The role of As2O3 on the stability and some physical properties of PbO-Sb2O3 glasses

PbO-Sb₂O₃ glasses added with different concentrations of As₂O₃ (10-55 mol%) were prepared to understand their IR spectra, elastic properties (Young's modulus E, Shear modulus G, microhardness H), optical absorption and dielectric properties (constant ε, loss tan δ, ac conductivity σ_ac over a moderately wide range of frequency and temperature and breakdown strength in air medium at room temperature). Results have indicated that the structure of the PbO-Sb₂O₃-As₂O₃ glass is more rigid when the concentration of As₂O₃ is around 40 mol%.     

Effects of vitrification suppression on structure morphology, conductivity and dielectric properties of vanadium phosphate glasses

Vitrification suppression in the (V₂O₅)_1−x (P₂O₅)_x glasses where x=0.10, 0.15, 0.20, and 0.25 was controlled by changing the rate of quenching glasses. The structure variations occurring in the glasses were detected by differential thermal analysis and optical microscope. The results implied the separation and growth of V₂O₅ orthorhombic microcrystal in the samples with x=0.10 and 0.15 whereas other samples did not illustrate remarkable changes in their microstructure. However, in temperature range between 300 and 473 K a semiconducting behavior for all samples appears during the study of electrical conductivity-temperature dependence. A decrease in conductivity values accompanied with some variations in activation energies by reducing quenching rate was observed. The conductivity results suggested that the conduction occurs by the phonon assisted hopping of a small polaron between V⁴⁺ and V⁵⁺ states at relatively higher temperature range above θ_D/2. Whereas at relatively low temperatures the conduction may occur by electron jumping between filled and empty states at Fermi level in the disordered matrix besides polaronic conduction. Reasonable values for the density of localized states, carrier concentration and carrier mobility were estimated and discussed. Also, dielectric constant and dielectric loss were studied as a function of frequency at different temperatures confirming the structure variations in the glass system.     

An efficient lasing action from pyrromethene 556 dye-doped organically modified silicates

Organically modified solid-state silicates (ORMOSILS) doped with a new laser dye 1,3,5,7,8-pentamethylpyrromethene-2,6-disulfonate-BF₂ complex (pyrromethene 556) have been synthesized by a sol-gel method and the compositional effects on pore characteristics, fluorescence and lasing properties have been investigated. It is found that the use of dimethylsulfoxide and γ-glycidoxypropyltrimethoxysilane could greatly change the structure properties of sol-gel derived ORMOSILS cage, and thus the fluorescence and lasing properties of the materials could improve significantly. A successful laser oscillation from this dye-doped ORMOSILS sample has been achieved upon pumping with a Q-switched frequency-doubled Nd:YAG laser at 532 nm. A slope efficiency of 54% with a useful lifetime greater than 10,000 shots has been demonstrated at a pump repetition rate of 1 Hz and a pump intensity of 1 J/cm² by using the new ORMOSILS cage on our newly designed laser system. Our results have shown that it is possible to obtain a high-efficiency with a long-lifetime for a compact new laser device by low cost dye-doped solid-state ORMOSILS.     

Generalized excluded volume and the diffusivity and viscosity of supercooled liquids and glasses over the entire fragility spectrum

Transport properties of glass-formers near glass transition reflect the varying degrees of the sensitivity of the solid-like dynamics and structures with respect to temperature, depending on their fragility. Notably, however, most glasses resume Arrehenius transport behavior upon onset of vitrification. To address this phenomenon a theory of the self-diffusion coefficient and viscosity is developed on the basis of a model constructed for the generalized excluded volume of glass-formers described by the generic van der Waals equation of state. The molecular clustering behavior of a glass-former is exploited in terms of an order parameter that measures the concentration of glassy, clustered molecules, which is then related to the excluded volume. The formulas arrived therefrom are shown to excellently account for the self-diffusion coefficient and viscosity of various glass-formers over the entire fragility spectrum studied experimentally: e.g., _GeO2${\mathrm{GeO}}_2$, silica, ethanol, glycerol, diopside, propylene carbonate, o$o$-terphenyl, tris-napthylbenzene, toluene, and so on. The excluded volume effect thus investigated is shown to essentially characterize the fragility of the glass-formers. The resulting theory not only predicts for fragile glass-formers to resume Arrehenius transport behavior upon the onset of the glass transition, but also explains a crossover between strong and fragile glass-formers in their diffusivity and viscosity profiles as vitrification sets in.     

Structural and short-range order analysis of glassy system

To understand the effects of structural features and to locate their signatures in the As-Ag-Te glassy system, various properties were studied as a function of average coordination number, 〈r〉. The structure of the sample is analyzed by X-ray diffraction technique and is found to be crystalline. The d-spacing and the lattice parameters of the samples were calculated. The structural parameters were discussed on the basis of Ag (silver) effect on As-Ag-Te glassy system. Structural investigations on these compositions revealed the polycrystalline nature of compositions with the presence of hexagonal As-Ag-Te phases. Grain size increased with the Ag content and parameters of unit cell are determined. The variations in the mean atomic volume, V, and the glass transition temperature, T_g, for glass transition, with composition have been reported. The change in thermal parameters was measured using differential thermal analysis (DTA). The results of the program are in agreement with those of analytical method and realized by binding energy represented by the cohesive energy values. The generalized ‘8-n’ rule was used to estimate the average coordination number. Obtained results were treated in the frame of chemical bond approach. We estimated some of physical parameters viz. mean bond energy, glass transition temperature, cohesive energy, average single bond energy, density, compactness and molar volume of all bulk samples. Our experimental and theoretical results were discussed in light of the topological bonding structure, which involves a hierarchy of correlation ranges in short-range order.     

