Inter-relationships between composition and near surface mechanical properties of silicate glasses

The surfaces of silicate glasses undergo hydration in normal atmospheric environments. The hydrated region will have different mechanical properties to the bulk glass and this work assesses the inter-relationships between composition and the near surface mechanical properties of silicate glasses through the use of nanoindentation. The effect of glass composition and hydration on the near surface mechanical properties is considered for poorly and highly durable silicate glasses. With poorly durable glasses the hydrated layer depth is much greater than the indentation depth and thus the results obtained on these glasses are used to help interpret the more complex results obtained on more durable glasses where the hydrated layer is smaller than the indentation depth. Based on the results the application of nanoindentation for measuring the near surface mechanical properties of glasses and studying hydration is discussed.     

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.     

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.     

Hydration of soda-lime glass

The hydration of soda-lime glass is studied using resonant nuclear reactions to measure the hydrogen and sodium profiles of hydrated glasses. The rate of growth of the surface layer of hydrated glass is initially proportional to the square root of time as is characteristic of diffusion controlled processes. After longer exposure a steady-state hydration profile is observed, which indicates that in addition to the diffusion controlled reaction there is a slow etching of the glass surface. The measured hydration profiles are discussed in relationship to the Doremus model of interdiffusing ions, which is found to be in good agreement with the data. This model is also discussed in relationship to measured hydration profiles of vacuum heated samples of hydrated glass.     

Inward cationic diffusion in glass

We report that inward diffusion of network-modifying divalent cations can occur in iron-containing silicate glasses when they are treated in a reducing atmosphere near the glass transition temperature. As a result of the inward diffusion, a silica-rich nanolayer forms on the glass surface, which increases the hardness and chemical durability. The thickness of the layer can be controlled by varying the heat-treatment conditions. We clarify the mechanism of the inward diffusion and calculate the diffusion coefficient for the network-modifying divalent cations. We demonstrate that the diffusion of these ions is the rate-limiting factor for the reduction process.     

Structure and electric conductivity of reduced lead–germanate,bismuth–germanate and bismuth–silicate glasses modified with potassium

Lead–germanate, bismuth–germanate and bismuth–silicate glasses, as potential materials for detectors production, have been modified with potassium with the purpose of improvement of mechanical properties. Studies on the influence of potassium modification on the structure and electric properties have been conducted with AFM, DSC and conductivity measurements. It has been observed that potassium modification improves the mechanical and technological properties of glasses and simultaneously changes slightly their electric properties. The studies have confirmed that bismuth–silicate and bismuth–germanate glasses are good materials for microchannel plates or channeltrons.     

Hydration of phosphate and borate glasses in an autoclave

Kinetics of hydration of CaO---Al₂O₃---P₂O₅ and Na₂O---CaO---B₂O₃---Al₂O₃ glasses in an autoclave at high temperatures and high pressures has been investigated. The hydration of the phosphate glasses may occur as a result of hydrolysis of glass constituents to form orthophosphate crystals. Cabal glasses which do not contain any alkali oxides have shown a quite high resistance to water. Substitution of sodium for calcium deteriorates the chemical durability of Cabal glasses.     

Field-driven redistribution of “guest protons” within protonated silicate glasses

Protonated layers of lithium silicate glasses generated by electrolysis were penetrated by lithium ions from appropriate anodic solutions during a second electrolysis. As the electric fields were applied in the same direction during both electrolyses, the number of protons within the glasses was unchanged. As is made apparent in the discussions of the local resistivities and the resulting profiles of the electric fields within the electrolysed membranes, the steady state of the protonated layer was disturbed by the lithium ions making the migrating front of the less mobile protons unstable. The protons were diluted, while simultaneously the layer thickness was increased.

