Structural, dielectric, impedance and optical properties of CaBi2B2O7 glasses and glass-nanocrystal composites

Optically clear glasses were fabricated by quenching the melt of CaCO3-Bi2O3-B2O3 (in equimolecular ratio). The amorphous and glassy characteristics of the as-quenched samples were confirmed via the X-ray powder diffraction (XRD) and differential scanning calorimetric (DSC) studies These glasses were found to. have high thermal stability parameter (S). The optical transmission studies carried out in the 200-2500 nm wavelength range confirmed both the as-quenched and heat-treated samples to be transparent between 400 nm and 2500 nm. The glass-plates that were heat-treated just above the glass transition temperature (723 K) for 6 h retained approximate to 60% transparency despite having nano-crystallites (approximate to 50-100 nm) of CaBi2B2O7 (CBBO) as confirmed by both the XRD and transmission electron microscopy (TEM) studies. The dielectric properties and impedance characteristics of the as-quenched and heat-treated (723 K/6 h) samples were studied as a function of frequency at different temperatures. Cole-Cole equation was employed to rationalize the impedance data.

Spinodal Decomposition in Tellurite-Based Glasses Induced by Excimer Laser Irradiation

Tellurite-based glasses in the TeO2-K3Li2Nb5O15, TeO2-Ba5Li2Ti2Nb8O30, and V2Te2O9 were fabricated by the conventional melt-quenching technique. Amorphous and glassy characteristics of the as-quenched samples were established via the X-ray powder diffraction technique and differential thermal analysis, respectively. The as-quenched samples were irradiated by an excimer laser (248 nm). The effect of laser power, duration of irradiation, and the frequency of the laser pulses on the surface features of the above glasses were studied. The optical microscopic studies carried out on the above systems revealed the presence of quasi-periodic and periodic structures on their surfaces. The local compositional variations of these structures were confirmed by back-scattered electron imaging using scanning electron microscope accompanied by energy-dispersive X-ray analysis. These results were convincing enough to state that the glasses in the present investigations had undergone spinodal decomposition on laser irradiation. The incidence of the interconnected texture of two different phases was observed owing to the quenching effect produced by the heating and cooling cycle of the successive laser pulses. Ring- and line-shaped patterns were also observed, respectively, when the pulse frequency of the laser and the duration of irradiation were increased.

Mixed mode (I and II) crack tip fields in bulk metallic glasses

Stationary crack tip fields in bulk metallic glasses under mixed mode (I and II) loading are studied through detailed finite element simulations assuming plane strain, small scale yielding conditions. The influence of internal friction or pressure sensitivity on the plastic zones. notch deformation, stress and plastic strain fields is examined for different mode mixities. Under mixed mode loading, the notch deforms into a shape such that one part of its surface sharpens while the other part blunts. Increase in mode If component of loading dramatically enhances the normalized plastic zone size, lowers the stresses but significantly elevates the plastic strain levels near the notch tip. Higher internal friction reduces the peak tangential stress but increases the plastic strain and stretching near the blunted part of the notch. The simulated shear bands are straight and extend over a long distance ahead of the notch tip under mode II dominant loading. The possible variations of fracture toughness with mode mixity corresponding to failure by brittle micro-cracking and ductile shear banding are predicted employing two simple fracture criteria. The salient results from finite element simulations are validated by comparison with those from mixed mode (I and II) fracture experiments on a Zr-based bulk metallic glass.

Possible mechanism of charge transport and dielectric relaxation in SrO-Bi2O3-B2O3 glasses

Transparent SrBi2B2O7 glasses were prepared via melt-quenching technique and characterized using differential scanning calorimetry and x-ray powder diffraction. The ac conductivities of the glasses were studied as a function of frequency (100 Hz-10 MHz) at different temperatures. The frequency dependence of conductivity has been analyzed using Almond-West expression. The exponent n was nearly unaffected by temperature. Impedance and modulus spectroscopies were employed to further examine the electrical data. Dielectric relaxation exhibited a stretched exponential behavior with a stretching exponent beta independent of temperature. From conductivity analysis we have proposed that the charge transport occurs through the participation of nonbridging oxygen (NBO), which switches positions in a facile manner. The stretched exponential behavior appears to be a direct consequence of the NBO switching mechanism of charge transport.

The composition dependence of electrical switching behavior of Ge7Se93-xSbx glasses

Bulk Ge7Se93-xSbx (21 <= x <= 32) glasses are prepared by melt quenching method and electrical switching studies have been undertaken on these samples to elucidate the type of switching and the composition and thickness dependence of switching voltages. On the basis of the compressibility and atomic radii, it has been previously observed that Se-based glasses exhibit memory switching behavior. However, the present results indicate that Ge7Se93-xSbx glasses exhibit threshold type electrical switching with high switching voltages. Further, these samples are found to show fluctuations in the current-voltage (I-V) characteristics. The observed threshold behavior of Ge7Se93-xSbx glasses has been understood on the basis of larger atomic radii and lesser compressibilities of Sb and Ge. Further. the high switching voltages and fluctuations in the I-V characteristics of Ge-Se-Sb samples can be attributed to the high resistance of the samples and the difference in thermal conductivities of different structural units constituting the local structure of these glasses. The switching voltages of Ge7Se93-xSbx glasses have been found to decrease with the increase in the Sb concentration. The observed composition dependence of switching voltages has been understood on the basis of higher metallicity of the Sb additive and also in the light of the Chemically Ordered Network (CON) model. Further, the thickness dependence of switching voltages has been studied to reassert the mechanism of switching.

