Universal scaling between structural relaxation and caged dynamics in glass-forming systems: Free volume and time scales

It is shown that the Debye-Waller factor (DW), a measure of the cage dynamics, is contributed by free-volume in o-terphenyl (OTP) and glycerol. An elementary ansatz provides an alternative way to get the reduced DW from Positron Annihilation Lifetime Spectroscopy (PALS). The ansatz supports the scaling of the slow relaxation with the fast caged dynamics over about ten decades in relaxation times in OTP and glycerol. Both PALS and neutron scattering experiments show that, in order to evidence the scaling, the observation times must be shorter than the time scales of the relaxation processes.     

Hidden slow time scale of correlated motions in supercooled liquids: Multi-time correlation function approach

A three-time correlation function of particle displacements is introduced and numerically calculated by performing molecular dynamics simulations of binary soft-sphere supercooled systems. It is found that the two-dimensional representations of the three-time correlation function reveal couplings of particle motions that exist over a wide range of time scales. Furthermore, it is demonstrated that the systematic change in the second time interval in the three-time correlation function enables us to analyze how the correlations in mobility decay with time. From this analysis, the characteristic time scale of dynamical heterogeneity is quantified. We find that the dynamical heterogeneity time scale becomes much slower than the α-relaxation time as the temperature decreased.     

Second harmonic generation studies of intrinsic and extrinsic relaxation dynamics in poly(methy1 methacrylate)

Second harmonic generation (SHG) is used to monitor the reorientation a dopant chromophore in slightly entangled poly(methy1 methacrylate) (PMMA). The effect of charge and temperature on both the decay and the much less studied onset modes of SHG signal at temperatures above the glass transition has been examined. At variance with the theoretical predictions, it is shown that the onset and the decay times are not coincident. An isothermal experiment above the glass transition shows a lengthening of relaxation time of the decay mode due to successive poling process, which is ascribed to charge memory effects. In contrast, the latter do not affect the onset characteristic time. The effect of temperature above the glass transition on dopant rotation and polymer relaxations has been also examined. As temperature increases the relaxation times of both the onset and the decay modes decrease. If the surface charge and the charge memory effect are erased, the decay time compares quite well with the structural relaxation time. Differently, the onset time exhibits a partial decoupling.     

The role of primitive relaxation in the dynamics of aqueous mixtures, nano-confined water and hydrated proteins

The relaxation scenario in aqueous systems, such as mixtures of water with hydrophilic solutes, nano-confined water and hydrated biomolecules, has been shown to exhibit general features, in spite of the huge differences in structure, chemical composition and complexity. Dynamics, in all these systems, invariably shows at least two relaxations: (i) a slower process, related to cooperative and structural motions of water and solute molecules (in the case of mixtures) or related to interfacial processes in the case of confined water and (ii) a faster process, with non-cooperative character originating from water. The latter has properties including timescale and temperature dependence similar or related in all the aqueous systems. This water-specific relaxation can be identified as the primitive relaxation, or the Johari-Goldstein β-relaxation. The primitive process is the precursor of the many-body relaxation process which increases in length-scale with time until the terminal α-relaxation is reached.Using new experimental data (at atmospheric and high pressure) along with a revision of most of the recent literature on the dynamics of confined water and aqueous mixtures, we show that the two abovementioned relaxation processes are inter-related as evidenced by correlations in their properties. For instance, both relaxation time and dielectric strength of the water-specific relaxation exhibit a crossover from a stronger to a weaker dependence with decreasing T, at the temperature where the slow process attains a very long timescale (> 1 ks) and becomes structurally arrested, exactly analogous to that found for β-relaxation in van der Waals liquids. Moreover, the primitive relaxation of water is shown to play a pivotal role in determining the dynamics of hydrated biomolecules in general, including the “dynamic transition” observed by neutron scattering and Mössbauer spectroscopy. We show that the primitive relaxation of the solvent is responsible for the dynamic transition, even in the case that the solvent is not pure water or an aqueous mixture.     

Universal critical-like scaling of dynamics in plastic crystals

Many theoretical models for the glassy dynamics have been proposed so far describing the changes in molecular dynamics along the extraordinary slowing down in the vitrification process of a disordered phase on cooling. Many of these theories share the concept of cooperative rearranging regions firstly proposed by Adam and Gibbs. Among them, the dynamical scaling model (DSM) is based on the random diffusion of free volume which creates random walking clusters formed by cooperatively rearranging entities.Within this framework a critical phenomenon relating a hidden phase transition at T_C (below T_g) implies the divergence of the relaxation time (τ) or viscosity (η) τ, η ∝ (T − T_C) ^− ? with a universal scaling exponent φ → 9. In this work we apply the DSM model to orientational glasses, obtained from the quenching of orientationally disordered phases (plastic crystals) via the application of the linearized derivative-based transformation of dielectric spectroscopy τ(T) data.     

