Theory of fluidity of liquids, glass transition, and melting

This is a presentation of a rigorous theory of fluidity of liquids, glass transition and melting of solids in the frame of an asymmetric double well potential model. Potential wells are doubled time to time by the local density fluctuations caused by the thermal longitudinal waves. The average frequency of doubling of potential wells is equal to the frequency of the most energetic waves which obey a law similar to Wein’s displacement law in black body radiation. Based on the equilibrium thermodynamic theory of fluctuations and the displacement law, a law of linear pre-diffusion mean-square displacement of particles in a solid is derived: the mean-square displacement of molecules within their potential wells increases linearly with temperature. It is shown that when this is broken-down (where the mean-square displacement at a certain temperature rapidly changes its slope as a function of temperature) glass devitrifies and crystal melts, and all possible solid-liquid transitions of a substance occur at the same critical mean-square displacement: any solid (not only crystals) transforms into liquid when the mean-square displacement, as a fraction of the average intermolecular distance, acquires a certain universal critical value - the same for different substances. It is proved that molecules in a liquid perform specific Brownian motion. The average jump distance is a function of temperature and it is much smaller than the nearest intermolecular distances. At a certain temperature, shown to be the Kauzmann temperature, the average jump distance of Brownian motion becomes equal to zero: the super-cooled liquid undergoes glass transition. The transition was proven to be a phase transition of the fourth order: the free energy of the system and its first, second and third derivatives are all continuous functions, but its fourth derivative with respect to temperature is discontinuous. Molecular mobility, diffusion and viscosity are obtained as functions of temperature.     

The dynamic crossover temperature and the characteristic length of glass transition in accordance with the extended Adam–Gibbs theory

Adam–Gibbs factor at the dynamic phase transition temperature is found out to be ‘universal,’ as it is at the glass transition temperature. A new scaling has been suggested collecting known ‘universalities’ related with the relaxation time. The fragility has been discussed in terms of the characteristic length at the glass-transition temperature. The transformation of the activation hopping into free diffusion dynamics in polymers is investigated.     

Volume and viscosity of Zr–Cu–Al glass-forming liquid alloys

We examined the volume and viscosity of Zr–Cu–Al glass-forming liquid alloys to clarify the origin of a frozen free volume in glassy alloys. Since an excess free volume imparts toughness and ductility to glassy alloys, we attempted to increase this volume in glass structures so that they could be used as engineering materials. The maximum frozen excess free volume was observed in the ternary eutectic composition of the Zr–Cu–Al alloy system; however, its origin remains unclear. We attempted to reveal the mechanism of the formation of the frozen excess free volume in Zr–Cu–Al glassy alloys.     

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.     

Principles of electrical behavior of amorphous semiconductor alloys

A new approach to understanding amorphous semiconductors is provided by a model whose novel concepts are necessary consequences of transport and recombination fundamentals. The amorphous semiconductors are examples of the ‘relaxation semiconductor’: When dielectric relaxation is slow compared with recombination, familiar transport behavior is drastically altered and the recombination characterized by cross sections for carrier capture which are extremely large. At thermal equilibrium, ‘equality recombination’ obtains, with which local space-charge neutrality is maintained through equal total capture rates of electrons and holes per unit volume. In the alloys, such recombination after single free paths gives equal electron and hole conductivities, and thus pins the Fermi level at the position of minimum conductivity for a given band gap. Both mean free paths are equal and of the order of the electron wavelength. They determine the concentrations of centers positively and negatively ionized, which are equal and large compared with mobile carrier concentrations. Nearly all the centers are neutral, are donors near the valence band and acceptors near the conduction band, and may be in fairly short band tails. The recombination is mainly at the deeper levels of the acceptor centers, which act also as shallow electron traps. On a simple and unified electronic basis, this model accounts in detail for the various aspects of observed behavior. The threshold switching is due to characteristics ‘recombinative injection’ of minority electrons. This produces a region of injected space charge in which the net recombination rate is zero, and puts at the anode an adjoining ‘recombination front’ of a type in which carriers are activated by field equal to the threshold field. Other aspects treated include, for example: the small negative Hall coefficient; the positive thermoelectric power; preswitching; delay time; integrated current or total charge during preswitching in its quantitative dependence on delay time; the ‘blocked ON state’; and the field effect, analysis of which gives the ionized concentration. The model has further implications for theory of the band structure.     

