Structure-property correlation in BaO-TiO2-B2O3 glasses: glass stability, optical, hydrophobic, and dielectric properties

Glasses in the x(BaO-TiO2)-B2O3 (x = 0.25, 0.5, 0.75, and 1 mol.) system were fabricated via the conventional melt-quenching technique. Thermal stability and glass-forming ability as determined by differential thermal analysis (DTA) were found to increase with increasing BaO-TiO2 (BT) content. However, there was no noticeable change in the glass transition temperature (T-g). This was attributed to the active participation of TiO2 in the network formation especially at higher BT contents via the conversion of the TiO6 structural units into TiO4 units, which increased the connectivity and resulted in an increase in crystallization temperature. Dielectric and optical properties at room temperature were studied for all the glasses under investigation. Interestingly, these glasses were found to be hydrophobic. The results obtained were correlated with different structural units and their connectivity in the glasses.

Mechanical properties of glasses and TiO2 nanocrystal glass composites in BaO-TiO2-B2O3 system

Glasses and glass-nanocrystal (anatase TiO2) composites in BaO-TiO2-B2O3 system were fabricated by conventional melt-quenching technique and controlled heat treatment respectively. Poisson's ratio and Young's moduli were predicted through Makishima-Mackenzie theoretical equation for the as-quenched glasses by taking the four and three coordinated borons into account. Mechanical properties of the glasses and glass-nanocrystal composites were investigated in detail through nanoindentation and microindentation studies. Predicted Young's moduli of glasses were found to be in reasonable agreement with nanoindentation Measurements. Hardness and Young's modulus were enhanced with increasing volume fraction of nanocrystallites of TiO2 in glass matrix whereas fracture toughness was found susceptible to the surface features. The results were correlated to the structural units and nanocrystals present in the glasses. (C) 2013 Elsevier B.V. All rights reserved.

Role of Crystal Field in Mixed Alkali Metal Effect: Electron Paramagnetic Resonance Study of Mixed Alkali Metal Oxyfluoro Vanadate Glasses

The mixed alkali metal effect is a long-standing problem in glasses. Electron paramagnetic resonance (EPR) is used by several researchers to study the mixed alkali metal effect, but a detailed analysis of the nearest neighbor environment of the glass former using spin-Hamiltonian parameters was elusive. In this study we have prepared a series of vanadate glasses having general formula (mol %) 40 V2O5-30BaF(2)-(30 - x)LiF-xRbF with x = 5, 10, 15, 20, 25, and 30. Spin-Hamiltonian parameters of V4+ ions were extracted by simulating and fitting to the experimental spectra using EasySpin. From the analysis of these parameters it is observed that the replacement of lithium ions by rubidium ions follows a ``preferential substitution model''. Using this proposed model, we were able to account for the observed variation in the ratio of the g parameter, which goes through a maximum. This reflects an asymmetric to symmetric changeover of. the alkali metal ion environment around the vanadium site. Further, this model also accounts for the variation in oxidation state of vanadium ion, which was confirmed from the variation in signal intensity of EPR spectra.

Raman signatures of intermediate phase in quaternary Ge15Te80 (-) xIn5Agx glasses

Micro-Raman studies are conducted on as-quenched and annealed Ge15Te80 -_xIn5Agx glasses to probe the structural network and its evolution with composition. These studies reveal the presence of tetrahedral GeTe4 structural units in as-quenched samples. Specific signatures of the intermediate phase (IP) are observed in the composition dependence of Raman frequencies and corresponding intensities of different modes in the composition range, 8 <= x <= 16. In addition, the Raman peak positions are found to shift with silver doping. Apart from the Raman results, the compositional dependence of density, molar volume and thermal diffusivity, observed in the present study, confirms the presence of the intermediate phase. In thermally annealed samples, a unique variation of Raman wave-numbers in the intermediate region is observed due to the retention of some of the local structure even after the sample is crystallized. The observed Raman peaks are attributed to crystalline tellurium and silver lattice vibrational modes. Based on our present and earlier studies, we propose the occurrence of three thresholds in Ge15Te80 - xIn5Agx glasses, namely percolation of rigidity, percolation of stress and the onset of chemical phase separation on a nanoscale at 8%, 16% and 20% of silver concentration respectively. (C) 2014 Elsevier B.V. All rights reserved.

