Adam-Gibbs Relation for Glass-Forming Liquids in Two, Three, and Four Dimensions

The Adam-Gibbs relation between relaxation times and the configurational entropy has been tested extensively for glass formers using experimental data and computer simulation results. Although the form of the relation contains no dependence on the spatial dimensionality in the original formulation, subsequent derivations of the Adam-Gibbs relation allow for such a possibility. We test the Adam-Gibbs relation in two, three, and four spatial dimensions using computer simulations of model glass formers. We find that the relation is valid in three and four dimensions. But in two dimensions, the relation does not hold, and interestingly, no single alternate relation describes the results for the different model systems we study.

On the microstructure-tensile property correlations in bulk metallic glass matrix composites with crystalline dendrites

Bulk metallic glass (BMG) matrix composites with crystalline dendrites as reinforcements exhibit a wide variance in their microstructures (and thus mechanical properties), which in turn can be attributed to the processing route employed, which affects the size and distribution of the dendrites. A critical investigation on the microstructure and tensile properties of Zr/Ti-based BMG composites of the same composition, but produced by different routes, was conducted so as to identify ``structure-property'' connections in these materials. This was accomplished by employing four different processing methods-arc melting, suction casting, semi-solid forging and induction melting on a water-cooled copper boat-on composites with two different dendrite volume fractions, V-d. The change in processing parameters only affects microstructural length scales such as the interdendritic spacing, lambda, and dendrite size, delta, whereas compositions of the matrix and dendrite are unaffected. Broadly, the composite's properties are insensitive to the microstructural length scales when V-d is high (similar to 75%), whereas they become process dependent for relatively lower V-d (similar to 55%). Larger delta in arc-melted and forged specimens result in higher ductility (7-9%) and lower hardening rates, whereas smaller dendrites increase the hardening rate. A bimodal distribution of dendrites offers excellent ductility at a marginal cost of yield strength. Finer lambda result in marked improvements in both ductility and yield strength, due to the confinement of shear band nucleation sites in smaller volumes of the glassy phase. Forging in the semi-solid state imparts such a microstructure. (c) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Nanocrystallization of TiO2 Anatase Phase in Hydrophobic BaO-TiO2-B2O3 Glass System

Transparent colorless glasses in the ternary BaOTiO2B2O3 system were fabricated via conventional melt-quenching technique. The glasses with certain molar concentrations of BaO and TiO2 on heat treatment at appropriate temperatures yielded nanocrystalline phase of TiO2 associated with the crystallite size in the 515 nm range. Nanocrystallized glasses exhibited high refractive index (n = 2.15) measured at lambda = 543 nm. These glasses were found to be hydrophobic in nature associated with the contact angle of 90 degrees. These high-index glass nanocrystal composites would be of potential interest for optical device applications.

Meso-Structured Silica-Nafion Hybrid Membranes for Direct Methanol Fuel Cells

A series of novel organic-inorganic hybrid membranes have been prepared employing Nafion and acid-functionalized meso-structured molecular sieves (MMS) with varying structures and surface area. Acid-functionalized silica nanopowder of surface area 60 m(2)/g, silica meso-structured cellular foam (MSU-F) of surface area 470 m(2)/g and silica meso-structured hexagonal frame network (MCM-41) of surface area 900 m(2)/g have been employed as potential filler materials to form hybrid membranes with Nafion framework. The structural behavior, water uptake, proton conductivity and methanol permeability of these hybrid membranes have been investigated. DMFCs employing Nafion-silica MSU-F and Nafion-silica MCM-41 hybrid membranes deliver peak-power densities of 127 mW/cm(2) and 100 mW/cm(2), respectively; while a peak-power density of only 48 mW/cm(2) is obtained with the DMFC employing pristine recast Nafion membrane under identical operating conditions. The aforesaid characteristics of the hybrid membranes could be exclusively attributed to the presence of pendant sulfonic acid groups in the filler, which provide fairly continuous proton-conducting pathways between filler and matrix in the hybrid membranes facilitating proton transport without any trade-off between its proton conductivity and methanol crossover. (C) 2012 The Electrochemical Society. DOI: 10.1149/2.036211jes] All rights reserved.