A remarkable change in the ir spectrum observed after the second electrolysis and indicating that Beer's law is not valid is explained by the tendency of protons to occupy preferred sites. It is proposed that mixed twin siloxy groups containing one lithium ion and one proton with different bond energies and thus different probabilities for leaving the entity act as proton traps and function as single sites for migrating lithium ions. The effect was observed with several lithium silicate glasses but not with a lithium aluminum silicate glass. Protons introduced as probes for alkali into glasses may thus contribute information on the glass structure.     

Influence of sol-gel coatings on crack initiation by vickers indentation in soda-lime glass

In this work an indentation technique was used to study the effect of the sol-gel coatings of soda-lime glasses on crack formation. The tendency of samples to develop radial cracks has been evaluated by measuring their number in correspondence with the Vickers impressions as a function of the applied load. Silica coatings of different thickness were obtained from alcoholic solutions of TEOS by the dipping technique on glass sheets with different degrees of surface hydration.

All the coated samples show a lower crackability compared with the uncoated ones. It was found that this parameter is influenced by layer thickness, heat treatment temperature and by the degree of galss surface hydration.     

Effect of alumina on enthalpy of mixing of mixed alkali silicate glasses

The enthalpy of mixing of mixed alkali (Na₂O and K₂O) silicate glasses containing various concentrations of alumina was determined using an ion-exchange equilibrium method. For glasses with a constant alkali concentration, the enthalpy of mixing was found to become less negative with alumina addition. Consistent with our previous results on the enthalpy of mixing of alumina-free mixed alkali silicate glasses, the magnitude of enthalpy of mixing exhibited a good correlation with the molar volume mismatch of the corresponding two single alkali glasses as well as with the extent of conductivity mixed alkali effect, e.g. excess activation energy of conductivity, ΔE. The reduction of the magnitude of the enthalpy of mixing with alumina addition can be attributed to the reduction of non-bridging oxygen and ionic field strength. Combining the present results with results obtained earlier, the magnitude of the enthalpy of mixing for all mixed alkali (Na₂O and K₂O) silicate glasses with and without alumina was expressed by a simple function of a modified Tobolsky parameter, which takes into account the alkali concentration and the difference in cation-to-effective anion distances. The enthalpy of mixing data of the mixed alkali glasses was then compared with reported experimental data on the conductivity of mixed alkali aluminosilicate glasses. What appears to be conflicting experimental data can be understood in terms of the magnitude of the enthalpy of mixing and we can conclude that the mixed alkali effect is closely correlated with the negative enthalpy of mixing.     

Influence of alkali and alkali-earth metal oxide substitutions on the properties of lithium-iron-phosphate glasses

The influences of different alkali and alkali-earth oxide substitutions on the properties of lithium-iron-phosphate (LIP) glasses have been studied. Na₂O, K₂O, MgO, CaO and BaO were used to substitute Li₂O to prepare LIP glasses with molar compositions of (20 − x)Li₂O − xR₂O(RO) − 30Fe₂O₃ − 50P₂O₅ (x = 2.4, 4, 5.6 and 7.2). The glass transition temperature (T_g) was determined by the differential thermal analysis technique. The density and chemical durability of the prepared glasses were measured based on the Archimedes principle and the weight losses after the glasses were boiled in water. The results show that T_g decreases with the initial substitutions, whereas the density and chemical durability increase. The diminution of the aggregation effect of Li⁺ ions on the glass structure due to the decrease in Li⁺ concentration, the larger molecule weights of the substitutes, the mixed-alkali and depressing effects as well the slower mobility of substitute ions mainly contribute to the initial changes in T_g, density and chemical durability of the LIP glasses, respectively. Further increasing the amounts of substitutes brings about increasing diminution of the aggregation effect of Li⁺ ions and breakage of the glass network on the one hand and increasing amounts of substitutes with larger molecule weights and ion radii on the other hand. Both aspects influence the glass properties oppositely and consequently non-monotonic variations in the properties of LIP glasses with the substitutions are observed.     