Electrical switching, SET-RESET, and Raman scattering studies on Ge15Te80-xIn5Agx glasses

Bulk Ge15Te85-xIn5Agx glasses are shown to exhibit electrical switching with switching/threshold voltages in the range of 70-120V for a sample thickness of 0.3 mm. Further, the samples exhibit threshold or memory behavior depending on the ON state current. The compositional studies confirm the presence of an intermediate phase in the range 8 <= x <= 16, revealed earlier by thermal studies. Further, SET-RESET studies have been performed by these glasses using a triangular pulse of 6 mA amplitude (for SET) and 21 mA amplitude (for RESET). Raman studies of the samples after the SET and RESET operations reveal that the SET state is a crystalline phase which is obtained by thermal annealing and the RESET state is the glassy state, similar to the as-quenched samples. It is interesting to note that the samples in the intermediate phase, especially compositions at x = 10, 12, and 14 withstand more set-reset cycles. This indicates compositions in the intermediate phase are better suited for phase change memory applications. (C) 2014 AIP Publishing LLC.

Effect of ultrasonic treatment on surface crystallization of calcium bismuth borate glasses

Transparent glasses in CaO-Bi2O3-B2O3 system were fabricated via the conventional melt-quenching technique. X-ray powder diffraction (XRD) and differential thermal analysis (DTA) carried out on the as-quenched samples confirmed their amorphous and glassy nature respectively. The surface crystallization behaviour of these glasses with and without ultrasonic surface treatment (UST) was monitored using XRD, optical microscopy and scanning electron microscopy (SEM). The volume fraction, depth of crystallization and the (001) orientation factor for the heat treated samples with and without UST were compared. The ultrasonically-treated samples on subsequent heat treatment were found to crystallize at lower temperatures associated with the highest degree of orientation factor (0.95) in contrast with those of non-UST samples. These surface crystallized glasses were found to exhibit nonlinear optical behaviour emitting green light (532 nm) when they were exposed to the infrared radiation (1064 nm) using Nd:YAG laser.

High pressure studies on the electrical resistivity of Ge-Te-Tl glasses

The variation of electrical resistivity in the system of glasses Ge17Te83-xTlx, with (1 <= x <= 13), has been studied as a function of high pressure for pressures up to 10 GPa. It is found that the normalized electrical resistivity decreases continuously with the increase in pressure and shows a sudden drop at a particular pressure (transition pressure), indicating the presence of a transition from semiconductor to near-metallic at these pressures which are in the range 3.0-5.0 GPa. This transition pressure is seen to decrease with the increase in the percentage content of thallium due to increasing metallicity of the thallium. The transition is reversible under application of pressure and X-ray diffraction of samples recovered after pressurization show that they remain amorphous after undergoing a pressurization decompression cycle.

Cavitation in brittle metallic glasses - Effects of stress state and distributed weak zones

Experimental studies and atomistic simulations have shown that brittle metallic glasses fail by a cavitation mechanism whose origin has been traced to the presence of intrinsic atomic density fluctuations which give rise to weak zones with reduced yield strength. It has been shown recently through continuum analysis that the presence of these zones can lower the cavitation stress considerably under equibiaxial loading. The objective of the present work is to study the effect of the applied stress state on the cavitation behavior of such a heterogeneous plastic solid with distributed weak zones. To this end, 2D plane strain finite element simulations are performed by subjecting a unit cell containing a weak zone to different (biaxiality) stress ratios. The volume fraction and yield strength of the weak zone are varied over a wide range. The results show that unlike in a homogeneous plastic solid, the cavitation stress of the heterogeneous aggregate does not reduce appreciably as the stress ratio decreases from unity when the yield strength of the weak zone is low. It is found that a non-dimensional parameter characterizing the stress state prevailing in the weak zone and its yield properties uniquely control the cavitation stress. The nature of cavitation bifurcation may change from unstable bifurcation to the left at sufficiently low stress ratio to one involving snap cavitation at high stress ratio. (C) 2014 Elsevier Ltd. All rights reserved.

Direct correlation between non-random distribution of cations and ion transport mechanism in soda-lime silicate glasses

We report a direct correlation between dissimilar ion pair formation and alkali ion transport in soda-lime silicate glasses established via broad band conductivity spectroscopy and local structural probe techniques. The combined Raman and Nuclear Magnetic Resonance (NMR) spectroscopy techniques on these glasses reveal the coexistence of different anionic species and the prevalence of Na+-Ca2+ dissimilar pairs as well as their distributions. The spectroscopic results further confirm the formation of dissimilar pairs atomistically, where it increases with increasing alkaline-earth oxide content These results, are the manifestation of local structural changes in the silicate network with composition which give rise to different environments into which the alkali ions hop. The Na+ ion mobility varies inversely with dissimilar pair formation, i.e. it decreases with increase of non-random formation of dissimilar pairs. Remarkably, we found that increased degree of non-randomness leads to temperature dependent variation in number density of sodium ions. Furthermore, the present study provides the strong link between the dynamics of the alkali ions and different sites associated with it in soda-lime silicate glasses. (C) 2014 Elsevier B.V. All rights reserved.