Rheological and thermodynamic behaviors of different calcium aluminosilicate melts with the same non-bridging oxygen content

The relationships between the chemical composition and the derivative rheological and thermodynamic values have been determined for two melt series in the anorthite-wollastonite-gehlenite (An-Wo-Geh) compatibility triangle. The melt series have 0.5 and 1 non-bridging oxygens per tetrahedrally coordinated cation (NBO/T), respectively. The influences of the ratio Si/(Si + AlCa_1/2) and NBO/T on the fragility and the configurational entropy at T_g are evaluated. Linear dependencies of the viscosity, the glass transition temperature and the fragility on the ratio Si/(Si + AlCa_1/2) are found for the two melt series. A crossover in the viscosity-temperature relationship is observed for both series, i.e. an inverse compositional dependence of viscosity in the high and low viscous range. The crossover presumably reflects different responses of the adjustment of melt structure to the substitution of Al³⁺ + 1/2Ca²⁺ for Si⁴⁺ in the low versus the high viscous ranges. The crossover shifts to higher temperature with increasing NBO/T.     

Glass formation and glass transition in supercooled liquids,with insights from study of related phenomena in crystals

We divide glass and viscous liquid sciences into two major research areas, the first dealing with how to avoid crystals and so access the viscous liquid state, and the second dealing with how liquids behave when no crystals form. We review some current efforts to elucidate each area, looking at strategies for vitrification of monatomic metals in the first, and the origin of the property ‘fragility’ in the second. Essential in the first is the ‘ideal glassformer’ concept. Essential in the second is the non-trivial behavior of the glassformer thermodynamics. We explore the findings on non-exponential relaxation and dynamic heterogeneities in viscous liquids, emphasizing the way in which direct excitation of the configurational modes has helped differentiate configurational from non-configurational contributions to the excess heat capacity. We then propose a scheme for understanding the relation between inorganic network and non-network glassformers which includes the anomalous case of water as an intermediate. In a final section we examine the additional insights to be gained by study of the glass-like, ergodicity-breaking transitions that occur in disordering crystals. Here we highlight systems in which the background thermodynamics is understood because the ergodic behavior is a lambda transition. Water, and the classical network glassformers, appear to be attenuated versions of the latter type of cooperative transition.     

The effect of solids and phase compositions on viscosity behaviour and TCV of slags from Australian bituminous coals

The flow behaviour of coal mineral matter at high temperatures is an important parameter for coal use in entrained flow gasification technologies. Slag flow behaviour is characterised by the temperature dependence of slag viscosity, including the temperature of critical viscosity (T_CV), which is strongly dependent on slag composition. Moreover, at temperatures below the liquidus temperature this compositional dependence is complicated by the precipitation of solids, and the resultant change in chemical composition of the liquid phase. In the present study, the viscosity behaviour of selected slag compositions is investigated in terms of the dynamics of solid precipitation, compositional changes, and the morphology of crystallised solids. Relationships between slag microstructure, phase composition and viscosity behaviour are described on the basis of viscosity measurements, thermodynamic calculations, and slag quenching experiments. It is shown that the viscosity-temperature behaviour of specific slag compositions was dependent on the amount and size of the solids in the slag, silica/alumina ratio (S/A) and compositional changes of the liquid phase due to solid phase precipitation.     

The defect diffusion model and the properties of glasses and liquids

Several previously unexplained relaxation phenomena are interpreted quantitatively in terms of the defect diffusion model (DDM). These include widely different pre-exponentials, exponents and consequently fragility. In addition, the DDM is used to give a qualitative explanation of many properties that glasses and liquids exhibit. This includes interpretations of the glass transition (T_g), the liquid–liquid transition (T_B), the crystalline melting temperature (T_m), and the different values of the characteristic temperature, T_C, that some materials exhibit for different types of physical measurements. Next, qualitative explanations of the origin of secondary relaxations such as the excess wing and the β relaxation are given. In addition, the boson peak is discussed in terms of the DDM. Finally, it is pointed out that in the DDM, universality is embodied in the defects i.e. free volume.     

