Sub-critical crack growth rate of soda-lime-silicate glass and less brittle glass as a function of fictive temperature

Sub-critical crack growth rates of soda-lime-silicate glass and less brittle glass with different fictive temperatures were compared using the DCDC method under both dry and humid atmospheres in order to investigate the origin of the unique mechanical features of the less brittle glass developed by Ito and his collaborators. In both dry and humid atmospheres, the crack velocity of the soda-lime-silicate glass was slower than that of the less brittle glass. For both glasses, the glass sample with higher fictive temperature showed a slower crack growth rate under both dry and humid atmospheres. These observations can be explained by the tendency for the plastic flow at the crack tip; the soda-lime-silicate glass is expected to show easier plastic flow under tension than the less brittle glass, and also the samples with higher fictive temperatures are expected to show easier plastic flow, leading to greater fracture toughness, K_IC, and slower crack growth rate.     

Deceleration of surface structural relaxation in chlorine-containing silica glass due to chlorine volatilization

Both surface and bulk fictive temperatures of chlorine-containing silica glass were measured using the IR method, after thermal, mechanical and chemical treatments. A metastable equilibrium state at 1200 °C was first established for the glass by heat-treatment and a uniform fictive temperature was observed except for the sample surface created by polishing after the heat-treatment. The densified layer of the polished surface shifted the IR peak wavenumber, making the fictive temperature appear higher than the bulk. During the second heat-treatment at 950 °C, the sample with the as-heat-treated surface and uniform fictive temperature of 1200 °C developed non-uniform fictive temperature distribution with the bulk fictive temperature becoming lower than the surface fictive temperature. Usually, surface structural relaxation is faster than bulk structural relaxation and the surface fictive temperature becomes lower than the bulk fictive temperature when heat-treated at a lower temperature than the initial fictive temperature. The observed anomalous feature was attributed to chlorine volatilization from the glass surface layer creating a high viscosity surface layer. This conclusion was supported by the diffusion data of chlorine in the glass available in the literature.     

Effect of organic acid vapors on the alteration of soda silicate glass

Organic acids were previously shown to be involved in the alteration of historic soda silicate glasses in humid atmospheres under museum storage conditions. The present study investigates the role of these pollutants on the visual, compositional and structural modification of soda silicate glasses. Replica glasses aged in humid or humid/acidic atmospheres under accelerated conditions were examined and compared using light microscopy, electron microprobe and Raman spectroscopy. The characteristic modifications induced by each atmosphere are described. In the acid polluted atmosphere the leaching process created a layer that retained the transparency of the glass but with a chemical structure hydrated and more polymerized following the loss of alkali and the associated non-bridging oxygens, and the formation of new bridging bonds. In an unpolluted humid atmosphere, the dissolution process caused disruption of the silicate network at the glass surface and formation of an opaque gel layer. The hydrated silicate species and the cations in this gel layer subsequently polymerized to form a new amorphous material, hydrated and more depolymerized than the original glass. This investigation confirms that organic acid pollutants are responsible for the modifications observed on altered historic soda silicate glasses in the collections of the National Museums of Scotland.     

Indentation-induced microhardness changes in glasses: Possible fictive temperature increase caused by plastic deformation

The microhardness around a large indentation was measured for different types of glasses. In soda-lime silicate glass, a typical normal glass, the region in the immediate vicinity of the indentation was found to exhibit a lower hardness than the region far removed from the indentation. In silica glass, a typical anomalous glass, the region in the immediate vicinity of a large indentation was found to exhibit a higher hardness than the region far removed from the indentation. Asahi less brittle glass, an intermediate glass between normal and anomalous glasses, was found to exhibit little change in hardness in the vicinity of the large indentation. These findings can be explained by a deformation-induced fictive temperature increase leading to a lower hardness for soda-lime silicate glass and a higher hardness for silica glass.     

Anomalous temperature dependence of sub-critical crack growth in silica glass

The effects of temperature, water vapor, and stress on the rate of sub-critical crack growth (SCG) in fused silica are reported. The crack velocity was measured using the double-cleavage-drilled compression method. In contrast to other inorganic oxide glasses, crack growth velocities (in region I) were found to decrease with increase in temperature. Hence a small temperature rise has the apparent effect of improving the mechanical strength of a stressed-glass part. Despite the anomalous temperature dependence, SCG in fused silica is still likely governed by the established water-enhanced stress-corrosion mechanism; another competing phenomenon is proposed to cause the observed temperature dependence. Measured crack velocities are described using an empirical model (for region I) and a mass-transport model limited by Knudsen diffusion (for region II).     