Rapid quenching and glass formation in chalcogenide glasses: Preparation and properties of Ge–As–Te glasses over an extended composition ranges

In Ge–As–Te system, the glass forming region determined by normal melt quenching method has two regions (GFR I and GFR II) separated by few compositions gap. With a simple laboratory built twin roller apparatus, we have succeeded in preparing Ge_7.5As_xTe_92.5−x glasses over extended composition ranges. A distinct change in T_g is observed at x = 40, exactly at which the separation of the glass forming regions occur indicating the changes in the connectivity and the rigidity of the structural network. The maximum observed in glass transition (T_g) at x = 55 corresponding to the average coordination number (Z_av) = 2.70 is an evidence for the shift of the rigidity percolation threshold (RPT) from Z_av = 2.40 as predicted by the recent theories. The glass forming tendency (K_gl) and ΔT (=T_c−T_g) is low for the glasses in the GFR I and high for the glasses in the GFR II.     

Nonlinear susceptibility measurements in a supercooled liquid close to Tg: Growth of the correlation length and possible critical behavior

The existence of a growing correlation length associated with the strong increase of relaxation times of glass-formers close to the glass transition is still a major open question in glass physics. It has been recently proposed that the ac nonlinear susceptibility of a supercooled liquid close to the glass transition temperature T_g would be a probe of dynamical correlations. As for spin glasses, where the nonlinear susceptibility diverges at the transition, this quantity is tailored to reveal the possible “hidden” critical behavior of the glass transition. We have developed a high sensitivity experimental device to measure the nonlinear dielectric susceptibility of an insulating material at finite frequency. It measures the third harmonics of the current flowing out of a capacitor with the supercooled liquid as the dielectric layer. It is based on a bridge with two capacitors, and reaches a sensitivity better than 10^− 7 (ratio of third to first harmonics). Our first results on supercooled glycerol are presented. They clearly reveal the growing of the correlations close to the glass transition.     

Isobaric and isothermal glass transition of PMMA: pressure-volume-temperature experiments and modelling predictions

The scaling law for relaxation times, recently proposed by Casalini and Roland, is utilized in the framework of KAHR (Kovacs, Aklonis, Hutchinson, and Ramos) phenomenological theory. With this approach it is shown that the pressure, volume, and temperature (PVT) data obtained on Poly(methyl-methacrylate) (PMMA) can be reliably predicted, in the region of the alpha-relaxation, by using only two fitting parameters, namely: the relaxation time in the reference state, τ_g, and the fractional exponent, β, that describes the dispersion of the alpha-relaxation.     

On the dependence of the properties of glasses on cooling and heating rates II: Prigogine-Defay ratio, fictive temperature and fictive pressure

In a previous analysis (J. Chem. Phys. 125 (2006) 094505) it was shown by us that - in contrast to earlier believe - a satisfactory theoretical interpretation of the experimentally measured values of the so-called Prigogine-Defay ratio, Π, can be given employing only one structural order parameter. According to this analysis, the value of this ratio has to be, in accordance with experimental findings, larger than one (Π > 1). This analysis is extended here and, in particular, the dependence of the value of Π on cooling and heating rates is studied. Finally, employing the general model-independent definition of internal (fictive) pressure and fictive temperature, developed by us (J. Non-Crystalline Solids 355 (2009) 653), it is shown how these parameters behave in dependence on temperature for different sets of cooling and heating rates. Some further consequences and possible extensions are discussed briefly.     

Structural and transport properties of quaternary glass system: LiF-Li2O-SrO-Bi2O3

Bismuth based glasses containing LiF, Li₂O and SrO were investigated by different physical, spectroscopic and transport techniques. The results show that density of the glass system increases whereas glass transition temperature decreases with increase in LiF content. The decrease in glass transition temperature is attributed to the entry of the fluoride ions into the glass network mainly substitutionally in place of oxygen ion. The increase in dc electrical conductivity in the present glasses with increase in the fluorine ions is due to the mixed contribution of the positively charged lithium cations throughout the glass network and the negatively charged fluorine, which may act as impurity and/or as terminal non-bridging halide ion. Infrared and Raman spectroscopic results indicate that the glass network consists of BiO₆ octahedral and BiO₃ pyramidal units.     

