Manifestation of intermediate phase in mechanical properties: Nano-indentation studies on Ge-Te-Si bulk chalcogenide glasses

Nano-indentation studies have been undertaken on bulk Ge15Te85-xSix glasses (0 <= x <= 9), to estimate hardness, H and elastic modulus, E. It is found that E and H increase initially with the increase in the atomic percent of Si. Further, a plateau is seen in the composition dependence of E and H in the composition range 2 <= x <= 6. It is also seen that the addition of up to 2 at% Si increases the density rho of the glass considerably; however, further additions of Si lead to a near linear reduction in rho, in the range 2 <= x <= 6. Beyond x=6, rho increases again with Si content. The variation of molar volume V-m brings out a more fascinating picture. A plateau is seen in the intermediate phase suggesting that the molecular structure of the glasses is adapting to keep the count of constraints fixed in this particular phase. The observed variations in mechanical properties are associated with the Boolchand's intermediate phase in the present glassy system, in the composition range 2 <= x <= 6, suggested earlier from calorimetric and electrical switching studies. The present results reveal rather directly the existence of the intermediate phase in elastic and plastic properties of chalcogenide glasses. (C) 2012 Elsevier Ltd. All rights reserved.

Pressure Dependence of Glass Transition in As2Te3 Glass

Amorphous solids prepared from their melt state exhibit glass transition phenomenon upon heating. Viscosity, specific heat, and thermal expansion coefficient of the amorphous solids show rapid changes at the glass transition temperature (T-g). Generally, application of high pressure increases the T-g and this increase (a positive dT(g)/dP) has been understood adequately with free volume and entropy models which are purely thermodynamic in origin. In this study, the electrical resistivity of semiconducting As2Te3 glass at high pressures as a function of temperature has been measured in a Bridgman anvil apparatus. Electrical resistivity showed a pronounced change at T-g. The T-g estimated from the slope change in the resistivity-temperature plot shows a decreasing trend (negative dT(g)/dP). The dT(g)/dP was found to be -2.36 degrees C/kbar for a linear fit and -2.99 degrees C/kbar for a polynomial fit in the pressure range 1 bar to 9 kbar. Chalcogenide glasses like Se, As2Se3, and As30Se30Te40 show a positive dT(g)/dP which is very well understood in terms of the thermodynamic models. The negative dT(g)/dP (which is generally uncommon in liquids) observed for As2Te3 glass is against the predictions of the thermodynamic models. The Adam-Gibbs model of viscosity suggests a direct relationship between the isothermal pressure derivative of viscosity and the relaxational expansion coefficient. When the sign of the thermal expansion coefficient is negative, dT(g)/dP = Delta k/Delta alpha will be less than zero, which can result in a negative dT(g)/dP. In general, chalcogenides rich in tellurium show a negative thermal expansion coefficient (NTE) in the supercooled and stable liquid states. Hence, the negative dT(g)/dP observed in this study can be understood on the basis of the Adams-Gibbs model. An electronic model proposed by deNeufville and Rockstad finds a linear relation between T-g and the optical band gap (E-g for covalent semiconducting glasses when they are grouped according to their average coordination number. The electrical band gap (Delta E) of As2Te3 glass decreases with pressure. The optical and electrical band gaps are related as Delta E-g = 2 Delta E; thus, a negative dT(g)/dP is expected when As2Te3 glass is subjected to high pressures. In this sense, As2Te3 is a unique glass where its variation of T-g with pressure can be understood by both electronic and thermodynamic models.

Micropillar compression studies on a bulk metallic glass in different structural states

Uniaxial compression experiments on 0.3, 1 and 3 mu m diameter micropillars of a Zr-based bulk metallic glass in as-cast, shot-peened and structurally relaxed conditions were conducted. Shear band formation and stable propagation is observed to be the plastic deformation mode in all cases, with no detectable difference in yield strength according to either size or condition. The limitations of uniaxial compression tests in assessing the influence of various material conditions on plasticity, when it is inhomogeneous in nature, are illustrated.