Dielectric investigation of organic-inorganic hybrid based on titanium oxocluster-crosslinked elastomer

In this paper, we have prepared new type of organic-inorganic hybrid materials based on covalent bond between the two constituents: elastomer and titanium oxocluster. Commercial hydrogenated acrylonitrile-butadiene rubber (HNBR)-Therban^® 3407 was selected as the matrix for mixing the titanium oxocluster. Three different samples containing the elastomer and peroxide, elastomer, peroxide and titanate, and elastomer and titanate, respectively were prepared. The dielectric permittivity have been scanned over a wide range of frequencies and temperatures in order to determine the how the titanate and the peroxide influences the molecular mobility. Complementary DSC and mechanical analysis were performed. We found that the presence of titanates-compounds strongly influences the mobility of the ions and it’s reflected in the low activation energy for the ionic conductivity. In spite that the glass transition temperature is held constant, the temperature dependence of the α process, as well as the free volume at the glass transition, the fragility parameter and the ΔCp during the glass transition are strongly influenced by the composition.     

Fragility measures and mode-coupling theory

The pressure-dependence of the elastic moduli of a Lennard-Jones (LJ) system is studied within mode-coupling theory (MCT). Assuming a recently proposed link between these quantities and Angell’s fragility to hold, this implies that the fragility of the LJ system increases with pressure, and that this increase is mainly connected to a change in the equation of state of the liquid, and not glassy dynamics as such.     

Short-range order and dynamic viscosity of liquid Cu–Ge alloys

We report an investigation of the dynamic viscosity and the atomic structure of liquid Cu–Ge alloys. The concentration as well as the temperature dependence of the viscosity obtained experimentally has been modelled by use of a thermodynamic approach. An excess viscosity above mixing rules has been observed for Cu-rich alloys which – in relation with the diffraction experiments – can be explained in terms of a micro-heterogeneous structure.     

Study of the microdynamics of liquid lithium and lithium-hydrogen melt by inelastic neutron scattering

The frequency spectra of vibrations of Li atoms at temperatures of 22, 227, 397, and 557°C and the lithium-hydrogen melt (98 at % ⁷Li, 2 at % H) at 557°C have been obtained from the experimental neutron inelastic scattering data. On the basis of the frequency spectra, the temperature dependences of the mean-square displacement of Li atoms, the mean-square amplitudes of atomic vibrations, and the velocity autocorrelation function of atoms have been calculated. The speed of sound in liquid lithium has been estimated within the Debye model. The frequency spectra of lithium-hydrogen melt and solid lithium hydride are compared. A generalized frequency spectrum of vibrations of hydrogen atoms in lithium-hydrogen melt is obtained.     

Investigations on glass-to-mold sticking in the hot forming process

The sticking behavior of various mold materials and coatings for hot glass melt forming processes, like, e.g. glass container manufacturing, was investigated using a new testing procedure. The mold material specimens under test were subjected to frequent contact with hot viscous glass gobs in a pressing process with presetting well defined non-isothermal pressing parameters to simulate industrial working conditions. Three different glass compositions were used in this investigation, soda-lime silicate glass, lead crystal glass, and borosilicate glass. The sticking characteristics of the tested mold materials and coatings were described by two quantities, a ‘lower’ and an ‘upper’ sticking temperature, which are specific for each mold material and type of glass in the non-isothermal pressing process. The ‘lower’ sticking temperatures of uncoated mold materials were found to depend monotonically on the thermal effusivity (heat penetration coefficient) of the bulk mold materials. All of the coating materials applied to various substrate mold materials were found to reduce the ‘lower’ sticking temperature as compared to the uncoated materials. Most of the coating materials were found to reduce also the ‘upper’ sticking temperature.     

