DC conductivity and secondary structural relaxations in high-conducting Li glasses

In the course of investigating the mechanism of conductivity of fast-conducting, multicomponent lithium fluoroborate-type glasses, an isothermal drift in the conductivities has been found at temperatures so far below the normal glass transition ( 300°) that an origin in normal glass annealing effects appears improbable. Analysis of the 1st order kinetics of this relaxation in the temperature range 150–250°C yields an activation energy more than an order of magnitude less than that of the primary structural relaxation, suggesting the processunder observation is a secondary structural relaxation of the type frequently seen in polymer glasses.     

Sound velocity in liquid and glassy selenium

The speed of longitudinal sound waves at 7 and 22 MHz has been measured in liquid, supercooled, and amorphous selenium, including the region around the glass transition temperature, T_g, near 35 °C. In amorphous selenium the speed of shear waves at 7 MHz was also measured. The experiments were performed with high purity Se (99.9999%) hermetically sealed in an evacuated silica ampoule. Four temperature regions with strongly different relaxation times can be distinguished between room temperature and the melting point: (1) a glassy state below T_g, which is stable on the time scale of the experiments, (2) a glassy state above T_g, which is metastable on the time scale of the experiments, (3) a region where homogeneous crystal nucleation occurs, and (4) a supercooled liquid, which is stable on the time scale of the experiments. Each region is marked by a change in the slope of the temperature dependence of the sound velocity. Near the glass transition temperature the velocities of longitudinal and transverse sound exhibit hysteresis with a step-like drop on heating and a more continuous rise on cooling. The step-like anomaly in sound velocity may be a general property of the glass transition.     

The review of possible interrelations between ionic conductivity, internal friction and the viscosity of glasses and glass forming melts within the framework of Maxwell equations

The review contains the results of application of Maxwell equations for mechanical relaxation and electrical conductivity, to the systematization of large amount of experimental data related to mechanical, viscous, and electrical properties of inorganic glasses and glass forming melts. The generalization of internal friction results shows the existence of characteristic values for the ratios of temperatures, responsible for α-, β- and ionic relaxations; they are independent on the frequency and chemical composition. This is the evidence for the main role of elastic deformations at various corpuscular processes and the existence of characteristic scale of activation barriers predetermined by local volumes of deformation. It is shown the possibility of very precise calculation of the temperature of “ionic” internal friction maximum for one-alkali oxide glasses directly from Maxwell equation and d.c. conductivity experimental data. The volumes of particles overcoming the potential barrier at viscous flow practically coincide with the results of direct structural determinations. The existence of universal relation between d.c. conductivity and viscosity for the extremely wide temperature intervals (Littleton relation) is proved for silicate and phosphate melts. The theory of this dependence is proposed. The results show the effectiveness of the attempts to unite the continual and discrete approaches within the framework of Maxwell equations to obtain the simplest understanding the mechanisms of different types of relaxation. The review comprises many Russian papers unknown in English scientific literature.     

The effect of cooling rate on the glass transition of an amorphous polymer

Cooling down from the equilibrium state at different rates reveals the dynamic behavior of glass forming materials. In particular, the dependence of the glass transition region on the cooling rate, q is commonly agreed to contain information regarding the activation energy of the relaxation time, τ. In this work experimental and theoretical aspects of such a relationship have been highlighted. Experimentally, the glass transition zone of amorphous polystyrene films has been investigated over two decades of cooling rate (0.5–50 K/min) by using refractive index measurements. The shift of the glass transition temperature and the broadening of the transition zone at increased cooling rate have been characterized. Theoretically, the cooling experiments have been simulated within the integral formulation of the Kovacs–Aklonis–Hutchinson–Ramos (KAHR) model using the Vogel temperature dependence for the relaxation time. The Frenkel–Kobeko–Reiner equation, τq = constant, provided the needed relationship between the experiments and the theory, enabling the evaluation of the relevant parameter of the kinetic model, i.e. the Vogel activation energy and the zero configurational entropy temperature, from the shift of the glass transition temperature with cooling rate.     

Viscosity of germanium sulfide melts

Viscosities of Ge_xS_1−x melts (0.30⩽x⩽0.44) have been measured by penetration viscometry from 10⁷ to 10¹³ Pa s. The temperature dependence of equilibrium viscosities in this range can be expressed approximately by a simple Arrhenius equation. Both the heat capacity change at the glass transition and the activation energy of viscous flow monotonously increase with germanium content as predicted by the Adam–Gibbs theory. Therefore, the connectivity of the germanium–sulfur network is reduced due to decreasing concentration of sulfur which causes increasing fragility of the undercooled liquid. The glass transition temperature exhibits a maximum near the GeS₂ composition where heteropolar bonds are predominantly formed.     