Effect of antimony addition on the thermal and electrical-switching behavior of bulk Se-Te glasses

The thermal properties and electrical-switching behavior of semiconducting chalcogenide SbxSe55-xTe45 (2 <= x <= 9) glasses have been investigated by alternating differential scanning calorimetry and electrical-switching experiments, respectively. The addition of Sb is found to enhance the glass forming tendency and stability as revealed by the decrease in non-reversing enthalpy Delta H-nr. and an increase in the glass-transition width Delta T-g. Further, the glass-transition temperature of SbxSe55-xTe45 glasses, which is a measure of network connectivity, exhibits a subtle increase, suggesting a meager network growth with the addition of Sb. The crystallization temperature is also observed to increase with Sb content. The SbxSe55-xTe45 glasses (2 <= x <= 9) are found to exhibit memory type of electrical switching, which can be attributed to the polymeric nature of network and high devitrifying ability. The metallicity factor has been found to dominate over the network connectivity and rigidity in the compositional dependence of switching voltage. which shows a profound decrease with the addition of Sb.

Glass forming ability and stability: Ternary Cu bearing Ti, Zr, Hf alloys

Four Cu bearing alloys of nominal composition Zr25Ti25Cu50, Zr34Ti16Cu50, Zr25Hf25Cu50 and Ti25Hf25Cu50 have been rapidly solidified in order to produce ribbons. All the alloys become amorphous after meltspinning. In the Zr34Ti16Cu50 alloy localized precipitation of cF24 Cu5Zr phase can be observed in the amorphous matrix. The alloys show a tendency of phase separation at the initial stages of crystallization. The difference in crystallization behavior of these alloys with Ni bearing ternary alloys can be explained by atomic size, binary heat of mixing and Mendeleev number. It has been observed that both Laves and Anti-Laves phase forming compositions are suitable for glass formation. The structures of the phases, precipitated during rapid solidification and crystallization can be viewed in terms of Bernal deltahedra and Frank-Kasper polyhedra.

Genome sequencing of cells that live inside glass cages reveals their past history

One-quarter of the total primary production on earth is contributed by diatoms1. These are photosynthetic, unicellular algae with ornamented silica shells found in all aquatic and moist environments. They form the base of energy-efficient food webs that support all aquatic life forms. More than 250 genera of living diatoms, with as many as 100,000 species are known2. Fossil diatoms are known as early as the Cretaceous, 144–65 m.y. ago3. In India, deposits of diatoms occur in Rajasthan and are known as ‘multani mitti’. Multani mitti or Indian Fuller’s earth or diatomaceous earth as it is called in the West, is applied as a paste on the surface of the skin for 15–20 min and then washed-off. This leaves the skin feeling smooth, soft, moist and rejuvenated. Diatomaceous earth is now being used in the formulation of soaps, cleansing products, face powders and skincare preparations. Diatomaceous earth is a mineral material consisting mainly of siliceous fragments of various species of fossilized remains of diatoms.

Growing length and time scales in glass-forming liquids

The glass transition, whereby liquids transform into amorphous solids at low temperatures, is a subject of intense research despite decades of investigation. Explaining the enormous increase in relaxation times of a liquid upon supercooling is essential for understanding the glass transition. Although many theories, such as the Adam-Gibbs theory, have sought to relate growing relaxation times to length scales associated with spatial correlations in liquid structure or motion of molecules, the role of length scales in glassy dynamics is not well established. Recent studies of spatially correlated rearrangements of molecules leading to structural relaxation, termed ``spatially heterogeneous dynamics,'' provide fresh impetus in this direction. A powerful approach to extract length scales in critical phenomena is finite-size scaling, wherein a system is studied for sizes traversing the length scales of interest. We perform finite-size scaling for a realistic glass-former, using computer simulations, to evaluate the length scale associated with spatially heterogeneous dynamics, which grows as temperature decreases. However, relaxation times that also grow with decreasing temperature do not exhibit standard finite-size scaling with this length. We show that relaxation times are instead determined, for all studied system sizes and temperatures, by configurational entropy, in accordance with the Adam-Gibbs relation, but in disagreement with theoretical expectations based on spin-glass models that configurational entropy is not relevant at temperatures substantially above the critical temperature of mode-coupling theory. Our results provide new insights into the dynamics of glass-forming liquids and pose serious challenges to existing theoretical descriptions.