Electrical and optical properties of GexFexSe100−2x chalcogenide thin films

Optical absorption at room temperature and electrical conductivity at temperatures between 283 and 333 K of vacuum evaporated Ge_xFe_xSe_100−2x (0≤x≤15) amorphous thin films have been studied as a function of composition and film thickness. It was found that the optical absorption is due to indirect transition and the energy gap increases with increasing both Ge and Fe content; on the other hand, the width of the band tail exhibits the opposite behavior. The optical band gap E_opt was found to be almost thickness independent. The electrical conductivity show two types of conduction, at higher temperature the conduction is due to extended states, while the conduction at low temperature is due to variable range hopping in the localized states near Fermi level. Increasing Ge and Fe contents were found to decrease the localized state density N(E_F), electrical conductivity and increase the activation energy for conduction, which is nearly thickness independent. Variation of the atomic densities ρ, molar volume V, glass transition temperature T_g cohesive energy C.E and number of constraints N_Co with average coordination number Z was investigated. The relationship between the optical gap and chemical composition is discussed in terms of the cohesive energy C.E, average heat of atomization and coordination numbers.     

The Chemistry of the Noncrystalline State

This article sets out to describe and account for the chemical and physical consequences of the presence of gross disorder in solids. Knowledge of the structure of such disordered materials is an obvious prerequisite to a further understanding of other properties and behavior, and our current knowledge of the structure of various noncrystalline systems is discussed together with the experimental techniques which need to be employed in order to obtain such information. The so-called glass transition, which takes place as a liquid is supercooled below the crystallization temperature, is discussed in terms of the various models which have been proposed to account for this phenomenon. The effect of noncrystallinity on electronic properties is also discussed, and we highlight new developments in the understanding of electron localization and transport processes. Finally, two applications of amorphous solids are considered in some detail: optical fibers for use in communication networks and “superionic” glasses for possible use in solid-state batteries.     

Frozen capillary waves on glass surfaces: an AFM study

Using atomic force microscopy on silica and float glass surfaces, we give evidence that the roughness of melted glass surfaces can be quantitatively accounted for by frozen capillary waves. In this framework the height spatial correlations are shown to obey a logarithmic scaling law; the identification of this behaviour allows to estimate the ratio kT_F/πγ where k is the Boltzmann constant, γ the interface tension and T_F the temperature corresponding to the “freezing” of the capillary waves. Variations of interface tension and (to a lesser extent) temperatures of annealing treatments are shown to be directly measurable from a statistical analysis of the roughness spectrum of the glass surfaces.     

Mossbauer, infrared and magnetic susceptibility studies of iron sodium borate glasses doped by sulphur

The affect of sulphur on the structural properties of iron sodium diborate glasses having the composition {(100−x)Na₂B₄O₇+xFe₂O₃}+yS, where x=0.05, 0.15 and 0.25 mol% and Y=0, 2.5 and 5 wt% was studied by infrared, Mossbauer spectroscopy and magnetic susceptibility measurements. It was found that, for samples having 5 mol% Fe₂O₃ and free from sulphur, the iron ions are present in both Fe²⁺ and Fe³⁺ states and also 92% of the total iron enters the glass network as a glass former. The ratio of Fe³⁺/Fe²⁺ increases with increasing the iron content for sulphur-free samples and others containing sulphur. This ratio also decreases with increasing the sulphur content. The magnetic susceptibility was found to decrease with increasing the sulphur content. Also, the increase of Fe₂O₃ content led to a less symmetrical environment of Fe³⁺ ions and vice versa for the Fe²⁺ environment.     

EPR study of RLi2O.V2O5, RNa2O.V2O5, RCaO.V2O5, and RBaO.V2O5 modified vanadate glass systems

Experimental EPR spectra in several modified vanadate glass systems reveal hyperfine structure (hfs) lines whose widths vary with the molar ratio of modifier to vanadium pentoxide, R. In the RNa₂O.V₂O₅ system, for example, hfs lines show no resolution at low R values (near 0.1); by contrast, these lines exhibit dramatic narrowing as R approaches 0.5. In the model proposed here, this narrowing is due to an increase in hopping time for small polarons associated with V⁴⁺ ions in these systems. Increases in polaron hopping times are accompanied by increases in electron spin-spin relaxation times T₂'s, and, an associated narrowing of EPR linewidths. Experiments confirm that spectral widths are limited by electron T₂'s due to the fact that EPR linewidths do not vary with temperature down to 4.2 K. Resolved spectra in RNa₂O.V₂O₅ at R = 0.5 reveal a hyperfine coupling parameter of 0.0177 ± 0.0008 T, corresponding to an upper-limit polaron hopping frequency of 487 ± 20 MHz. By similar analyses, the systems of RCaO.V₂O₅, RBaO.V₂O₅, and RLi₂O.V₂O₅ exhibit comparable polaron hopping frequencies limits of 480 ± 20 MHz, 469 ± 20 MHz, and 468 ± 20 MHz, respectively, when R is near 1.0. In addition to the relaxation effects discussed here, results of modeling of resolved spectra to obtain hyperfine coupling constants A_|| and A_┴, and g_┴ values g_|| and g_┴ are presented and discussed.