Stabilization of metallic glass studied by internal friction measurement

The internal friction Q^?1 and the oscillation frequency f of Zr–Ti–Cu–Ni–Be metallic glass specimens were measured using an inverted torsion pendulum with the free decay method. A single-roller melt-spinning apparatus was used for preparing the specimens. Isothermal annealing near the glass transition temperature T_g was performed to investigate the stabilization of the specimens. Q^?1 decreased with annealing time t due to the stabilization. Q^?1-vs-t was measured at various annealing temperatures T_a, and the values of relaxation time τ for the stabilization process were determined. The dependence of τ on T_a showed that the hydrodynamic behavior represented by the Vogel–Tammann–Fulcher form and the hopping behavior represented by the Arrhenius form were observed in high- and low-temperature regions, respectively. The crossover of the two behaviors was seen at a temperature near and somewhat higher than T_g. The result was discussed on the basis of the viscoelastic relaxation in glassy materials.     

An electrospray technique for hyperquenched glass calorimetry studies: Propylene glycol and di-n-butyl phthalate

We describe an electrospray technique for in situ preparation, for differential scanning calorimetry study, of samples of molecular liquids quenched into the glassy state on extremely short time scales (hyperquenched). We study the cases of a hydrogen-bonded liquid, propylene glycol, PG and a Van der Waals liquid, di-n-butyl phthalate DBP. Using a fictive temperature method of obtaining the temperature dependence of enthalpy relaxation, we show that the electrospray method yields quenching rates of ∼10⁵ K/s, while the more common method, dropping a sealed pan of sample into liquid nitrogen, yields only 120 K/s. These hyperquenched samples start to relax, exothermically, far below the glass temperature, at a temperature (0.75T_g) where the thermal energy permits escape from the shallow traps in which the system becomes localized during hyperquenching. This permits estimation of the trap depths, which are then compared with the activation energy estimated from the fictive temperature of the glass and the relaxation time at the fictive temperature. The trap depth in molar energy units is compared with the ‘height of the landscape’ for PG, the quasi-lattice energy of the liquid based on the enthalpy of vaporization, and the single molecule activation energy for diffusion in crystals. The findings are consistent with the mechanism of relaxation invoked in a current model of relaxation in glassforming liquids. In the case of di-n-butyl phthalate we investigate the additional question of sub-T_g annealing effects. We find the ‘shadow’ glass transition, (an annealing prepeak) seen previously only in multicomponent mineral and metallic glasses. The phenomenon is important for understanding microheterogeneities in viscous liquid structures.     

An analysis of the suitability of the Lillie number to characterize the glass transition of real glass-forming substances

The Lillie Number, the negative product of the cooling rate and the temperature dependence of the structural relaxation time, characterizes the glass transition for systems with a single relaxation time. In this paper the utility of the concept is examined in “real” glasses, where a spectrum of relaxation times is necessary. While the principle is still useful, the simplicity and elegance of the approach are diminished for the “real” glass.     

Elastic constant anomaly in Fe80−xMoxB20 metallic glasses

The extensional sound velocities V_E of Fe_80−xMo_xB₂₀(x = 6, 7, 8) metallic glasses have been measured between 100 and 600 K in a saturating magnetic field. Young's modulus (E = _E², = density) shows anomalous temperature dependence at and below the magnetic transition temperature of each glass studied. These anomalies are interpreted as arising from the change of long-range spin coupling energy at the Curie temperature in a molecular field approximation. Comparison is made with similar effects in other crystalline and non-crystalline magnetic materials.     

Characteristic temperatures of enthalpy relaxation in glass

The glass transition temperature, T_g, directly measured by differential scanning calorimetry at 10 K/min is compared with the T_g indirectly determined by fitting viscosity data to a viscosity model for oxide glasses. The results show good match between the two T_g values. A standard, unified approach for measuring T_g is proposed. Characteristic temperatures of enthalpy relaxation in glass are defined, and the relationships between these temperatures are illustrated by performing aging and calorimetric experiments on hyperquenched glasses. The features of the energy release peak, the endothermic pre-peak, and the real glass transition are discussed with respect to their physical origins.     