Crystallization kinetics of SrBi2B2O7 glasses by non-isothermal methods

Transparent glasses of SrBi2B2O7 (SBBO) were fabricated via the conventional melt-quenching technique. The amorphous and the glassy nature of the as-quenched samples were, respectively, confirmed by X-ray powder diffraction (XRD) and differential scanning calorimetry (DSC). The glass transition (T (g)) and the crystallization parameters [crystallization activation energy (E (cr)) and Avrami exponent (n)] were evaluated under non-isothermal conditions using DSC. There was a close agreement between the activation energies for the crystallization process determined by Augis and Bennet and Kissinger methods. The variation of local activation energy [E (c)(x)] that was determined by Ozawa method, decreased with the fraction of crystallization (x). The Avrami exponent (n(x)) increased with the increase in fraction of crystallization (x) suggesting that there was a change over in the crystallization process from the surface to the bulk.

Thermal anomalies in ternary Ge42-xPbxSe58 glasses near the charge carrier reversal threshold

The carrier type reversal (CTR) from p- to n-type in semiconducting chalcogenide glasses is an important and a long standing problem in glass science. Ge-Se glasses exhibit CTR when the metallic elements Bi and Pb are added. For example, bulk Ge42-xSe58Pbx glasses exhibit CTR around 8-9 at. % of Pb. These glasses have been prepared by melt quenching method. Glass transition temperature (T-g), Specific heat change between the liquid and the glassy states (Delta C-p) at T-g and the nonreversing heat flow (Delta H-nr) measured by modulated differential scanning calorimetry exhibit anomalies at 9 at. % of Pb. These observed anomalies are interpreted on the basis of the nano scale phase separation occurring in these glasses.

Low loss and frequency (1 kHz-1 MHz) independent dielectric characteristics of 3BaO-3TiO(2)-B2O3 glasses

X-ray powder diffraction along with differential thermal analysis carried out on the as-quenched samples in the 3BaO-3TiO(2)-B2O3 system confirmed their amorphous and glassy nature, respectively. The dielectric constants in the 1 kHz-1 MHz frequency range were measured as a function of temperature (323-748 K). The dielectric constant and loss were found to be frequency independent in the 323-473 K temperature range. The temperature coefficient of dielectric constant was estimated using Havinga's formula and found to be 16 ppm K-1. The electrical relaxation was rationalized using the electric modulus formalism. The dielectric constant and loss were 17 +/- 0.5 and 0.005 +/- 0.001, respectively at 323 K in the 1 kHz-1 MHz frequency range which may be of considerable interest to capacitor industry.

High field electrical switching behavior of Ge10Se90-xTlx glasses

Electrical Switching Studies on bulk Ge10Se90-xTlx ( 15 <= x <= 34) glasses have been undertaken to examine the type of switching, composition and thickness dependence of switching voltages. Unlike Ge-Se-Tl thin films which exhibit memory switching, the bulk Ge10Se90-xTlx glasses are found to exhibit threshold type switching with fluctuations seen in their current-voltage (I-V) characteristics. Further, it is observed that the switching voltages (V-T) of Ge10Se90-xTlx glasses decrease with the increase in the Tl concentration. An effort has been made to understand the observed composition dependence on the basis of nature of bonding of Tl atoms and a decrease in the chemical disorder with composition. In addition. the network connectivity and metallicity factors also contribute for the observed decrease in the switching voltages of Ge10Se90-xTlx glasses with Tl addition. It is also interesting to note that the composition dependence of switching voltages of Ge10Se90-xTlx glasses exhibit a small Cusp around the composition x = 22. which is understood on the basis of a thermally reversing window in this system in the composition range 22 <= x <= 30. The thickness dependence of switching voltages has been found to provide an insight about the type of switching mechanism involved in these samples. (C) 2009 Elsevier B.V. All rights reserved

The glass transition and crystallization kinetic studies on BaNaB9O15 glasses

Transparent glasses of BaNaB9O15 (BNBO) were fabricated via the conventional melt-quenching technique. The amorphous and the glassy nature of the as-quenched samples were, respectively, confirmed by x-ray powder diffraction and differential scanning calorimetry (DSC). The glass transition and crystallization parameters were evaluated under non-isothermal conditions using DSC. The correlation between the heating rate dependent glass transition and the crystallization temperatures was studied and the Kauzmann temperature was deduced for BNBO glass plates and powdered samples. The values of the Kauzmann temperature for the plates and powdered samples were 776 K and 768 K, respectively. An approximation- free method was used to evaluate the crystallization kinetic parameters for the BNBO glass samples. The effect of the sample thickness on the crystallization kinetics of BNBO glasses was also investigated.

