On the constitution of silicate groupings in binary lead silicate glasses

Direct chemical methods have been used to determine the type and the percentage of silicate groupings present in binary lead silicate glasses within the composition range 4PbO · SiO₂PbO · SiO₂. The results obtained indicate that the constitution and the relative amounts of various silicate groupings change with the changing total amount of SiO₂ in the glass. Glasses containing small amounts of SiO₂ are characterized by the presence of few low-molecular silicate units; increasing the percentage of SiO₂ promotes the formation of higher polymerized silicate groupings. The results are discussed with regard to stoichiometry, and are consistent with Hägg's concept of glassiness.     

Vibrational spectroscopic studies of some lead silicate glasses

Results are presented of measurements on the infrared and laser Raman spectra of some lead silicate glasses of general formula (PbO)_x(SiO₂)_y.For the infrared spectra, the frequency dependence of the imaginary component of the complex dielectric constant was determined from a Kramers-Krönig analysis of the reflectance spectra of the glasses at normal incidence. Apparently the addition of small amounts of PbO to vitreous silica serves to modify the continuous three-dimensional silica network; whereas in those glasses with a high lead content, the influence of the cation, Pb²⁺, appears to lie between that of network former and network modifier.     

Leaching of some lithium silicate glasses and glass-ceramics by HCl

The leaching of some binary and ternary lithium silicate glasses and their respective glass-ceramics by HCl is reported.The leaching rate of lithium silicate glasses gradually decreases with the decrease of the percentage of Li₂O or by the introduction of small amounts of a third component, e.g. Al₂O₃, MgO, ZnO or B₂O₃. With a further increase in the proportions of B₂O₃ or ZnO the rate of leaching increases. The rate of leaching is also substantially modified by the conversion of glasses into glasses-ceramics.The results obtained are discussed in terms of the effects of the different ions on the rate of the interdifussion of the lithium and hydrogen ions in the glass and the leached layer, the phase separation developed in the glass, the type and concentration of crystalline phases developed in glass-ceramics and the composition of the residual glass phase.     

Raman spectroscopic investigation of the structure of silicate glasses (II). Soda-alkaline earth-alumina ternary and quaternary glasses

Raman spectra of some ternary and quaternary glasses in the system Na₂OCaOMgOAl₂O₃SiO₂ are presented. The spectra are interpreted in terms of the structural alteration of the glass as the composition is altered from the binary end members to more complicated glasses. Addition of CaO and MgO to soda-silica glasses act only to increase the disorder of the network slightly. Addition of Al₂O₃ greatly modifies the network. In some soda-lime-aluminosiliscate compositions an estimate can be made of the amount of aluminum in four- and six-fold coordination. It is shown that the amounts of four- and sixfold coordinated aluminum depend on the glass composition.     

Structure and lattice dynamics of binary lead silicate glasses investigated by infrared spectroscopy

The polar lattices dynamics of seven binary lead silicate glasses have been studied by infrared spectroscopy. The analysis of the reflectivity spectra with a dielectric function model, based on a modified Gaussian profile, allows a quantitative evaluation of the presence of lead cations within different structural sites. From the role of the lead cations versus the degree of polymerization of the silicate network and the comparison with literature results, we may to give a scenario for explaining the observed structural evolution of the glass matrix and more particularly the drastic change occurring around 45% of lead content. Below this threshold, lead cations act only as modifiers of the silicate network. Above, the glass structure is deeply modified; a lead network involving around 10% of the lead content appears in glasses whose composition is just above the threshold and progressively grows at the expense of the silicate network with the increase of lead content. For high lead content, lead cations can act as modifiers of the silicate network or as network formers. Results also show that the analysis of far infrared measurements combined with the knowledge of the UV edge optical response is very promising to characterize the local disorder around cations in glasses.     

Fracture toughness-composition relationship in some binary and ternary glass systems

Measurements of the critical stress intensity factor K_Ic are reported for glasses in the Na₂OSiO₂, PbOSiO₂, ZnOB₂O₃, PbOB₂O₃, Na₂OGeO₂ and 20Na₂O?(80 ? x) B₂O₃ ? xSiO₂ systems. The variations of K_Ic with composition are not directly related to the simultaneous variations of Young's modulus. A tentative interpretation is given.     