Surface stress relaxation and resulting residual stress in glass fibers: A new mechanical strengthening mechanism of glasses

Glass surfaces exhibit faster relaxation than the bulk at a constant temperature in the presence of either a liquid water or water vapor atmosphere. Permanent bending of glass fibers at temperatures lower than their glass transition temperatures in an atmosphere containing water vapor or in liquid water was attributed to and analyzed in terms of surface stress relaxation and the resulting surface residual stress. It was found that the fiber bending kinetics are controlled by water diffusion into the glass surface and that glasses with a faster transition crack velocity from region I (linear relation between logarithm of crack velocity and stress intensity factor) to the fatigue limit exhibited a faster rate of surface stress relaxation. It was suggested that this surface stress relaxation and resulting residual stress is the cause of various strengthening phenomena of glasses such as static fatigue limit and coaxing.     

Modulus and internal friction in phosphate-silicate bioactive glass

The real and imaginary parts of the dynamic shear modulus, G′ and G″, respectively, of a “bioactive glass” Na₂O, CaO, SiO₂, P₂O₅ have been measured from 10^?4 Hz to 1 Hz at temperatures from 160 K to 610 K. The mechanical loss tangent of the glass (T_g = 816 K) at 1 Hz shows two relaxation regions: one centred at 312 K and the second at 585 K. The low-temperature peak appears in the same region as the peak attributed to Na ion motion in silicate glasses. The modulus of the glass is 32 GPa at 295 K. The spectrum of the high temperature peak has a broad distribution of relaxation times with a half width of five decades of frequency, and Arrhenius “activation energy” of 164 kJ mol.^?1, and the amplitude of this relaxation decreases on cooling. The similarity of these features with those observed in rigid molecular and other types of glasses suggests that the relaxations observed in the bioglass may be more appropriately considered as an intrinsic property of the non-periodic arrangement of atoms or ions in a solid than as being due to the diffusion of specific types of ions in it. It is pointed out that isothermal and isochronal measurements of internal friction in glasses do not give the same relaxation rate at the same temperature, due mainly to a rapid decrease in the amplitude of relaxation with temperature. The shear, Young's and bulk moduli of the glass are, 31.9, 76.6 and 43.0 GPa, respectively, and the Poisson's ratio is 0.20.A sample of the same bioglass containing 0.05% more water showed a shoulder in its tan φ at ～ 400 K and a peak at ～ 560 K, with little change in its modulus or T_g. Thus the presence of water above a certain amount had less significant effect on the internal friction of the bioactive glass.     

Alloying effect on the viscous flow in metallic glasses

The temperature dependence of viscosities near the glass transition is measured from the rates of thermal transformation for metallic glasses PtNiP, PdNiP, NiPBA1 and (Fe, Co)PBA1. Alloying among metallic elements which lowers the glass transition temperature T_g lowers the ideal glass transition temperature T₀, but raises the residual configurational entropy S_g and the activation energies for “diffusive” rearrangement, $\text{Δμ}{}^1$, of the alloying glasses, while compositional ordering associated with the addition of metalloids raises the T_g and T₀ and lowers the S_g and $\text{Δμ}{}^1$. Results are correlated to the atomic ordering and stability of the glasses. The extracted free volume and the critical diffusive volume are much smaller, by a factor of 4, for metallic glasses than for many other glasses.     

Composition dependence of the optical absorption spectra of cupric ion in sodium borosilicate glass melts

Optical absorption spectra of Cu²⁺ d–d transition peak in sodium borosilicate glasses and their melts were measured from room temperature to 1100 K. In the case of borate glass free from silicon, increase of the temperature above T_g shifts the peak position to the low energy side and decreases the peak height. Peak width is gradually increased with the increase in temperature. On the other hand, in the case of silicate glass free from boron, peak width is decreased with the increase in temperature from room temperature to liquidus temperature. In addition, peak height is slightly decreased with the temperature increase in this temperature range. Further increase of the temperature makes the peak width large. In borosilicate glasses, temperature dependence of the optical absorption spectra is different both from borate and from silicate, and the temperature dependences of the peak position and of the peak height are very small. Temperature dependence of the peak width depends on the boron/silicon ratio.     