Heterogeneities at short and long time scales of the dynamics of a probe molecule in different model glass formers

The correlations, namely dynamic heterogeneity, and different relaxation time and length scales were investigated in two model glass formers. Decoupling phenomena were observed on the transport coefficients, which would correspond to different averages over these heterogeneities. The temperature dependence of the rotational dynamics of a nearly cylindrical molecular tracer in phenyl salicylate (SALOL) was investigated over the short time scale of the Longitudinal Detected Electron Spin Resonance spectroscopy (LODESR). A comparison with the dynamics of the same probe dissolved in either o-terphenyl (OTP) or SALOL is also reported on the short and long time scales of the rotational relaxation, the latter being provided by linear Electron Spin Resonance (ESR) studies. The rotational dynamics, at short and long times, exhibited a similar behavior in both glass formers with exponential relaxation and coupling to the viscous flow at higher temperatures, and with selective decouplings on cooling. Interestingly, by proper scaling, the dynamics at long times and the viscosity of the host matrices collapse in a single curve in a wide temperature range. The scaling does not work at short times.     

A novel strategy for the preparation of yttria-stabilized zirconia powders: Deposition and scratching of thin films obtained by the sol-gel method

In the present work, an alternative to the traditional sol-gel method is reported. The gel is deposited on a wide flat glassy surface so that a very thin film of solid is obtained after evaporation of the solvent. The yttria-stabilized zirconia powders are recovered by removing the referred film from the glassy surface and subsequent milling. The samples have been characterized by Scanning Electron Microscopy (SEM), nitrogen adsorption at −196 °C and Fourier Transform Infrared (FT-IR) spectroscopy. The experimental results show that the 3 mol% yttria-stabilized zirconia (3YSZ) powders prepared by drying of thin films at 100 °C exhibit extremely low values of specific surface area and pore volumes. Furthermore, the proportion of solvent or the type of alcohol used in the preparation of the powders play a very important role in the textural properties of the 3YSZ powders. In this connection, for samples prepared by varying the propanol proportion an increase in the volume of this solvent leads to larger values of specific surface area and pore volumes. On the other hand, an increase in the molecular size of the alcohol used as the solvent leads to a noticeable development of the textural parameters.     

On the dependence of the properties of glasses on cooling and heating rates: I. Entropy, entropy production, and glass transition temperature

The glass transition is theoretically described in terms of a generic non-equilibrium thermodynamics approach employing De Donder's structural order parameter method, appropriate expressions for the relaxation behavior of glass-forming systems and a simplified but qualitative correct model of glass-forming melts with one order parameter related to the free volume of the system. Employing this approach the behavior of a variety of thermodynamic quantities describing glass-forming systems in vitrification and devitrification processes is interpreted theoretically. The present paper is devoted to the computation of the entropy, the entropy production and the glass transition temperature in dependence on the cooling and heating rates, varying latter parameter in a broad interval. A comparison with experimental results is given and some further consequences and possible extensions are discussed briefly.     

Nanocrystalline ZnS dispersed in polymer electrolyte (PEO :NH4I): Preparation and electrical conductivity measurements

Nano-composites of a polymer electrolyte PEO:NH₄I (80:20) have been prepared by dispersing nano-size ZnS crystallites in it. The measured band gap of dispersed ZnS is 3.9 eV and its particle size as estimated from the XRD linewidths is 11 nm. Detailed I–V and polarisation studies show that the composite polymer film is a mixed (ionic+electronic) conductor and that the dispersoid ZnS is n-type. The total electrical conductivity Vs composition studies show two peaks at the ZnS concentrations of 4 and 10wt% which can be qualitatively explained on the basis of two-percolation threshold model.     

Influence of the polymer architecture on the high temperature behavior of SiCO glasses: A comparison between linear- and cyclic-derived precursors

Two series of cross-linked polysiloxanes, precursors for silicon oxycarbide glasses, have been synthesized from a linear and a cyclic Si-H-containing siloxane having the same chemical formula (SiCOH₄). The crosslinking has been achieved by hydrosilylation reaction with various amounts of divinylbenzene (DVB). A detailed structural characterization has been performed by ²⁹Si and ¹³C MAS NMR, FT-IR and chemical analysis. As a result, two different structural models have been proposed for the two series of resins. The two resins have been pyrolyzed at 1400 °C and the resulting SiCO ceramics characterized by X-ray diffraction. It has been shown that the stability of the amorphous silica phase present in the SiCO ceramics is strongly influenced by the molecular organization of the starting precursors. The presence of siloxane rings in the cyclic-derived polysiloxane decreases the stability of the amorphous SiO₂ and promotes the crystallization of cristobalite.     