A study of optical absorption in some sodium titanium silicate glasses

A series of glass specimens was prepared from mixtures of SiO₂, TiO₂ and Na₂O, and their optical absorption coefficients measured as functions of photon energy in the range 2.1–3.3 eV. From the results, values of the optical energy gap are calculated and found to be dependent on the glass compositions. The results are analysed in terms of a mechanism of optical absorption arising from forbidden indirect transitions.     

Ultraviolet spectra of silicate glasses: A review of some experimental evidence

Ultraviolet spectroscopy is a useful experimental tool for the determination of the electronic structure of glasses. This paper discusses the ultraviolet spectra of SiO₂ and high-purity silicate glasses. It considers in turn, absorption intrinsic to the SiO network, the effects of network modifiers, impurity-induced absorption, luminescence and radiation damage, both permanent and transient, in the wavelength region extending from 90 to 350 nm.     

Surface hydration and nanoindentation of silicate glasses

The near-surface mechanical properties of glasses and differences in mechanical behaviour between high and low durability silicate glasses are investigated. Nanoindentation is used to examine the effect of hydration on the near-surface mechanical properties of silicate glasses with varying degrees of chemical durability. It is shown that hydration has little if any effect on high durability glasses even at long immersion times, whereas in low durable glasses hydration reduces the near-surface mechanical properties significantly and the thickness of hydrated layer may exceed the indentation depth. In addition an attempt is made to measure the thickness and mechanical properties of hydrated layer in low durability glasses where influence of the substrate is negligible.     

Density fluctuations in silicate glasses

The potential use of inorganic glasses as waveguides at optical wavelengths has precipitated the need to understand the relationship between intrinsic optical loss and glass composition. The contribution to optical loss due to scattering from density fluctuations, is analyzed and discussed for various homogeneous (non-phase-separated) silicate glasses. The results show that binary alkali silicates in certain composition ranges form homogeneous glasses with density fluctuations less intense than that of pure silica glass. As third components added to these binary compositions alkali oxides (different from the one already present in the base glass), alkaline earth oxide (CaO) and Al₂O₃ cause further reductions in the magnitude of the density fluctuations.     

High-chromium containing lithium silicate glasses

Chromium as a transition metal oxide is incorporated into lithium silicate glass compositions. It supplies to these glasses adequate absorption and reflectance characteristics for electromagnetic radiation. This will make it possible to attain appropriate materials to apply as absorbers of solar energy. Properties of the glass and glass ceramics produced are investigated.     

Large-scale simulations of sodium silicate glasses

Half million and million atom systems of sodium silicate glass have been simulated using classical molecular dynamics, and their structures have been examined. Although the structural features are reasonable for the intended glasses, and have a lower configurational energy than smaller systems, they contain features which are indicative of an effective internal, or configurational, temperature higher than the target temperature. This observation is ascribed to the use of a thermostat which controls only the kinetic energy, or momenta, of the particles, and because of the non-equilibrium nature of the simulations, there is no requirement that the potential, or configurational, energy and kinetic energy be coupled. The use of alternative thermostats is suggested.     

The structure of alkali silicate glasses

Pulsed neutron diffraction has been used to study the structure of three alkali silicate glasses of nominal composition SiO₂ · (M₂O)_0.5, with M = K, K_0.46Li_0.54 and Li. The data are quantitatively consistent with the modified random network model. Lithium is coordinated by two oxygen atoms with an interatomic distance of 1.97 Å. The potassium-oxygen distance is similar to the tetrahedral oxygen-oxygen distance, 2.66 Å, with potassium being coordinated by approximately four oxygen atoms.     

Optical and structural properties of calcium silicate glasses

A detailed analysis of the reflectance and transmittance spectra of a set of glasses allowed retrieval, besides the optical functions, of quantitative information on the structural changes occurring in the calcium silicate glass system. The occurrence of a threshold around 46% of CaO content is confirmed and is connected to the appearance in the glass structure of a new configuration of calcium cations. It was also shown that the calcium cations that exceeds the compositional threshold does not act as modifiers of the silicate network since they form Ca–O–Ca bonds in the glass structure. Obvious changes occurring at the threshold in the physical or chemical properties can be understood in the light of the structural changes observed in the system.