Physical ageing in Se-Te-Sb glasses

Bulk Se60-xTe40Sbx glasses in the composition range 0 <= x <= 14 were prepared by the melt quenching method. Differential Scanning Calorimetric (DSC) and thermal crystallization studies were performed to understand the thermodynamic property like glass transition and structural transformations. These glasses exhibit sharp endothermic peak at the glass transition (T-g). Disappearance of the endothermic peak at T-g in the rejuvenated samples clearly indicates the ageing effect in these glasses. Addition of Sb to Se-Te increases the connectivity of the structural network which is evidenced from the increase in T-g. A distinct change in the slope of the T-g at x=6, indicates a major change in the way the network is connected. The glass forming ability and the thermal stability also exhibit a maximum at x=6. T-g increases with the ageing time and the corresponding fictive temperature (T-f) calculated from the specific heat curves shows a decreasing trend. The molecular movements along the polymeric Se chains might cause the structural relaxation and the physical ageing. The physical ageing effect has been understood on the basis of the Bond Free Solid Angle (BFSA) model proposed by Kastner. Thermally crystallized samples show the formation of rhombohedral Sb2Te3, rhombohedral Sb2Se3 and hexagonal Te phases.

A new approach for understanding ion transport in glasses; example of complex alkali diborate glasses containing lead, bismuth and tellurium oxides

Mechanism of ion transport in glasses continues to be incompletely understood. Several of the theoretical models in vogue fail to rationalize conductivity behaviour when d.c. and a.c. measurements are considered together. While they seem to involve the presence of at least two components in d.c. activation energy, experiments fail to reveal that feature. Further, only minor importance is given to the influence of structure of the glass on the ionic conductivity behaviour. In this paper, we have examined several general aspects of ion transport taking the example of ionically conducting glasses in pseudo binary, yNa(2)B(4)O(7)center dot(1-y) M (a) O (b) (with y = 0 center dot 25-0 center dot 79 and M (a) O (b) = PbO, TeO2 and Bi2O3) system of glasses which have also been recently characterized. Ion transport in them has been studied in detail. We have proposed that non-bridging oxygen (NBO) participation is crucial to the understanding of the observed conductivity behaviour. NBO-BO switching is projected as the first important step in ion transport and alkali ion jump is a subsequent event with a characteristically lower barrier which is, therefore, not observed in any study. All important observations in d.c. and a.c. transport in glasses are found consistent with this model.

Design and analysis of novel compression fracture specimen with constant form factor: Edge cracked semicircular disk (ECSD)

Inspired by the Brazilian disk geometry we examine the utility of an edge cracked semicircular disk (ECSD) specimen for rapid assessment of fracture toughness of brittle materials using compressive loading. It is desirable to optimize the geometry towards a constant form factor F for evaluating K-I. In this investigation photoelastic and finite element results for K-I evaluation highlight the effect of loading modeled using a Hertzian. A Hertzian loading subtending 4 degrees at the center leads to a surprisingly constant form factor of 1.36. This special case is further analyzed by applying uniform pressure over a chord for facilitating testing.

Study of the effect of alkali mixture on V-O bond length in Oxyfluoro Vanadate glasses using Raman spectroscopy

Raman spectroscopic study on Oxyfluoro Vanadate glasses containing various proportions of lithium fluoride and rubidium fluoride was carried out to see an effect of mixture of alkali on vanadium-oxygen (V-O) bond length. Glasses with a general formula 40V(2)O(5) - 30BaF(2) - (30 - x) LiF - xRbF (x = 0-30) were prepared. Room temperature Raman spectra of these glass samples were recorded in back scattering geometry. The data presented is in ``reduced Raman intensity'' form with maximum peak scaled to 100. We have used v = Aexp(BR), where A and B are fitting parameters, to correlate the bond length R with Raman scattering frequency v. We observed that variation in bond length and its distribution about a most probable value can be correlated to the alkali environment present in these glasses. We also observed that all rubidium environment around the network forming unit is more homogenous than all lithium environment.

Crossover from photodarkening to photobleaching in a-GexSe100-x thin films

In this Letter, we present the interesting results of photodarkening (PD), transition toward photostability, and a slow crossover from PD to photobleaching when composition of the chalcogenide glassy thin film changes from Ge-deficient to rich. A subsequent Raman analysis on these as-prepared and irradiated samples provide the direct evidence of photoinduced structural rearrangement, i.e., photocrystallization of Se and the removal of edge-sharing GeSe4 tetrahedra. Further, our experimental results clearly demonstrate that light-induced effects can be effectively controlled by choosing the right composition and provide valuable information on synthesizing photostable/sensitive glasses.

Nanoindentation studies on waveguides inscribed in chalcogenide glasses using ultrafast laser

Optical straight waveguides are inscribed in GeGaS and GeGaSSb glasses using a high repetition-rate sub-picosecond laser. The mechanical properties of the glasses in the inscribed regions, which have undergone photo induced changes, have been evaluated by using the nanoindentation technique. Results show that the hardness and elastic modulus of the photo-modified glasses are significantly lower as compared to the other locations in the waveguide, which tend to be similar to those of the unexposed areas. The observed mechanical effects are found to correlate well with the optical properties of the waveguides. Further, based on the results, the minimum threshold values of hardness and elastic modulus for the particular propagation mode of the waveguide (single or multi), has been established.