Photocatalytic degradation of gaseous toluene by using immobilized titania/silica on aluminum sheets

The aim of this study was to prepare a highly active immobilized titania/silica photocatalyst and to test its performance in situ toward degradation of toluene as one of the major toxic indoor contaminants. In this work, two different titania layers immobilized on Al sheets were synthesized via low temperature sol-gel method employing presynthesized highly active titania powders (Degussa P25 and Millennium PC500, mass ratio 1:1): (a) with a silica/titania binder and a protective layer and (b) without the binder. The photocatalysts were characterized by X-ray diffraction, nitrogen sorption measurements, scanning electron microscopy (SEM), infrared spectroscopy, and UV-vis diffuse reflectance spectroscopy (DRS). The in situ photocatalytic degradation of gaseous toluene was selected as a probe reaction to test photocatalytic activity and to verify the potential application of these materials for air remediation. Results show that nontransparent highly photocatalytically active coatings based on the silica/titania binder and homogeneously dispersed TiO2 powders were obtained on the Al sheets. The crystalline structure of titania was not altered upon addition of the binder, which also prevented inhomogeneous agglomeration of particles on the photocatalyst surface. The photoactivity results indicate that the adsorption properties and photocatalytic activity of immobilized photocatalysts with the silica/titania binder and an underlying protective layer were very effective and additionally, they exhibited considerably improved adhesion and uniformity. We present a new highly photocatalytically active immobilized catalyst on a convenient metallic support, which has a potential application in an air cleaning device.

Direct ultrafast laser written C-band waveguide amplifier in Er-doped chalcogenide glass

This paper reports the fabrication and characterization of an ultrafast laser written Er-doped chalcogenide glass buried waveguide amplifier; Er-doped GeGaS glass has been synthesized by the vacuum sealed melt quenching technique. Waveguides have been fabricated inside the 4 mm long sample by direct ultrafast laser writing. The total passive fiber-to-fiber insertion loss is 2.58 +/- 0.02 dB at 1600 nm, including a propagation loss of 1.6 +/- 0.3 dB. Active characterization shows a relative gain of 2.524 +/- 0.002 dB/cm and 1.359 +/- 0.005 dB/cm at 1541 nm and 1550 nm respectively, for a pump power of 500 mW at a wavelength of 980 nm. (C) 2012 Optical Society of America

Indentation size effect and shear transformation zone size in a bulk metallic glass in two different structural states

The existence of an indentation size effect (ISE) in the onset of yield in a Zr-based bulk metallic glass (BMG) is investigated by employing spherical-tip nanoindentation experiments. Statistically significant data on the load at which the first pop-in in the displacement occurs were obtained for three different tip radii and in two different structural states (as-cast and structurally relaxed) of the BMG. Hertzian contact mechanics were employed to convert the pop-in loads to the maximum shear stress underneath the indenter. Results establish the existence of an ISE in the BMG of both structural states, with shear yield stress increasing with decreasing tip radius. Structural relaxation was found to increase the yield stress and decrease the variability in the data, indicating ``structural homogenization'' with annealing. Statistical analysis of the data was employed to estimate the shear transformation zone (STZ) size. Results of this analysis indicate an STZ size of similar to 25 atoms, which increases to similar to 34 atoms upon annealing. These observations are discussed in terms of internal structure changes that occur during structural relaxation and their interaction with the stressed volumes in spherical indentation of a metallic glass. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Variation in glass transition temperature of polymer nanocomposite films driven by morphological transitions

We report the variation of glass transition temperature in supported thin films of polymer nanocomposites, consisting of polymer grafted nanoparticles embedded in a homopolymer matrix. We observe a systematic variation of the estimated glass transition temperature T-g, with the volume fraction of added polymer grafted nanoparticles. We have correlated the observed T-g variation with the underlying morphological transitions of the nanoparticle dispersion in the films. Our data also suggest the possibility of formation of a low-mobility glass or gel-like layer of nanoparticles at the interface, which could play a significant role in determining T-g of the films provided. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4773442]

A 12 V Substrate-Integrated PbO2-Activated Carbon Asymmetric Hybrid Ultracapacitor with Silica-Gel-Based Inorganic-Polymer Electrolyte

A 12 V Substrate-Integrated PbO2-Activated Carbon hybrid ultracapacitor (SI-PbO2-AC HUCs) with silica-gel sulfuric acid electrolyte is developed and performance tested. The performance of the silica-gel based hybrid ultracapacitor is compared with flooded and AGM-based HUCs. These HUCs comprise substrate-integrated PbO2 (SI-PbO2) as positive electrodes and high surface-area activated carbon with dense graphite-sheet substrate as negative electrodes. 12 V SI-PbO2-AC HUCs with flooded, AGM and gel electrolytes are found to have capacitance values of 308 F, 184 F, and 269 F at C-rate and can be pulse charged and discharged for 100,000 cycles with only a nominal decrease in their capacitance values. The best performance is exhibited by gel-electrolyte HUCs.