‘Star‐like’ defects in Cd‐annealed CdZnTe crystals—an experimental study of their origin and formation mechanism

We conducted low‐temperature annealing experiments at temperatures slightly above and below the melting point of Te to clarify the effects of the state of Te inclusions (solid or liquid) upon the formation of ‘star‐like’ defects in Cd‐annealed CdZnTe (CZT). We also carried out post‐growth annealing experiments with and without using Cd vapor to clarify the mechanism of formation of such defects. We demonstrated that these ‘star‐like’ defects are due to the reaction between in‐diffused Cd atoms and the molten Te inclusions, but we found no observable ‘one‐to‐one’ correlation between ‘star‐like’ defects and Te inclusions. The non‐uniform distribution of Te inclusions in the CZT matrix could account for this phenomenon since the punching distance of the dislocations depends on the volume fraction of inclusions within the matrix.     

Molecular dynamics simulation of viscosity in supercooled liquid and glassy AgCu alloy

The viscosity of the model AgCu alloy is simulated by several methods using (i) correlation functions through the Green–Kubo formalism, (ii) a non-equilibrium molecular dynamics approach and (iii) creep tests under constant stress. Temperature dependences of the shear viscosity and the diffusion coefficient show the breakdown of the Stokes–Einstein relation well above the glass-transition temperature T_g. This observation is interpreted as a manifestation of the development of heterogeneities in the supercooled liquid approaching T_g. Based on a generalized Einstein formula for the viscosity of liquid, a temperature dependence of heterogeneity degree of supercooled liquid is estimated. Using the dependence of the deformation rate on external stress, the activation volume is evaluated to be four atomic volumes in liquid state. However, below the mode-coupling temperature T_c the activation volume increases by several times.     

High pressure effects on liquid viscosity and glass transition behaviour,polyamorphic phase transitions and structural properties of glasses and liquids

Since the pioneering work of Bridgman it has been known that pressure affects the glass transition of polymers and liquid state viscosities. Usually the T_g and viscosity both increase as a function of pressure as expected from ‘free volume’ theories. However, H₂O provided a notable exception in that the viscosity passes through a minimum at low temperature. It was thought that this might be linked to the anomalous thermal expansion behavior. However further research on geologically important aluminosilicate liquids revealed that they could show anomalous viscosity decreases with increasing pressure and this behavior is given a structural interpretation as five-fold coordinated Si⁴⁺ and Al³⁺ species are formed. Also the existence of polyamorphism or density-driven liquid–liquid phase transitions in certain systems can lead to anomalies in the T_g or η vs. P relations. This may be the case for H₂O, for example. Current research is focusing on investigating structural changes in liquids and glasses at high pressure as the rich variety of behavior is becoming recognized. Both experimental studies and computer simulations are important as the underlying phenomonology is linked to changes in the glass or liquid structure as a function of densification.     

Transport property measurements in tungsten sulphoselenide single crystals grown by a CVT technique

The transport properties of ternary mixed WS_xSe_2‐x single crystals have been studied by measuring the thermo power, electrical conductivities and Hall parameters in a small temperature range 303‐423 K. The electrical conductivity was highest for selenium rich WSe₂ and lowest for sulphur rich WS₂ crystals. All the crystals showed semiconducting behaviour from the temperature dependence of ‘ρ’, ‘R_H’ and ‘S’. The Hall coefficients showed that the samples are p‐type conducting. The temperature dependence of resistivity, Hall coefficients, carrier concentration showed that all of them are thermally activated. The values of activation energies, pre‐exponential factors and the scattering parameters have been determined. The dominant scattering mechanism for the charge carriers has been explained. The relation between the TEP and the concentration of charge carriers and electrical conductivity was studied. The effective masses of holes and the effective density of states have been determined. These parameters show an increase with increase in sulphur content. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Viscosity of (GeS2)x(Sb2S3)1−x supercooled melts

Viscosity of (GeS₂)_x(Sb₂S₃)_1−x melts (x = 0.1–0.9) has been measured by penetration method and parallel-plate method as a function of temperature. The temperature dependence of viscosity can be expressed by a simple equation of Arrhenius type. The kinetic fragility obtained from these plots varies linearly with composition. The Sb₂S₃ component probably affects the network structure and, consequently, the kinetic fragility of a supercooled melt increases. As expected, the heat capacity change at the glass transition, ΔC_p, exhibits similar (though non-linear) compositional dependence.