Studies on glass transition and starch re-crystallization in wheat bread during staling using electrical impedance spectroscopy

Bread staling is a very complex phenomenon that is not yet completely understood. The present work explains how the electrical impedance spectroscopy technique can be utilized to investigate the effect of staling on the physicochemical properties of wheat bread during storage. An instrument based on electrical impedance spectroscopy technique is developed to study the electrical properties of wheat bread both at its crumb and crust with the help of designed multi-channel ring electrodes. Electrical impedance behavior, mainly capacitance and resistance, of wheat bread at crust and crumb during storage (up to 120 h) is investigated. The variation in capacitance showed the glass transition phenomenon at room temperature in bread crust after 96 h of storage with 18% of moisture in it. The resistance changes at bread crumb showed the starch recrystallization during staling.

Analysis of Raman bandwidths and bandshapes of glasses through their glass-transition temperatures

Raman bandwidths and bandshapes of some molecular and ionic glasses have been investigated through the glass-transition region. Widths of both polarised and depolarised bands exhibit step-like changes during the glass transition. Molecular and ionic glasses differ with respect to the magnitude and the nature of variations in bandwidths and reorientational times. An attempt has been made to understand the changes in bandwidths around the glass-transition temperature.

Cluster model of the glass transition

A cluster model of the glass transition has been developed, treating the relative size of the cluster as an order parameter. The model accounts for some of the features of the glass transition.

Pressure and temperature dependence of the electrical resistivity of bulk Al23 Te77 glass

Electrical resistivity of bulk amorphous Al23T77 samples has been studied as a function of pressure (up to 80 kbar) and temperature (down to 77 K). At atmospheric pressure the temperature dependence of resistivity obeys the relation = π0 exp(δE/RT) with two activation energies. In the temperature range 300 K T > 234 K the activation energy is 0.58 eV and for 234 >T 185 K the value is δE = 0.30 ev. The activation energy has been measured as a function of pressure. The electrical resistivity decreases exponentially with the increase of pressure and at 70 kbar pressure the electrical behaviour of the sample shows a metallic nature with a positive temperature coefficient. The high pressure phase of the sample is found to be a crystalline hexagonal phase.

Crystallization studies on bulk SixTe100-x glasses

Bulk SixTe100-x (10 less-than-or-equals, slant x less-than-or-equals, slant 28) glasses have been prepared by the melt quenching technique. The crystallization of these glasses has been studied by using differential scanning calorimetry. The composition dependence of the glass transition temperature Tg, the recrystallization temperature Tcr and the melting temperature Tm show an unusual behaviour at the composition x congruent with 20. The glasses with 10 less-than-or-equals, slant x less-than-or-equals, slant 20 undergo double glass transition and double stage crystallization phenomena. On the other hand, glasses with 22 less-than-or-equals, slant x less-than-or-equals, slant 28 exhibit eutectic crystallization. The phases at different stages of crystallization have been identified by using X-ray diffraction techniques. The unusual behaviour at x congruent with 20 can be explained on the basis of the changes in the network topologies of IV-VI chalcogenide glasses.

Pressure induced polymorphous crystallization in bulk Ge20Te80 glass

The pressure and temperature dependence of the electrical resistivity of bulk glassy Ge20Te80 is reported. The effect of annealing is also studied. The glass undergoes a polymorphous or congruent crystallization under high pressures. The high pressure phase is found to have fcc structure with Image . Under thermal treatment the glass undergoes the double stage crystallization. The sample annealed at the first crystallization temperature shows a pressure induced semiconductor-to-metal transition at 4.0 GPa pressure and the crystalline Ge20Te80 samples show the transition at 7 GPa pressure.