Chemical durability of lead silicate glass in HNO3, HCl and H2SO4 aqueous acid solutions

Acid dissolution of silicate glasses with different lead contents was rigorously investigated. Aqueous solutions containing 0.5, 1, and 2 N HNO₃, HCl and H₂SO₄ were used to measure the durability of the glass probes. Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), Inductively Coupled Plasma (ICP), X-ray Diffraction (XRD) and weight loss analyses were used to evaluate the morphological/compositional changes of the probes, the ash deposit, and the aqueous solutions produced due to the dissolution of the glass specimens. Empirical results showed that any increase in the lead content of the probes deteriorated the durability of the glasses by accelerating the hydrolysis of the silica network. ZrO₂ and TiO₂ additions had inverse effect and improved the chemical durability and the practical life-time of the lead glasses.     

Influence of the mixed alkali effect on the chemical durability of Na2O---TiO2---SiO2 glasses

The influence of the mixed alkali effect on the chemical durability of Na₂O---TiO₂---SiO₂ glasses during substitution of K₂O for Na₂O in 21Na₂O---26TiO₂---53SiO₂ glasses was investigated. The best chemical durability was found at K₂O/Na₂O = 2.5 where the minimum was close to K⁺ ions of larger size. It was shown that the water corrosion process of the system was predominantly controlled by both the mobility and the exchange function of K⁺ ions resulting in the generation of a titanium-rich and silicon-rich layer at the surface. The mixed alkali effect can therefore be applied to lower the rate of water corrosion and increase chemical durability so that optical glasses with higher chemical durability can be obtained.     

Spectroscopic properties and simulation of white-light in Dy-doped silicate glass

Spectroscopic properties of various concentrations Dy³⁺-doped silicate glasses were characterized by excitation and emission spectra. The optimal doping concentration of Dy³⁺ ions was found to be 3.0 wt%, and the nature of resonance energy transfer was confirmed to be electric dipole-dipole interaction according to Huang’s rule. Simulation of white-light for these glasses was also performed by varying the excitation wavelength. The results show that the white-light luminescence color could be tuned to various wavelength excitations, and the present silicate glass is more suitable for generation of white-light for blue LED chips.     

Structure and lithium ion diffusion in lithium silicate glasses and at their interfaces with lithium lanthanum titanate crystals

Solid state lithium ion electrolytes are important to the development of next generation safer and high power density lithium ion batteries. Lithium containing glasses such as lithium silicate glasses have been widely studied due to their high ionic conductivity. Recently, lithium silicate glasses were introduced in polycrystalline lithium lanthanum titanate (LLT) ceramics as intergranular thin films between the crystalline grains to achieve higher lithium ion conductivities in these solid state electrolytes. In this work, we present investigations of the structure and diffusion behavior of lithium silicate glasses and their interfaces with LLT crystals using molecular dynamics simulations. The short and medium range structures of the lithium silicate glasses were characterized and the ceramic/glass interface models were obtained using MD simulations. Lithium ion diffusion behaviors in the glass and across the glass/ceramic interfaces, as well as the effect of atomic structure on diffusion behaviors, were investigated. It was found that there existed a minor segregation of lithium ions at the glass/crystal interface. The interface lithium ion diffusion energy barrier was found to be dominated by the glass phase.     

Raman-scattering measurements of silicate glasses containing sulphate

Raman spectra of silicate glasses containing sulphate are reported. Sulphate was introduced into the glass by addition of sulphate to the batch, by reaction of a molten sulphate layer with a glass melt or by reaction of SO₂ vapour with a glass melt. Thin sections parallel to the surface of the glass were cut and Raman spectra were recorded of each section as a function of depth from the surface. The effect of carbon on the sulphate content of the glass was investigated. The results are discussed in relation to the fining and homogenizing action of sulphate in silicate glasses.     