Room-temperature anelasticity and viscoplasticity of Cu-Zr bulk metallic glasses evaluated using nanoindentation

Anelastic and viscoplastic characteristics of Cu50Zr50 and Cu65Zr35 binary bulk metallic glasses at room temperature were examined through nanoindentation creep experiments. Results show that both the deformations are relatively more pronounced in Cu50Zr50 than in Cu65Zr35, and their amount increases with the loading rate. The results are analyzed in terms of the influences of structural defects and loading rate on the room temperature indentation creep.

Ion transport studies in lithium phospho-molybdate glasses containing Cl- ion

Ion conducting glasses in xLiCl-20Li(2)O-(80-x) 0.80P(2)O(5)-0.20MoO(3)] glass system have been prepared over a wide range of composition (X = 5, 10, 15, 20 and 25 mol%). The electrical conductivity and dielectric relaxation of these glasses were analyzed using impedance spectroscopy in the frequency range of 10 Hz-10 MHz and in the temperature range of 313-353 K. D.c. activation energies extracted from Arrhenius plots using regression analysis, decreases with increasing LiCl mol%. A.c. conductivity data has been fitted to both single and double power law equation with both fixed and variable parameters. The increased conductivity in the present glass system has been correlated with the volume increasing effect and the coordination changes that occur due to structural modification resulting in the creation of non-bridging oxygens (NBO's) of the type O-Mo-O- bonds in the glass network. Dielectric relaxation mechanism in these glasses is analyzed using Kohlrausch-Williams-Watts (KWW) stretched exponential function and stretched exponent (beta) is found to be insensitive to temperature.

Synthesis and application of weight function for edge cracked semicircular disk (ECSD)

We analyze the utility of edge cracked semicircular disk (ECSD) for rapid assessment of fracture toughness using compressive loading. Continuing our earlier work on ECSD, a theoretical examination here leads to a novel way for synthesizing weight functions using two distinct form factors. The efficacy of ECSD mode-I weight function synthesized using displacement and form factor methods is demonstrated by comparing with finite element results. Theory of elasticity in conjunction with finite element method is utilized to analyze crack opening potency of ECSD under eccentric compression to explore newer configurations of ECSD for fracture testing.

Comparative study on optical properties of Se-Zn-In and Se-Zn-Te-In chalcogenide glasses

In contemporary world optoelectronics materials are used in daily life owing to its verity of applications. Utility of these materials makes them attractive for investigations. Specifically study regarding optical properties of recent developed materials is worth for technical uses. Therefore, this work demonstrates a comparative study of extinction coefficient (K), real dielectric (epsilon') and imaginary dielectric (epsilon `') constants, refractive index (n) and optical energy band gap (E-g) with structural unit < r > for Se98-xZn2Inx (0 <= X-In <= 10) and Se93-yZn2Te5Iny (0 <= Y-In <= 10) chalcogenide glasses. Fixed amount of Te with increasing In concentration as cost of Se is largely influence the optical parameters of the materials. Values of optical parameters are obtained higher and lower respectively at thresholds structural units values. This comparative study demonstrates that enhanced values of optical parameters have been obtained for Te containing Se-Zn-In glasses.

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.

Dynamics of edge dislocations in a sheared lamellar mesophase

The dynamics and interactions of edge dislocations in a nearly aligned sheared lamellar mesophase is analysed to provide insights into the relationship between disorder and rheology. First, the mesoscale permeation and momentum equations for the displacement field in the presence of external forces are derived from the model H equations for the concentration and momentum field. The secondary flow generated due to the mean shear around an isolated defect is calculated, and the excess viscosity due to the presence of the defect is determined from the excess energy dissipation due to the secondary flow. The excess viscosity for an isolated defect is found to increase with system size in the cross-stream direction as L-3/2 for an isolated defect, though this divergence is cut-off due to interactions in a defect suspension. As the defects are sheared past each other due to the mean flow, the Peach-Koehler force due to elastic interaction between pairs of defects is found to cause no net displacement relative to each other as they approach from large separation to the distance of closest approach. The equivalent force due to viscous interactions is found to increase the separation for defects of opposite sign, and decrease the separation for defects of same sign. During defect interactions, we find that there is no buckling instability due to dilation of layers for systems of realistic size. However, there is another mechanism, which is the velocity difference generated across a slightly deformed bilayer due to the mean shear, which could result in the creation of new defects. (C) 2013 AIP Publishing LLC.

Facile synthesis of Cu2CoSnS4 nanoparticles exhibiting red-edge-effect: Application in hybrid photonic devices

Cu2CoSnS4 (CCTS) quaternary semiconducting nanoparticles with size distribution from 20 nm to 60 nm were synthesized by one-pot low temperature time and surfactant dependent hydrothermal route. Nanoparticles were characterized structurally and optically. Excitation dependent fluorescence exhibited a dynamic stoke shift referring to the Red-Edge-Effect with peak shifting by a greater magnitude (>100 nm) towards red side, in all the samples. Hybrid devices, fabricated from CCTS nanoparticle inorganic counterparts benefitting from the conjugation of organic P3HT polymer matrix, were demonstrated for photodetection under infra-red and A. M 1.5 solar light illuminations. Faster rise and decay constants of 37 ms and 166 ms, with one order photocurrent amplification from 1.6 x 10(-6) A in the dark to 6.55 x 10(-5) A, upon the 18.50 mW cm(-2) IR lamp illumination, make CCTS a potential candidate for photodetector and photovoltaic applications. (C) 2013 AIP Publishing LLC.

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.