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The viscosity of silica glasses with different water contents was measured by penetration of sapphire microspheres in the range from 1012-1014·7 Pas at ambient pressure. Commercial silica glasses were used together with hydrous silica glasses, which were prepared by melting glass powder plus water in an internally heated pressure vessel at 2-3 kbar and 1350-1450°C. The temperature dependence of the viscosity of silica glasses with total water contents Cw of 5·4×10-4, 7·0×10-4, 1·00×10-2, and 1·55×10-2(Cw in mass fractions) can be described by Arrhenius equations. From the results, the linear dependence of the T12 isokom (K) with the logarithm of the water content was determined as T12=192-409 logCw. The analysis of the compositional dependence of the T12 isokom in the H2O-Na2O-SiO2 system reveals a temperature depression of up to 200 K for mixed water- and sodium-bearing glasses compared to H2O-SiO2 and Na2O-SiO2 glasses with same molar silica content. From these findings we conclude that protons may contribute significantly to the mixed alkali effect in glasses.
Physical storage of gaseous hydrogen under high-pressure in glassy micro-containers such as spheres and capillaries is a promising concept for enhancing safety and the volumetric capacity of mobile hydrogen storage systems. As very low permeation through the container wall is required for storage of compressed hydrogen, development of glasses of minimal hydrogen permeability is needed. For this purpose, one has to understand better the dependence of hydrogen permeability on glass structure. The paper points out that minimizing the accessible free volume is as one strategy to minimize hydrogen permeability. Based on previously measured and comprehensive literature data, it is shown that permeation is independently controlled by ionic porosity and network modifier content. Thus, ionic porosity in modified and fully polymerized networks can be decreased equally to the lowest hydrogen permeability among the glasses under study. Applying this concept, a drop of up to 30,000 with respect to the permeation of hydrogen molecules through silica glass is attainable.
Hydrogen gas diffusivity of fourteen glasses of the Na2O-Al2O3-SiO2 system are studied along the joins quartzalbite-jadeite-nepheline (Qz-Ab-Jd-Np, fully polymerized) and albite-sodium disilicate (Ab-Ds, depolymerized).
Density measurements show that ionic porosity decreases from 54.4% (Qz) to 51.5% (Np) and from 52.4% (Ab) to 50.2% (Ds). Hydrogen diffusivity D follows similar trends but at another scale. D at 523 K decreases from 4×10−12 to 3×10−14m2 s−1 (Qz-Np) and from 4×10−13 to 3×10−15m2 s−1 (Ab-Ds). Charge compensating Na+ acting as a filling agent in fully polymerized network structures leads to up to one order of Magnitude higher diffusivities as depolymerized glass structures of the same SiO2 content where Na+ takes the role of a
modifier ion. Temperature dependence of the diffusivity indicates that both the activation energy involved with the moving H2 molecule as well as the accessible volume in the structure contribute to this compositional trend.
Crack growth velocity in alkali silicate glasses was measured in vacuum across 10 orders of magnitude with double cantilever beam technique. Measured and literature crack growth data were compared with calculated intrinsic fracture toughness data obtained from Young´s moduli and the theoretical fracture surface energy estimated from chemical bond energies. Data analysis reveals significant deviations from this intrinsic brittle fracture behavior. These deviations do not follow simple compositional trends. Two opposing processes may explain this finding: a decrease in the apparent fracture surface energy due to stress-induced chemical changes at the crack tip and its increase due to energy dissipation during fracture.
Stable crack growth was measured for nominal dry and water-bearing (6 wt%) soda-lime silicate glasses in double cantilever beam geometry and combined with DMA studies on the effects of dissolved water on internal friction and glass transition, respectively. In vacuum, a decreased slope of logarithmic crack growth velocity versus stress intensity factor is evident for the hydrous glass in line with an increase of b-relaxation intensity indicating more energy Dissipation during fracture. Further, inert crack growth in hydrous glass is found to be divided into sections of different slope, which indicates different water related crack propagation mechanism. In ambient air, a largely extended region II is observed for the hydrous glass, which indicates that crack growth is more sensitive to ambient water.
We present an easy-to-apply method to predict structural trends in the internal nucleation tendency of oxide glasses. The approach is based on calculated crystal fracture surface energies derived from easily accessible diatomic bond energy and crystal lattice data. The applicability of the method is demonstrated on literature nucleation data for isochemically crystallizing oxide glasses.
The H2 effusion from H2 saturated glass powders, H2 permeation through the wall of blown glass bulbs, and H2 permeation through the wall of glass capillaries were applied to evaluate the permeability of hydrogen gas in a barium-aluminoborosilicate (BABS) glass. To validate these methods, two commercial glasses (vitreous silica and borosilicate) were used as a reference. Permeation values obtained from the different experiments agreed within a factor of 3 or less. The H2 permeability of BABS glass at temperatures close to ambient was found to be at least 3 orders of magnitude below that of borosilicate and silica glasses. The powder method, which requires minimal sample preparation efforts, turned out to provide easy access to the measurement of H2 permeability of glasses down to P = 3.9 × 10- 21 mol s- 1 Pa- 1 m- 1.