The selenium based chalcogenide glasses with low content of As and Sb: DSC, StepScan DSC and Raman spectroscopy study

Thermal properties and structure of As_xSe_100−x and Sb_xSe_100−x glass-forming systems (x = 0, 1, 2, 4, 8 and 16) were studied by conventional and StepScan DSCs and Raman spectroscopy. Compositional dependence of the glass transition temperature, T_g, was determined from reversible part of StepScan DSC records and discussed. The attention was also focused on the crystallization of undercooled melts of these systems. It was found that only selenium crystallizes from undercooled melts of As–Se system and its tendency to crystallize decreases markedly with increasing As content, for arsenic content higher than 4 at.% no crystallization was observed. In the case of Sb–Se system Sb₂Se₃ crystallizes in the first step followed by trigonal selenium crystallization from non-stoichiometric undercooled melt. Sb₂Se₃ crystallizes from incongruent melt with crystallization enthalpy ΔH_c(Sb₂Se₃) = −52 ± 2 J/(g of Sb₂Se₃), Johnson–Mehl–Avrami kinetics of crystallization and kinetic exponent close to 3 was found. Raman spectra were measured to obtain basic information on the structure of both glassy systems.     

Surface chemistry and transport effects in GaN hydride vapor phase epitaxy

A simple quasi-thermodynamic model of surface chemistry in GaN hydride vapor phase epitaxy (HVPE) is presented. The model is coupled with the detailed 3D simulations of species transport in a horizontal-tube reactor and validated by the comparison with the data on the GaN growth rate obtained by laser reflectometry. Parametric study of the growth rate as a function of temperature and species flow rates has been performed over a wide range of growth conditions. The important role of species transport in an HVPE reactor is demonstrated. In particular, a strong effect of the natural concentration convection resulting in the formation of recirculation zones and in a non-uniform vapor composition is revealed by modeling. The impact of these effects on the GaN growth rate and V/III ratio on the growth surface is discussed in detail.     

Solute trapping and the effects of anti-trapping currents on phase-field models of coupled thermo-solutal solidification

We explore how the inclusion of an anti-trapping current within a phase-field model of coupled thermo-solutal growth formulated in the thin interface limit actually affects the observed levels of solute trapping during dendritic growth. The problem is made computationally tractable by the use of advanced numerical techniques including local mesh adaptivity, implicit temporal discretization and a multigrid solver. Contrary to published results for pure solutal models we find that the inclusion of such an anti-trapping current does not lead to the recovery of the equilibrium partition coefficient, except in the limit of vanishing growth velocity. At higher growth velocities non-vanishing amounts of solute trapping are observed.     

Effect of impurity (Te and Zn) incorporation in the density of defect states in thin films of Se90In10 and Se75In25 glassy alloys

In this paper we report the effect of Te and Zn incorporation on the density of defect states of two binary Se–In glassy systems. For this purpose, we have chosen here two well known Se₉₀In₁₀ and Se₇₅In₂₅ binary glassy alloys. Thin films of Se₉₀In₁₀, Se₇₅In₂₅, Se₇₅In₁₀Te₁₅ and Se₇₅In₁₀Zn₁₅ glassy alloys prepared by quenching method, were deposited on glass substrate using thermal evaporation technique. Current–voltage characteristics have been measured at various fixed temperatures in the thin films under study. Ohmic behavior was observed at low electric fields while at high electric fields current becomes superohmic. An analysis of the experimental data confirms the presence of space charge limited conduction in Se₉₀In₁₀, Se₇₅In₁₀Te₁₅ and Se₇₅In₁₀Zn₁₅ glassy alloys. It was found that the absence of space charge limited conduction in Se₇₅In₂₅ may be due to joule's heating at high fields. By applying the theory of space charge limited conduction, the density of defect states near Fermi level was calculated. The peculiar role of the additives (Te and Zn) in the pure binary Se₉₀In₁₀ and Se₇₅In₂₅ glassy alloys is also discussed in terms of electro-negativity difference between the elements involved.