Crack nucleation in ultrathin blown silicate glasses

Ultrathin blown glasses, owing to the very high cooling rate, have an open structure, characterized by lower hardness and higher deformability, and no tempering residual stresses. In these glasses, due to their high densificability, the threshold load for crack nucleation is higher than in air-cooled plates, and it is also above the values estimated by present theoretical formulations.     

Structural aspects of volume nucleation in silicate glasses

An interrelationship between parameters of short and intermediate range order in silicate glasses and the tendency to nucleate homogeneously in the volume is tested. Changes in the average coordination number and metal-oxygen distance of network modifying cations as well as changes in the concentration of constitutive silica tetrahedra accompanied with the crystallization of 18 stoichiometric glass compositions into their crystalline analogs are determined. The intermediate range structure of the glasses is investigated by configurational entropy and flow birefringence. The changes in structural parameters are analyzed in terms of the reduced glass transition temperature T_rg, which is negatively correlated with the maximal rate of volume nucleation. The results indicate that the short-range structure in stoichiometric glasses is, in general, very similar to the corresponding crystal structure but independent of the T_rg-scale and for this reason independent of nucleation properties. In contrast to the short range of the glass structure, birefringence induced by a forced flow above the glass transition temperature and configurational entropy are positively correlated with increasing T_rg. The results indicate increased structural order in the intermediate range for melts with a high supercool limit (T_rg < 0.58). It is concluded that this order phenomena may promote nucleation events and may help to explain the tendency to volume nucleation of silicate glasses with T_rg < 0.58.     

Homogeneous nucleation in cooling crystallization

Nielsen's equation has been applied for cooling crystallization of KCl from watery solutions. In the calculations activities are used instead of concentrations, the temperature and concentration dependence of both the activity and diffusion coefficients are considered. It is found that A) the interfacial tension between the crystal and its saturated solution is < 2.5 erg/cm², which is less by two orders of magnitude than that of between crystal and vacuum; B) homogeneous nucleation can take place even at very small supersaturations (ln S < < 0.01), which is unusual in precipitation.     

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.     

A test of classical nucleation theory: crystal nucleation of lithium disilicate glass

For several inorganic glasses predictions have been made of the homogeneous crystal nucleation rate using classical nucleation theory. However, in none of these cases were comparisons made with experiment, due primarily to the inability of being able to guarantee homogeneous conditions. Evidence has been provided that crystalline formation in Li₂O · 2 SiO₂ glass may initiate by a homogeneous mechanism. Thus, we have computed the nucleation rate curve of lithium disilicate crystals in this glass. It is found that not only do all forms of the classical theory predict nucleation rates many orders of magnitude smaller than those observed, but also that the temperature dependence of the theoretical rate is quite different from that observed.     

Verification of an analytical method for measuring crystal nucleation rates in glasses from DTA data

A recently proposed analytical (DTA) method for estimating the nucleation rates in glasses has been evaluated by comparing experimental data with numerically computed nucleation rates for a model lithium disilicate glass. The time and temperature dependent nucleation rates were predicted using the model and compared with those values extracted from an analysis of numerically calculated DTA curves. The validity of the numerical approach was demonstrated earlier by a comparison with experimental data. The excellent agreement between the nucleation rates from the model calculations and the computer generated DTA data demonstrates the validity of the proposed analytical DTA method.     

Sodium-hydrogen interdiffusion in sodium silicate glasses

The hydration of Na₂O · 3 SiO₂ glasses is studied using the sputter-induced photon spectrometry technique (SIPS) to measure the depth-profiles of hydrogen and sodium. The results clearly show a penetration of hydrogen and a leaching of sodium in the glass. The thicknesses of the hydrated layers are determined as functions of time and temperature. The thicknes dependence on the square root of time indicates that a diffusion process is in operation. The data are fitted to he Doremus model of interdiffusing ions and the diffusion coefficients for hydrogen and sodium are calculated.     

Polymer mass distribution in silicate glasses

The polymer mass distribution in silicate melts and glasses in still an active subject of investigation. This paper contains first a short review of the methods developed recently for its theoretical calculation and some of the results obtained by different authors, including the present ones, for the melts of the Na₂O---CaO---SiO₂ system. Experimental methods and data obtained recently are also presented. Special attention is given to liquid chromatography and to potentiometry, applied by the authors to polymer mass distribution measurements. In section 5 the papers which evidenced the influence of the polymer mass distribution in melts on glass properties are quoted.     