Effect of indium doping on the electrical switching behaviour of Ge-Te glasses

Bulk Ge15Te85-xInx (1 <= x <= 11) series of glasses have been found to exhibit a threshold switching behaviour for an input current of 2 mA. An initial decrease is seen in the switching voltages (V-T) with the addition of indium, which is due to the higher metallicity of indium. An increase is seen in V-T above 3 at.% of indium, which proceeds until 8 at.%, with a change in slope (lower to higher) seen around 7 at.%. Beyond x = 8, a reversal in trend is exhibited in the variation of V-T, with a well-defined minimum around x = 9 at.%. Based on the composition dependence of V-T, it is proposed that Ge15Te85-xInx glasses exhibit an extended rigidity percolation threshold. The composition, x = 3, at which the V-T starts to increase and the composition, x = 7, at which a slope change is exhibited correspond to the onset and completion, respectively, of the extended stiffness transition. Thermal studies and photoconductivity e85-xInx glasses. In addition, the minimum seen in V-T at x = 9 is associated with the chemical threshold (CT) of this glassy system.

Effect of the addition of B2O3 and BaO-B2O3-SiO2 glasses on the microstructure and dielectric properties of giant dielectric constant material CaCu3Ti4O12

The effect of the addition of glassy phases on the microstructure and dielectric properties of CaCu3Ti4O12 (CCTO) ceramics was investigated. Both single-component (B2O3) and multi-cornponent (30wt% BaO-60wt% B2O3-10wt% SiO2 (BBS)) glass systems were chosen to study their effect on the density, microstructure and dielectric properties of CCTO. Addition of an optimum amount of B2O3 glass facilitated grain growth and an increase in dielectric constant. However, further increase in the B2O3 content resulted in its segregation at the grain boundaries associated with a reduction in the grain size. In contrast, BBS glass addition resulted in well-faceted grains and increase in the dielectric constant and decrease in the dielectric loss. An internal barrier layer capacitance (IBLC) model was invoked to correlate the dielectric constant with the grain size in these samples. (c) 2007 Elsevier Inc. All rights reserved.

Ion irradiation enhances the mechanical performance of metallic glasses

We demonstrate that irradiation may enhance the plasticity in metallic glasses by increasing the free-volume content via micropillar compression experiments on an ion-irradiated bulk metallic glass (BMG). Results show that irradiation decreases the flow stress and enhances the shear band formation by lowering the magnitude of stress serrations in plastic flow regime. These results highlight that amorphous alloys can mitigate the deleterious affects of severe ion irradiation as compared to their crystalline counterparts. (C) 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Spectroscopic investigations and luminescence spectra of Nd3+ and Dy3+ doped different phosphate glasses

Spectral properties of Nd3+ and Dy3+ ions in different phosphate glasses were studied and several spectroscopic parameters were reported. Covalency of rare-earth-oxygen bond was studied in these phosphate glass matrices with the variation of modifier in host glass matrix Using Judd-Ofelt intensity parameters (Omega(2), Omega(4) and Omega(6)), radiative transition probabilities (A) and radiative lifetimes (tau(R)) of certain excited states of Nd3+ and Dy3+ ions are estimated in these glass matrices. From the magnitudes of branching ratios (beta(R)) and integrated absorption cross-sections (Sigma), certain transitions of both the ions are identified for laser excitation. From the emission spectra, peak stimulated emission cross-sections (sigma(P)) are evaluated for the emission transitions observed in all these phosphate glass matrices for both Nd3+ and Dy3+ ions. (C) 2009 Elsevier B.V. All rights reserved.

Evidence for a thermally reversing window in bulk Ge-Te-Si glasses revealed by alternating differential scanning calorimetry

Experiments on Ge15Tc85-xSix glasses (2 <= x <= 12) using alternating differential scanning calorimetry (ADSC) indicate that these glasses exhibit one glass transition and two crystallization reactions upon heating. The glass transition temperature has been found to increase almost linearly with silicon content, in the entire composition tie-line. The first crystallization temperature (T-cl) exhibits an increase with silicon content for x<5; T-cl remains almost a constant in the composition range 5 < x <= 10 and it increases comparatively more sharply with silicon content thereafter. The specific heat change (Delta C-p) is found to decrease with an increase in silicon content, exhibiting a minimum at x=5 (average coordination number, (r) = 2.4); a continuous increase is seen in Delta C-p with silicon concentration above x = 5. The effects seen in the variation with composition of T-cl and Delta C-p at x=5, are the specific signatures of the mean-field stiffness threshold at (r) = 2.4. Furthermore, a broad trough is seen in the enthalpy change (Delta H-NR), which is indicative of a thermally reversing window in Ge15Te85-xSix glasses in the composition range 2 <= x <= 6 (2.34 <= (r) <= 2.42).