Exponential structural relaxation of a high purity silica glass

While most other glasses exhibit non-exponential structural relaxation characteristics even when the change of fictive temperature is small, a high purity silica glass exhibited exponential structural relaxation. This was demonstrated by showing that the non-exponential exponent or β value of the KWW function of the high purity silica glass approaches unity when the change of the fictive temperature approaches zero both from higher and lower temperature sides of the heat-treatment temperature. The non-exponentiality of the structural relaxation of this glass when fictive temperature change is finite is due to the change of relaxation time during the structural relaxation.     

SAXS study of the micro-inhomogeneity of industrial soda lime silica glass

The microstructure of a variety of industrial multicomponent soda lime glasses for container and glazing and of a lead alkali silicate glass for pressed tableware articles was analyzed using small angle X-ray scattering (SAXS). No inhomogeneity with size >0.5 nm was found in the industrial samples, while ternary soda lime glass samples with a suitable composition when heat treated developed a phase separation which SAXS detected without difficulty. The results obtained disprove earlier reports which attributed problems of rheology and strength affecting container production (‘bad workability’) to microstructure formation.     

IR investigation of density changes of silica glass and soda-lime silicate glass caused by microhardness indentation

Density changes of silica glass and soda-lime silicate glass caused by ball indentation and Vickers indentation were investigated. The IR reflection peak shift of the silica structural band was monitored to determine the extent of the fictive temperature change and the corresponding density change. Under the central portion of the ball indentation, the density of silica glass increased while a change in the soda-lime silicate glass structure was not clear. On the other hand, in the vicinity of the Vickers indentation, the opposite trend was observed. Namely, soda-lime silicate glass exhibited the structural change corresponding to the density decrease, while the structural change of the silica glass was uncertain. The initial density of the silica glass influenced the change of density under ball indentation in such a way that the initial density difference of the glass samples was reduced.     

Mechanical properties and adhesion of hydrated glass surface layers

This paper reviews results for interfacial adhesion and fracture of silicate glasses that demonstrate the effect of hydrated glass surface layers on the mechanical properties of glass. First, it is shown how the generation of hydrated surface layers formed on alkali borosilicate glasses can control crack propagation rates. Crack growth data, solution analysis and surface stress measurements are used to support a fracture model that involves the generation of surface stress on the crack walls behind the crack tip. A fracture mechanics based model is used to show that stressed layers can contribute to the crack tip stress intensity in a way that either increases or decreases the rate of crack propagation. In the case of alkali containing silicate glasses, tensile stresses formed on the crack walls increase the crack tip stress and contribute to the formation of a low velocity plateau in the stress intensity vs. crack velocity curve. Second, fracture mechanics test techniques are used to examine the adhesive bond formed between hydrated surface layers and bulk silicate glass. The adhesive bonds formed by sol-gel precursors composed of colloidal silica, hydrolyzed organosilanes and alkali silicate solutions are compared to determine the mechanism of interfacial bonding to dense silica substrates. The formation of siloxane bonds across the interface depends upon the nature of the silicate polyanions in solution. For the case of soluble alkali silicate derived films, heat treatments at temperatures as low as 200°C can result interferfacial adhesion energies as large as the fracture energy of silica glass. These results have important implications to the aging and repair of surface damage in glass as well as the adhesion of sol-gel derived thin films.     