DC conductivity in single and mixed alkali vanadophosphate glasses

Three different series of single and mixed alkali vanadium phosphate glasses have been prepared by a melt quench method. DSC studies were carried out on few of these samples and their glass transition temperatures were determined. The glass transition temperatures were found to decrease with alkali content in single alkali systems and increase with second alkali content in mixed alkali systems. The dc electrical conductivity has been measured as a function of temperature. The data has been analyzed in the light of Mott’s small polaron hopping model and activation energies were determined. In one set of single alkali glasses activation energies were found to increase with alkali content and in another set of single alkali systems a transition from predominantly electronic to ionic conduction has been observed above 0.16 mol fraction of alkali content. The mixed alkali glasses have shown higher activation energies and lower conductivities compared to single alkali doped glasses and this has been attributed to a mixed alkali influence on the electrical conduction in these systems.     

Statistical considerations on electronic behavior of the gap states in amorphous semiconductors

The equilibrium distribution functions of the gap states taking into account the effective intrasite electronic correlation energy have been employed to discuss the electronic behaviors of amorphous semiconductors, especially to interpret the temperature dependence of dc and ac conductivity and also the effect of foreign impurity atoms on the conductivity in chalcogenide glasses. The dc conductivity of thermal activation type has been explained without assuming a negligible density of states near the Fermi level, and the gradual decrease in activation energy of conductivity with increasing impurity concentration, even in melt-quenched chalcogenide glasses, has been deduced.     

Thermally modulated differential scanning calorimetry of a glass of composition 45Na2O-40B2O3-10Al2O3-5In2O3

The kinetics of structural relaxation and of glass transition of the 45Na₂O-40B₂O₃-10Al₂O₃-5In₂O₃ glassforming melt is studied by means of standard DSC and of temperature modulated DSC. In this way the dependence of the fictive temperature on cooling rate is determined simultaneously with the determination of the dependence of the dynamic glass transition temperature on modulation frequency. Both sets of data are fitted together in terms of the equation of Ritland-Bartenev. It was found that the activation energy of the structural relaxation exhibits a moderate dependence on temperature with the dimensionless fragility parameter α=3.3 (for strong systems, α is about 1 and increases to about 8 for some very fragile polymeric systems).     

Correlation of ion dynamics and structure in superionic glasses and nanocomposites

Ion dynamics of AgI-doped Ag₂O–TeO₂ glasses and Ag₂S doped glass nanocomposites have been studied using impedance spectroscopy and correlated with their structures investigated using Fourier transform infrared spectroscopy. The composition dependences of the dc conductivity and the activation energy of these glasses and nanocomposites have been compared with those of AgI-doped silver phosphate and borate glasses. We have studied the ion dynamics in the framework of the power-law and the electric modulus formalisms. We have established a correlation between the crossover rate of the mobile silver ions and the rearrangement of the structural units of glassy networks. The scaling of the conductivity spectra has been used to interpret the temperature and composition dependence of the relaxation dynamics. Analysis of the dielectric relaxation in the framework of modulus formalism indicates an increase in ion–ion cooperation in the glass compositions with increasing AgI content.     

Thermal stability and crystallization kinetics of new As–Ge–Se–Sb glasses

Thermal stability and crystallization kinetics of As₁₄Ge₁₄Se_72−xSb_x (where x = 3, 6, 9, 12 and 15 at.%) glasses are studied by the differential scanning calorimetry. The values of the glass transition temperature (T_g) and the peak temperature of crystallization (T_p) are found to be dependent on heating rate and antimony content. From the heating rate dependence of T_g and T_p the values of the activation energy for glass transition (E_t) and the activation energy for crystallization (E_c) are evaluated and their composition dependence discussed. Crystallization studies have been made under non-isothermal conditions with the samples heated at several uniform rates. Using a recent analysis developed for non-isothermal crystallization studies, information on some aspects of the crystallization process has been obtained. The stability calculations emphasized that the thermal stability decreases with increasing the Sb content.     

Thermal expansion of glasses in the As2Se3–AsI3 system

Thermal expansion coefficients (α) of glasses in the As₂Se₃–AsI₃ system are measured in the glass transition region and temperature dependence of the fictive temperature is calculated on the basis of relaxation model. It is found that the increase of AsI₃ content results in: an increase of α, decrease of the glass transition temperature (T_g), increase of the α change at T_g, an effect of quenching rate on α, and also changes in the structural relaxation times spectrum. The data are discussed within the framework of the assumption that the addition of AsI₃ to As₂Se₃ results in: (1) destruction of the As₂Se₃ glass network, (2) structural inhomogeneity of the glasses increase, (3) the temperature dependence of chemical–structural equilibria occurring in the liquid state increases.