On the mechanism and the length scales involved in the ductile fracture of a bulk metallic glass

Some bulk metallic glasses (BMGs) exhibit high crack initiation toughness due to shear band mediated plastic flow at the crack tip and yet do not display additional resistance to crack growth due to the lack of a microstructure. Thus, at crack initiation, the fracture behavior of BMGs transits from that of ductile alloys to that of brittle ceramics. In this paper, we attempt to understand the physics behind the characteristic length from the notch root at which this transition occurs, through testing of four-point bend specimens made of a nominally ductile Zr-based BMG in three different structural states. In the as-cast state, both symmetric (mode I) and asymmetric (mixed mode) bend specimens are tested. The process of shear band mediated plastic flow followed by crack initiation at the notch root was monitored through in situ imaging. Results show that stable crack growth occurs inside a dominant shear band through a distance of, similar to 60 mu m, irrespective of the structural state and mode mixity, before attaining criticality. Detailed finite element simulations show that this length corresponds to the distance from the notch root over which a positive hydrostatic stress gradient prevails. The mean ridge heights on fractured surfaces are found to correlate with the toughness of the BMG. The Argon and Salama model, which is based on the meniscus instability phenomenon at the notch root, is modified to explain the experimentally observed physics of fracture in ductile BMGs. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Probing hemoglobin confinement inside submicron silica tubes using synchrotron SAXS and electrochemical response

The configuration of hemoglobin in solution and confined inside silica nanotubes has been studied using synchrotron small angle X-ray scattering and electrochemical activity. Confinement inside submicron tubes of silica aid in preventing protein aggregation, which is vividly observed for unconfined protein in solution. The radius of gyration (R-g) and size polydispersity (p) of confined hemoglobin was found to be lower than that in solution. This was also recently demonstrated in case of confined hemoglobin inside layered polymer capsules. The confined hemoglobin displayed a higher thermal stability with Rg and p showing negligible changes in the temperature range 25-75 degrees C. The differences in configuration between the confined and unconfined protein were reflected in their electrochemical activity. Reversible electrochemical response (from cyclic voltammograms) obtained in case of the confined hemoglobin, in contrary to the observance of only a cathodic response for the unconfined protein, gave direct indication of the differences between the residences of the electroactive heme center in a different orientation compared to that in solution state. The confined Hb showed loss of reversibility only at higher temperatures. The electron transfer coefficient (alpha) and electron transfer rate constant (k(s)) were also different, providing additional evidence regarding structural differences between the unconfined and confined states of hemoglobin. Thus, absence of any adverse effects due to confinement of proteins inside the inorganic matrices such as silica nanotubes opens up new prospects for utilizing inorganic matrices as protein ``encapsulators'', as well as sensors at varying temperatures.

Comparison of ZnO films deposited on indium tin oxide and soda lime glass under identical conditions

ZnO films have been grown via a vapour phase transport (VPT) on soda lime glass (SLG) and indium-tin oxide (ITO) coated glass. ZnO film on ITO had traces of Zn and C which gives them a dark appearance while that appears yellowish-white on SLG. X-ray photoelectron spectroscopy studies confirm the traces of C in the form of C-O. The photoluminescence studies reveal a prominent green luminescence band for ZnO film on ITO. (C) 2013 Author(s).

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.

Role of silica nanoparticles in conductivity enhancement of nanocomposite solid polymer electrolytes: (PEG(x) NaBr): ySiO(2)

Nanocomposite solid polymer electrolytes (NCSPEs) with conducting species other than Li ions are being investigated for solid-state battery applications. Pristine solid polymer electrolytes (SPEs) do not show ionic conductivity suitable for batteries. Addition of inert fillers to SPEs is known to enhance the ionic conductivity. In this paper, we present the role of silica nanoparticles in enhancing the ionic conductivity in NCSPEs with sodium as conducting species. Sodium bromide is complexed with the host polyethylene glycol polymer by solution cast method and silica nanoparticles (SiO2, average particle size 7 nm) are incorporated into the complex in small amounts. The composites are characterized by powder XRD and IR spectroscopy. Conductivity measurements are undertaken as a function of concentration of salt and also as a function of temperature using impedance spectroscopy. Addition of silica nanoparticles shows an enhancement in conductivity by 1-2 orders of magnitude. The results are discussed in terms of interaction of nanoparticles with the nonconducting anions.

Low loss waveguide on chalcogenide glass using ultrafast laser at low repetition rate

In this work, we synthesized bulk amorphous GeGaS glass by conventional melt quenching technique. Amorphous nature of the glass is confirmed using X-ray diffraction. We fabricated the channel waveguides on this glass using the ultrafast laser inscription technique. The waveguides are written on this glass 100 mu m below the surface of the glass with a separation of 50 ae m by focusing the laser beam into the material using 0.67 NA lens. The laser parameters are set to 350 fs pulse duration at 100 KHz repetition rate. A range of writing energies with translation speeds 1 mm/s, 2 mm/s, 3 mm/s and 4 mm/s were investigated. After fabrication the waveguides facets were ground and polished to the optical quality to remove any tapering of the waveguide close to the edges. We characterized the loss measurement by butt coupling method and the mode field image of the waveguides has been captured to compare with the mode field image of fibers. Also we compared the asymmetry in the shape of the waveguide and its photo structural change using Raman spectra.