Controlling the cross-section of waveguides inscribed on bulk chalcogenide glasses using fast laser

Waveguides have been fabricated on melt-quenched, bulk chalcogenide glasses using the femto-second laser inscription technique at low repetition rates in the single scan regime. The inscribed waveguides have been characterized by butt-coupling method and the diameter of the waveguide calculated using the mode-field image of the waveguide. The waveguide cross-section symmetry is analyzed using the heat diffusion model by relating the energy and translation speed of the laser. The net-fluence and symmetry of the waveguides are correlated based on the theoretical values and experimental results of guiding cross-section.

On the strain rate sensitivity of plastic flow in metallic glasses

The nanoindentation technique was employed to examine the strain rate sensitivity, m, and its dependence on the structural state of a Zr-based bulk metallic glass (BMG). The free volume content in the BMG was varied by examining samples in the as-cast (AC), shot-peened (SP), and structurally relaxed (SR) states. Hardness values measured at different loading rates and over a temperature range of 300-423 K as well as the strain-rate jump tests conducted in the quasi-static regime at room temperature, show that m is always negative. All the load-displacement (P-h) curves in this temperature regime exhibit serrated load-displacement responses, indicating that the shear band mediated inhomogeneous plastic flow governs deformation. Such localization of flow and associated softening is the raison d'etre for the negative m. Significant levels of pile-up around the indents were also noted. The order in the average values of hardness, pile-up heights, and the displacement bursts on the P-h curves was always such that SR > AC > SP, which is also the order of increasing free volume content. These observations were utilized to discuss the reasons for the negative strain rate sensitivity, and its dependence on the structural state of metallic glasses. It is suggested that the positive values of m reported in the literature for them are possibly experimental artefacts that arise due to large pile ups around the indents which lead to erroneous estimation in hardness values. (C) 2014 Elsevier B.V. All rights reserved.

Fracture in metallic glasses: mechanics and mechanisms

Significant progress in understanding the mechanical behavior of metallic glasses (MGs) was made over the past decade, particularly on mechanisms of plastic deformation. However, recent research thrust has been on exploring the mechanics and physics of fracture. MGs can be very brittle with K-Ic values similar to silicate glasses and ceramics or very tough with K-Ic akin to high toughness crystalline metals. Even the tough MGs can become brittle with structural relaxation following annealing at temperatures close to glass transition temperature (T-g). Detailed experimental studies coupled with complementary numerical simulations of the recent past have provided insights on the micromechanisms of failure as well as nature of crack tip fields, and established the governing fracture criteria for ductile and brittle glasses. In this paper, the above advances are reviewed and outstanding issues in the context of fracture of amorphous alloys that need to be resolved are identified.

On the variability in fracture toughness of `ductile' bulk metallic glasses

The mode I fracture toughness, K-Ic, of ductile bulk metallic glasses (BMGs) exhibits a high degree of specimen-to-specimen variability. By conducting fracture experiments in modes I and II, we demonstrate that the observed high variability in mode I, vis-a-vis mode II, is a result of highly variable propensity for the conversion of shear bands into cracks in mode I whereas in mode II, crack growth direction is fixed. Thus, the measured variability in K-Ic is intrinsic to the nature of BMGs. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Variation of Electrical Resistivity with High Pressure in Ge-Te-Sn Glasses: A Composition Dependent Study

The variation of normalized electrical resistivity in the system of glasses Ge15Te85-xSnx with (1 <= x <= 5) has been studied as a function of high pressure for pressures up to 9.5 GPa. It is found that with the increase in pressure, the resistivity decreases initially and shows an abrupt fall at a particular pressure, indicating the phase transition from semiconductor to near metallic at these pressures, which lie in the range 1.5-2.5 GPa, and then continues being metallic up to 9.5 GPa. This transition pressure is seen to decrease with the increase in the percentage content of tin due to increasing metallicity of tin. The semiconductor to near metallic transition is exactly reversible and may have its origin in a reduction of the band gap due to high pressure.

Thermal and spectroscopic investigations of glasses in the system PbO-PbCl2-PbBr2

Glass formation has been examined in the system 15PbO.xPbCl(2).(85-x)PbBr2 (where 0 <= x <= 25)where the PbO concentration is kept constant while PbCl2 and PbBr2 concentrations are varied. The glasses have been examined using thermal and spectroscopic techniques. T-8, Delta C-p, refractive index, optical basicity have been found to remain unaffected by the composition which is a curious feature of these glasses. It is found that there is a wide infrared window available for use in the investigated glasses. The IR window extends from 1000 to 1500 cm(-1) and in glasses where PbCl2 is less than 20 mol%, the window extends up to 2260 cm(-1). X-ray photoelectron spectra (XPS) revealed that the 4f(5/2) and 4f(7/2) peaks due to f-level transitions have a constant difference in energies, but with energy and FWHM values that varying sensitively and systematically with composition. The observations are discussed and suitable explanations are provided.