Roughness of glass surfaces formed by sub-critical crack growth

This paper presents a study on the roughness of glass fracture surfaces formed as a consequence of sub-critical crack growth. Double-cantilever-beam specimens were used in these studies to form fracture surfaces with areas under well-defined crack velocities and stress intensity factors. Roughness depends on crack velocity: the slower the velocity, the rougher the surface. Ranging from approximately 1 × 10⁻¹⁰ m/s to approximately 10 m/s, the velocities were typical of those responsible for the formation of fracture mirrors in glass. Roughness measurements were made using atomic force microscopy on two glass compositions: silica glass and soda lime silica glass. For silica glass, the RMS roughness, R_q, decreased from about 0.5 nm at a velocity of 1 × 10⁻¹⁰ m/s to about 0.35 nm at a velocity of 10 m/s. For soda lime silica glass, the roughness decreased from about 2 nm to about 0.7 nm in a highly non-linear fashion over the same velocity range. We attributed the roughness and the change in roughness to microscopic stresses associated with nanometer scale compositional and structural variations within the glass microstructure. A theory developed to explain these results is in agreement with the data collected in the current paper. The RMS roughness of glass also depends on the area used to measure the roughness. As noted in other studies, fracture surfaces in glass exhibit a self-affine behavior. Over the velocities studied, the roughness exponent, ζ, was approximately 0.3 for silica glass and varied from 0.18 to 0.28 for soda lime silica glass. The area used for these measurements ranged from (0.5 μm)² to (5.0 μm)². These values of the roughness exponent are consistent with values obtained when the scale of the measurement tool exceeds a critical size, as reported earlier in the literature.     

Influence of thermal history on the structure and properties of silicate glasses

We studied a set of float glass samples prepared with different fictive temperatures by previous annealing around the glass transition temperature. We compared the results to previous measurements on a series of amorphous silica samples, also prepared with different fictive temperatures. We showed that the modifications on the structure at a local scale are very small, the changes of physical properties are moderate but the changes on density fluctuations at a nanometer scale are rather large: 12% and 20% in float glass and silica, for relative changes of fictive temperature equal to 13% and 25% respectively. Local order and mechanical properties of silica vary in the opposite way compared to float glass (anomalous behavior) but the density fluctuations in both glasses increase with temperature and fictive temperature.     

Water diffusion into a silica glass optical fiber

The diffusion coefficient and solubility of water in silica glass optical fiber cladding were measured in the temperature range of 600-800 °C and were compared with the corresponding values of bulk silica glasses. It was found that the diffusion coefficient was slightly lower and the solubility was appreciably higher in optical fiber, especially at low temperatures, compared with those in bulk silica glasses. The observed trend was consistent with the expected effect of fictive temperature.     

Oxygen and silver diffusion into float glass

In the float glass process, molten glass is floated on a molten metallic tin bath, such that tin penetrates the glass surface. Consequently, the glass has distinctly two different faces; the tin-penetrated face (bottom face) and the opposite face (top face). In this paper, the effects of tin on oxygen and silver diffusion into the top and bottom faces of a soda–lime–silica float glass are reported. It was revealed that oxygen diffusion from the atmosphere into the bottom face at temperatures above glass transition temperature was extremely suppressed near the surface region of the glass. This was not observed for the top face. This effect was ascribed to chemical reactions between the diffused oxygen and Sn²⁺ near the surface of the glass. Silver diffusion was also influenced by the tin due to chemical reactions of Ag⁺ ions with Sn²⁺, leading to the precipitation of nanometer-sized Ag crystals. As a result, the coloration due to the surface plasmon resonance of the Ag crystals was significantly different between the top and bottom faces because of differences in the nucleation and growth processes associated with the Ag crystals.     

A glass with high crack initiation load: Role of fictive temperature-independent mechanical properties

The crack initiation load of a series of calcium aluminosilicate glasses and selected commercial glasses were evaluated using Vickers indentation. The results showed that a calcium aluminosilicate glass containing 80 mol% SiO₂, 10 mol% Al₂O₃ and 10 mol% CaO exhibited a high crack initiation load comparable to that of the less-brittle glass (LB glass) developed by Asahi Glass Co., Ltd. It has previously been determined that glasses experience a fictive temperature increase by indentation. The indented region of a glass, therefore, acquires, in general, different mechanical properties, such as hardness and elastic moduli, from the original, unindented glass. The extent of these mechanical property changes depends upon the glass composition and a certain glass composition with fictive temperature-independent mechanical properties can have the deformed region with matching mechanical properties to those of the undeformed region of the glass. It was found that the calcium aluminosilicate glass having no fictive temperature dependence on elastic moduli gave the highest crack initiation load. However, this composition did not coincide with fictive temperature-independence of hardness or density.     