Multichannel conduction in alkali silicate glasses

The qualitative change of the electrical conduction of alkali silicate glasses with alkali mixing is discussed in connection with dielectric and mechanical relaxation. The observed conduction is understood as the additive effect of two kinds of independent diffusion processes — I and II. In single alkali glass, diffusion process-I is always observed as the dominant conduction process. However, when one alkali is progressively substituted by another, the dominant conduction process is altered from diffusion process-I to II. In the mixed alkali glass containing equal amounts of two alkali ions, diffusion process-I disappears, so that only diffusion process-II is observed. Consequently, it becomes evident that the mixed alkali effect is not only the successive change of conductivity, but the alternation of the dominant conduction process.     

Protein crystal nucleation: Recent notions

The nucleation of protein crystals is reconsidered taking into account the specificity of the protein molecules. In contrast to the homogeneous surface properties of small molecules, the protein molecule surface is highly inhomogeneous. Over their surfaces proteins exhibit high anisotropic distribution of patches, which are able to form crystalline bonds, the crystallization patch representing only a small fraction of the total surface of the protein molecule. Therefore, an appropriate spatial orientation of the colliding protein molecules is required in order to create a crystalline cluster. This scenario decreases considerably the success ratio of the attempt frequency for crystal nucleation. On the other hand a heterogeneous nucleation of (protein) crystals may be accelerated due to the arrival on some support of under‐critical clusters that are formed in bulk solution; when arriving there they may acquire the property of critical nuclei. Thus, a plausible explanation of important peculiarities of protein crystal nucleation, as inferred from the experimental data, is suggested. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

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.     

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.     

Rate of homogeneous nucleation in alkali disilicate glasses

Rates of crystal nucleation in alkali disilicate glasses were measured by counting the number of crystals under an optical microscope. The viscosities of these glasses were measured by the method of beam-bending and penetration. Using the data of rate of nucleation and viscosity obtained in the present study and the data of free energy measured by Takahashi and Yoshio, crystal-glass interfacial energies for alkali disilicate systems were estimated on the basis of homogeneous nucleation theory as follows: 196 erg/cm² for Li₂O·2SiO₂, 126–144 erg/cm² for Na₂O·2SiO₂ and 88–104 erg/cm² for K₂O·2SiO₂. The effects of the viscosity of glass, the free energy difference between crystal and glass and crystal-glass interfacial energy on the rate of nucleation were discussed, and the remarkably higher rate of crystal nucleation in the Li₂O·2SiO₂ glass was attributed to the larger free energy difference.     

Brillouin scattering and pockels coefficients in silicate glasses

The Brillouin spectra of binary and ternary silicate glasses were investigated and absolute values for the Pockets coefficients p₁₂ and p₄₄ and (p₁₁ – p₁₂) were calculated from the measured spectra. The results were interpreted as to the density and refractive index dependence of the Pockels coefficients in terms of the theoretical treatments by Carleton, Mueller and Sipe. From the measured p₁₂ and p₄₄ values the quantity (∂ε/∂p), the change of the dielectric constant with respect to density, was calculated and compared with (∂ε/∂) evaluated from the Lorentz-Lorenz equation, Drude equation and the Carleton model. The Lorentz-Lorenz and Drude equations overestimated the magnitude of (∂ε/∂), while the Carleton model with its two limiting cases set upper and lowe bounds to (∂ε/∂). From the (∂ε/∂) results the strain polarizability constant (λ₀) was determined and its physical significance discussed. In general, the alkali-oxide concentration dependence of the Pockels coefficients of various silicate glasses has been measured and qualitatively explained by several existing theoretical formulations.     

Water diffusion in silicate glasses under natural weathering conditions: evidence from buried medieval stained glasses

In this study, ion-microprobe analyses of four samples of buried medieval stained-glasses are used to demonstrate that water penetrates into the matrix of pristine glasses at low temperatures, thereby showing that glass alteration is not only a surface process. The diffusion coefficients of water determined from concentration profiles of hydrogen are found to be correlated with the bulk polymerization state of the glass. This observation is discussed with respect to glass structure and implies that ionic exchange between hydrogen and network modifying metal cations is the major process responsible for glass hydration.     

Barrier to crystal nucleation in anorthite

The kinetics of crystal nucleation in anorthite (CaAl₂Si₂O₈) have been determined over the range of undercooling between 475 and 600°C. The plot of In(I_vη) versus (ΔT_|staggered|r²T_|staggered|r³)^?1 is a straight line of negative slope over the temperature range investigated. The slope of this relation indicates a free energy barrier to crystal nucleation of about 82 kT1 (where $\text{T1 = 0.8T}{}_{\mathrm{E}}$). The intercept at (ΔT_|staggered|r²T_staggered|r³)^?1 = 0 is approximately 10²⁷ cm^?3 s^?1P. Samples of anorthite glass were also analyzed by differential thermal analysis, with the temperature of maximum crystallization rate being determined as a function of heating rate. From this variation, a nucleation barrier of about 80 kT1 was estimated. The combined results are in good agreement with predictions of the classical theory of homogeneous nucleation.