binary Alkali Borate Glasses

Alkali borate glasses with different contents of residual water are prepared by varying the synthesis conditions. The temperature dependences of the viscosity and thermal expansion of glasses are obtained. The structural relaxation parameters are calculated from the hysteresis dilatometric curves measured. The water content is determined using the IR absorption spectra in the range of stretching vibrations of hydroxyl groups at room temperature. It is found that an increase in the water concentration in alkali borate glasses leads to a decrease in the viscosity. The character of variations in the viscosity logarithm with a change in the water content depends on the alkali cation concentration. The glass transition temperatures determined from the dilatometric curves for all the studied glasses decrease with an increase in the water content. As the water concentration increases, the thermal expansion coefficient (above and below the glass transition range) and the degree of fragility decrease for glasses containing 25 mol % Na₂O, increase for glasses with an alkali oxide content of 15 mol %, and remain virtually unchanged for glasses involving 5.5 mol % Na₂O. A change in the water content in the concentration range under investigation does not affect the structural relaxation parameters.     

Enhancement of mechanical properties and chemical durability of Soda-lime silicate glasses treated by DC gas discharges

We report for the first time a study on non-contact thermal poling of soda lime silicate glasses using DC gas discharge. In this work, the formation of a glow discharge is evidenced during the thermal poling treatment (longer than 30 minutes). The hardness and the chemical durability of glasses poled under different conditions (contact or non-contact) and atmospheres (nitrogen or air) are measured and compared to that of un-poled reference glass. The results reveal enhanced mechanical and chemical properties for samples poled under nitrogen as compare to air poled or soda lime silicate glass samples. A structural and chemical analysis of surface of the glass using IR-reflectance measurement and ToF-SIMS is also presented. The formation of a “silica-like” layer on the surface of nitrogen poled glasses is observed, which is likely associated with the enhancement of surface properties. On the other hand, the introduction of protons beneath the surface of glasses poled under air leads to the formation of a hydrated alkaline earth silica layer. Based on the observations a mechanism behind the sustainability of the plasma under DC conditions is proposed.     

Electric field-assisted ion exchange strengthening of borosilicate and soda lime silicate glass

In this study, we investigate the effects of electric field-assisted ion exchange (EF-IE) on potassium for sodium ion exchanges of soda borosilicate and soda lime silicate glasses. The results show that applying an electric field (E-field) with the intensity of 1000 V cm⁻¹ for few minutes produces an exchanged layer with a thickness comparable to the conventional chemical strengthening for 4 hours. There is a critical E-field that increases the mobility and, therefore, the diffusion coefficient of the potassium ions in the glasses. The increase is, perhaps, related to the evolution of the glass structure due to the penetration of potassium ions under an E-field. Vickers indentations showed that strong compression is generated in the glass by EF-IE; however, the bending strength improvement is limited because of the presence of large surface defects and the stress distribution inhomogeneity.     

Low‐Energy Ion‐Scattering Spectroscopy of Modified Silicate Glasses

Low‐Energy Ion‐Scattering (LEIS) spectroscopy is a technique with a unique sensitivity to the elemental composition of the top atomic layer of a solid surface. LEIS measurements of ternary silicate glasses modified with Na₂O, Cs₂O, CaO, and BaO show that the compositions of the as‐cast (melt) surface and the in‐vacuum fracture surface often differ. While the as‐cast surface is usually depleted of alkali ions (Na⁺ or Cs⁺) compared to the nominal (batch) glass composition, there is often strong accumulation of the same mobile cations on the fresh fracture surface. Depth profiles obtained by sputter etching reveal elemental concentration gradients normal to the glass surface. The final concentrations often fail to reach the nominal glass composition, suggesting the likely presence of preferential sputtering effects and thereby the distortion of the measured concentration gradient. At present, the lack of reliable standards and preferential sputtering effects in the LEIS of multicomponent glasses limit somewhat the absolute chemical composition and structural information that can be obtained with this otherwise unique and powerful method of surface analysis.     

Manganous-Manganic Equilibrium in Alkali Borate Glasses

The manganous-manganic equilibrium was studied in potassium, sodium, and lithium borate glasses. The glasses were analyzed chemically for total and trivalent manganese. The manganese equilibrium shifts more toward the oxidized state when the alkali concentration in the glass is increased and/or when the molar equivalent of lithia is replaced by soda and soda is replaced by potash. A linear relation between log (Mn³⁺/Mn²⁺) and mole percent alkali oxide was observed. Straight lines were obtained for lithium, sodium, and potassium borates. The disadvantages of using a concentration equilibrium constant where the glass composition is varied are discussed.     

Effect of glass composition on the hardness of surface layers on aluminosilicate glasses formed through reaction with strong acid

The effect of glass composition on physico‐chemical properties of surface layers formed through reaction between strong acid and several silicate and aluminosilicate glasses was studied through transmission‐IR, ATR‐IR, XPS, SIMS, and nano‐indentation analyses. It was shown that aluminum is depleted from the surface while molecular water is diffused into the surface layer of glasses with high levels of aluminum. Nano‐indentation experiments indicated that the hardness of the surface layers were decreased compared to that of the bulk region and the degree of the softening was more significant in the high aluminum glass.     

EFFECT OF IRON OXIDE ON PROPERTIES OF SODA-DOLOMITE LIME-SILICA GLASS*

In two base glasses, the first containing 16% of sodium oxide, 10% of dolomite lime, and 74% of silica, and the second with 14% of sodium oxide, 12% of dolomite lime, and 74% of silica, iron oxide was systematically substituted for (a) Na₂O, (b) CaO·MgO, and (c) SiO₂ in amounts of 1, 3, and 5%. The effects of these substitutions on such properties as liquidus temperature, viscosity, deformation temperature, fiber softening point, density, coefficient of expansion, and the resistance of the glasses to dilute acid and distilled water, arc presented.     

Electronically Conductive Vanadate Glasses for Resistive Plate Chamber Particle Detectors

Particle detectors are constantly being built and refitted with new technology to improve the spatial resolution, radiation hardness, and speed at which the detector can capture particle events. One of the most crucial components of a modern collider experiment is the hadron calorimeter. One of the proposed improvements on future hadron calorimeters is to utilize resistive plate chambers (RPCs). They provide the spatial and energy resolution as well as could provide speed and radiation hardness. RPCs depend on manufacturing electrically conductive glasses that are mechanically strong, durable, radiation resistant, and not ionically conductive. To achieve such requirements, vanadate glasses were developed as alternatives to current prototypes which use soda lime silicate glasses. The conductivity, oxidation states of vanadium, radiation hardness, as well as the prototype performance, were tested on vanadate glasses. The prototype tests show that using 0.40ZnO−0.40TeO₂−0.20V₂O₅ can improve the RPC detector rate up to 100 times.