Dynamic condensation of water at crack tips in fused silica glass

Water molecules play a fundamental role in the physics of slow crack propagation in glasses. It is commonly understood that, during stress-corrosion, water molecules that move in the crack cavity effectively reduce the bond strength at the strained crack tip and, thus, support crack propagation. Yet the details of the environmental condition at the crack tip in moist air are not well determined. In a previous work, we reported direct evidence of the presence of a 100 nm long liquid condensate at the crack tip in fused silica glass during very slow crack propagation (10^?9–10^?10 m/s). These observations are based on in situ AFM phase imaging techniques applied on DCDC glass specimens in controlled atmosphere. Here, we discuss the physical origin of the AFM phase contrast between the liquid condensate and the glass surface in relation to tip-sample adhesion induced by capillary bridges. We then report new experimental data on the water condensation length increase with relative humidity in the atmosphere. The measured condensation lengths were much larger than what predicted using the Kelvin equation and expected geometry of the crack tip.     

An analytical model for combined radiative and conductive heat transfer in fiber-loaded silica aerogels

An improved analytical model for the total thermal conductivity of fiber-loaded silica aerogels was developed based on the complex refractive index, size, orientation, volume fraction and morphology of the fibers and silica aerogel. A cubic array of spherical porous secondary nanoparticles and a modified parallel-series model were proposed to model the combined solid and gaseous thermal conductivities. An anomalous diffraction theory (ADT) was used to predict the fiber extinction coefficient. Five common fiber types in the composites were studied including amorphous SiO₂ glass, silicon glass, common float glass, soda lime silica glass and borosilicate glass. The results show that the total extinction coefficient of the silica aerogel system is largest by loading with the common float glass fiber and lowest by loading with the soda lime silica glass among the five fiber types. The model provides theoretic guidelines for material designs with optimum parameters, such as the type, inclination angle, volume fraction and diameter of the fibers as well as the aerogel nanoparticle and pore sizes. The optimum fiber for improved thermal insulation should have a large spectral complex refractive index throughout the infrared region.     

Fictive temperature of GeO2 glass: Its determination by IR method and its effects on density and refractive index

A simple IR method of determining the fictive temperature of GeO₂ glass, both surface and bulk, was developed using the same technique developed earlier for silica glass. Specifically, IR absorption and reflection peak wavenumbers of GeO₂ structural bands were found to be correlated with the fictive temperature of the glass. Using this method structural relaxation kinetics can be investigated. Density and refractive index of GeO₂ glass were also measured as a function of fictive temperature.     

Effects of aluminum impurity on the structural relaxation in silica glass

To elucidate effects of Al impurity on the glass-forming process in silica glass, the structural relaxation in Al-containing silica glass, with alkali ions of only trace levels, was investigated by observing the fictive temperature. The fictive temperature was determined by infrared (IR) absorption analysis. Al, even at concentrations lower than 10 wtppm, increases the relaxation time and the activation energy of the -relaxation. It also suppresses the sub-relaxational process due to OH ions. These results indicated that Al should have other effects on structural relaxation than alkali–aluminate complex formation, as has been thought to be the cause for an increase in the -relaxation time and thus the viscosity of silica glass. Furthermore, the structural relaxation does not merely depend on the number of non-bridging oxygen atoms in the glass network.     

Field-assisted ion exchange between molten alloys and soda lime glass

Using molten alloys, the electrolysis of soda lime glass has been studied. Ions from a molten anode can be driven into soda lime glass by applying a modest electric potential. The anode current densities have been measured. The temperature and potential dependences have also been measured. The current-time behavior depends on the ion exchange. In a molten alloy the most easily oxidized metal is suited for exchange.     

Rayleigh scattering in silica glass with heat treatment

We investigated Rayleigh scattering in silica glass with heat treatment under various conditions, including quenching and slow cooling, and its relation to fictive temperature. The Rayleigh scattering intensity varied according to the conditions of the heat treatment. The scattering intensity in slowly cooled samples is less than that in quenched samples after heating at the same temperature. We evaluated fictive temperatures based on measurements of infrared absorption and Raman scattering. The Rayleigh scattering intensity was related to the fictive temperature regardless of the heat treatment conditions, and a linear relation between them was obtained. In addition, we suggest that the decrease in scattering intensity in slowly cooled samples results from structural relaxation due to viscous flow during the cooling process.