Photoacoustic Investigation of Glass Transition in AsxTe1-x Glasses

Photoacoustic (PA) technique is used to study glass transition and temperature dependence of thermal diffusivity in AsxTe1-x glasses with 0.25 0.60. PA amplitude goes through a minimum and the phase shows a maximum at glass transition temperature Tg. The variation of thermal diffusivity with temperature shows sharp decrease near Tg. The variation of thermal diffusivity with composition shows maximum at = 0.40 for all temperatures T Tg.

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]

Dependence of shear yield strain and shear transformation zone on the glass transition temperature in thin film metallic glasses

The dependence of shear yield strain, the activation energy and volume of shear transformation zone on the glass transition temperature was investigated through the analysis of statistical distributions of the first pop-in events during spherical indentation of four different thin film metallic glasses. Only the Cu-Zr metallic glass exhibits a bimodal distribution of the first pop-in loads, whereas W-Ru-B, Zr-Cu-Ni-Al and La-Co-Al metallic glasses show an unimodal distribution. Results show that shear yield strain and activation energy of shear transformation zone decrease whereas the volume of shear transformation zone increases with increasing homologous temperature, indicating that it is the activation energy rather than the volume of shear transformation zone that controls shear yield strain. (C) 2015 Elsevier B.V. All rights reserved.

The elastic manifestation of a spin-glass transition: a low-frequency study

The authors report here the first measurements of low-frequency dynamic elastic properties of a spin glass (Fe59Ni21Cr20) across the transition temperature (Tg approximately=16 K). A minimum in the sound velocity (V) and a maximum in the internal friction (Q-1) were found at temperatures close to but below Tg. The elastic data were compared with the AC susceptibility data taken at similar frequency.

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.

Glass transition. A new approach based on cluster model of glasses

The structure of real glasses has been considered to be microheterogeneous, composed of clusters and connective tissue. Particles in the cluster are assumed to be highly correlated in positions. The tissue is considered to have a truly amorphous structure with its particles vibrating in highly anharmonic potentials. Glass transition is recognized as corresponding to the melting of clusters. A simple mathematical model has been developed which accounts for various known features associated with glass transition, such as range of glass transition temperature,T g, variation ofT g with pressure, etc. Expressions for configurational thermodynamic properties and transport properties of glass forming systems are derived from the model. The relevence and limitations of the model are also discussed.

Behaviour of ultrasonic velocities in amorphous Se90Ge10 and Se85Ge15 alloys near their glass transition

Precise measurements of 10 MHz frequency longitudinal and shear wave velocities are reported in amorphous SeGe alloys near their glass transition temperature T g . There is a sharp decrease of the velocities near T g , but the reduction in velocities appears smaller than expected.

Resolution of conflicting views on thermodynamics of glass transition: A unified model

Classical description of thermodynamic properties during glass transition has been questioned by the entropy-loss model. The uncompensated loss of entropy at the glass transition temperature and zero residual entropy is at the heart of the controversy. Both the models are critically reviewed. A unified model is presented which incorporates features of both entropy loss and residual entropy. It implies two different types of contributions to the entropy of the supercooled liquid, one of which vanishes at the transition and the other which contributes to residual entropy. Entropy gain during spontaneous relaxation of glass, and the nature of heat capacity `hysteresis' during cooling and heating through the glass transition range support the proposed model. Experiments are outlined for differentiating between the models.

Structural Relaxation and Crystallization in a Pd40Cu30Ni10P20 Bulk Metallic Glass

The stability of a Pd40Cu30Ni10P20 bulk metallic glass (BMG) against structural relaxation is investigated by isothermal and isochronal annealing heat treatments below and above its glass transition temperature, Tg, for varying periods. Differential scanning calorimetry (DSC) of the annealed samples shows an excess endotherm at Tg, irrespective of the annealing temperature. This recovery peak evolves exponentially with annealing time and is due to the destruction of anneal-induced compositional short range ordering. The alloy exhibits a high resistance to crystallization on annealing below Tg and complex Pd- and Ni-phosphides evolve on annealing above Tg.

Effect of nanoparticle dispersion on glass transition in thin films of polymer nanocomposites

We present spectroscopic ellipsometry measurements on thin films of polymer nanocomposites consisting of gold nanoparticles embedded in poly(styrene). The temperature dependence of thickness variation is used to estimate the glass transition temperature, T(g). In these thin films we find a significant dependence of T(g) on the nature of dispersion of the embedded nanoparticles. Our work thus highlights the crucial role played by the particle polymer interface morphology in determining the glass transition in particular and thermo-mechanical properties of such nanocomposite films.

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.

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.

Thermo-chemical interpretation of polymer degradation

A correlation has been established between the heat of depolymerization (DeltaH) of vinyl polymers for going from solid polymer state to gaseous monomer state and the activation energy (E) of degradation. On this basis it has been shown that the rate controlling step in the degradation lies in the initiation step. Attempt has been made to correlate theE and DeltaH with glass transition temperature (Tg) and melting temperature (Tm) of the polymers.[/ p]

Electrical switching and thermal studies on Ge22Te78-xIx chalcohalide glasses: The effect of iodine on network-topology

Investigations on the electrical switching behavior and thermal studies using Alternating Differential Scanning Calorimetry have been undertaken on bulk, melt-quenched Ge22Te78-,Is (3 <= x <= 10) chalcohalide glasses. All the glasses studied have been found to exhibit memory-type electrical switching. The threshold voltages of Ge22Te78-I-x(x) glasses have been found to increase with the addition of iodine and the composition dependence of threshold voltages of Ge22Te78-xIx glasses exhibits a cusp at 5 at.% of iodine. Also, the variation with composition of the glass transition temperature (Tg) of Ge22Te78-I-x(x) glasses, exhibits a broad hump around this composition. Based on the present results, the composition x = 5 has been identified as the inverse rigidity percolation threshold at which Ge22Te78-I-x(x) glassy system exhibits a change from a stressed rigid amorphous solid to a flexible polymeric glass. Further, a sharp minimum is seen in the composition dependence of non-reversing enthalpy (Delta H-nr) of Ge22Te78-I-x(x) glasses at x = 5, which is suggestive of a thermally reversing window at this composition. (C) 2007 Elsevier Ltd. All rights reserved.

A chemical approach to an understanding of the fast ion conduction in silver iodide-silver oxysalt glasses

A number of AgI based fast ion conducting glasses, with a general formula AgI---Ag2O---MxOy (MxOy=MoO3, SeO3, WO3, V2O5, P2O5, GeO2, B2O3, As2O3, CrO3) have been studied. A chemical approach is made to investigate the origin of fast ion conduction in these glasses. An index known as Image tructural Image npinning Image umber, SUN (S), has been defined for the purpose, based on the unscreened nuclear charge of silver ions and the equilibrium lectronegativities of the halide-oxyanion matrix in these glasses. The variation of the glass transition temperature, Tg, conductivity, σ, and the energy of activation, Ea, with the concentration of AgI are discussed in the light of the structural unpinning number. Conductivities increase uniformly in any given glass series as a smooth function of S and level off at very high values. The entire range of conductivity appears to vary as ln Image , where ln σ0 corresponds roughly to the conductivity of the hypothetical AgI glass and “a” is a constant which could be obtained as the slope in the graph of ln Ea versus S. It is suggested that the increase in the concentration of AgI beyond 75–80 mole% in the glass is not advantageous from the conductivity point of view.