Synthesis and properties of cerium aluminosilicophosphate glasses

Cerium oxide is commonly added to silicate glasses as an optical property modifier. In particular, UV absorption, decoloration via redox coupling, and resistance to radiation-induced darkening are influenced by the addition of this rare-earth oxide. However, the limited solubility and visible color of rare-earth oxides in silicate glasses prevent any further beneficial enhancement of properties which might result from increasing the CeO₂ content. In contrast, rare-earth oxides are extremely soluble in phosphate glasses; for example, a binary cerium phosphate glass can incorporate up to 40 mol% CeO₂. Moreover, since the UV absorption edge of the phosphate network is blue-shifted compared to the silicate network, the effect of the Ce³⁺ absorption band tail on yellow coloration can be minimized.In this study, glasses in the cerium aluminosilicophosphate system were synthesized and a variety of physical and optical properties were measured including: density, refractive index, glass transition temperature, hardness, fracture toughness, and the location of the UV absorption edge. At ～9 mol% CeO₂, these cerium aluminosilicophosphate glasses exhibit similar coloration to commercially available silicate glasses which contain ～0.4 mol% CeO₂. Semi-quantitative photoemission analysis of the Ce oxidation states showed insignificant differences in the Ce³⁺/Ce⁴⁺ ratio between the phosphate and silicate glass systems.     

Experimental and theoretical studies of flame hydrolysis deposition process for making glasses for optical planar devices

We have here presented experimental and theoretical studies of a flame hydrolysis deposition (FHD) process for making glasses for optical planar devices. FHD involves deposition of soot particles generated in the flame on a planar surface to form a porous layer. In order to function as a waveguide core, the porous soot deposit must be sintered at high temperatures to form a dense glass. However, these temperatures are high enough to cause the dopants to volatilize at the surfaces of the deposit. As a result, dopant concentration gradients and compositional inhomogeneities are created in the densified glass layer which result in inferior optical properties. If the layers could be deposited pre-sintered during laydown, these problems could be minimized or avoided. To understand the FHD process and its effect on the morphology of the resulting deposit, a number of models have been developed. We present models to predict the structure of the soot-laden flame along with the methods to estimate soot number density and mean size at different locations in the flame. A simple method is presented to predict morphology of the suspended soot and soot deposit formed during deposition. Motivated by the predictions of the model, process changes were made which resulted in the morphology of the core layers to change from sooty to pre-sintered during deposition. These process changes resulted in core glasses with significantly improved core roughness, index uniformity and thickness uniformity which helped reduce the straight waveguide losses from 0.2-0.3 to 0.02-0.05 dB/cm. Details of underclad and overclad glasses which resulted in low warpage and polarization sensitivity of 0.1 nm for phasar or phasar-arrayed waveguide devices are also presented.     

Dealkalization of glass surfaces utilizing HCI gas

Surfaces of silicatee glasses can be dealkalized when exposed to SO₂⁻, chlorine- and fluorine-containing gases. The chemically modified near-surface regions display properties which are different from those of the bulk. Emphasis will be placed on the deakalization mechanism and the improvement of specific surface properties of various industrial glasses.     

Structural study of sol-gel silicate glasses by IR and Raman spectroscopies

A study of the structure and bonding configuration of sol-gel silicate glasses by Raman and infrared spectroscopies is presented. Moreover, a review of the Raman lines and infrared bands assignment, the identification of the non-bridging silicon-oxygen groups and the ring structures are also demonstrated. The evolution of the changes of the bonding configuration in the composition and the stabilization temperature of the bioactive glasses is discussed in terms of the structural and textural characteristics of the glasses. Raman and infrared analyses contribute to the improvement in understanding of the local symmetry for sol-gel silicate glasses. infrared spectroscopy has allowed to identify the vibration bands of the hydroxyl groups associated with various configurations of the terminal silanol bonds on the glass surface and the free molecular water in the glass matrix. Raman analysis has provided an alternative method of quantifying the network connectivity grade and predicting the textural properties of the sol-gel silicate glasses.