https://www.tcd.ie/Physics/people/Graham.Cross/SF%20Poster%202011/Inoue-ActaMater00-Stabilization%20of%20metallic%20supercooled%20liquid%20and%20bulk%20amorphous%20alloys.pdf

Stabilization of metallic supercooled liquid and bulk amorphous alloys

A molecular‐kinetic theory, which explains the temperature dependence of relaxation behavior in glass‐forming liquids in terms of the temperature variation of the size of the cooperatively rearranging region, is presented. The size of this cooperatively rearranging region is shown to be determined by configuration restrictions in these glass‐forming liquids and is expressed in terms of their configurational entropy. The result of the theory is a relation practically coinciding with the empirical WLF equation. Application of the theory to viscosimetric experiments permits evaluation of the ratio of the kinetic glass temperature Tg (derived from usual ``quasistatic'' experiments) to the equilibrium second‐order transition temperature T2 (indicated by either statistical‐mechanical theory or extrapolations of experimental data) as well as the hindrance‐free energy per molecule. These parameters have been evaluated for fifteen substances, the experimental data for which were available. Hindrance‐free energies ...

On the Temperature Dependence of Cooperative Relaxation Properties in Glass‐Forming Liquids

Microstructures and properties of high-entropy alloys

Glasses can be formed by many routes. In some cases, distinct polyamorphic forms are found. The normal mode of glass formation is cooling of a viscous liquid. Liquid behavior during cooling is classified between "strong" and "fragile," and the three canonical characteristics of relaxing liquids are correlated through the fragility. Strong liquids become fragile liquids on compression. In some cases, such conversions occur during cooling by a weak first-order transition. This behavior can be related to the polymorphism in a glass state through a recent simple modification of the van der Waals model for tetrahedrally bonded liquids. The sudden loss of some liquid degrees of freedom through such first-order transitions is suggestive of the polyamorphic transition between native and denatured hydrated proteins, which can be interpreted as single-chain glass-forming polymers plasticized by water and cross-linked by hydrogen bonds. The onset of a sharp change in d dT( is the Debye-Waller factor and T is temperature) in proteins, which is controversially indentified with the glass transition in liquids, is shown to be general for glass formers and observable in computer simulations of strong and fragile ionic liquids, where it proves to be close to the experimental glass transition temperature. The latter may originate in strong anharmonicity in modes ("bosons"), which permits the system to access multiple minima of its configuration space. These modes, the Kauzmann temperature T(K), and the fragility of the liquid, may thus be connected.

https://science.sciencemag.org/content/sci/267/5206/1924.full.pdf

Formation of glasses from liquids and biopolymers.

This review summarizes recent developments in the theory of spin glasses, as well as pertinent experimental data. The most characteristic properties of spin glass systems are described, and related phenomena in other glassy systems (dielectric and orientational glasses) are mentioned. The Edwards-Anderson model of spin glasses and its treatment within the replica method and mean-field theory are outlined, and concepts such as "frustration," "broken replica symmetry," "broken ergodicity," etc., are discussed. The dynamic approach to describing the spin glass transition is emphasized. Monte Carlo simulations of spin glasses and the insight gained by them are described. Other topics discussed include site-disorder models, phenomenological theories for the frozen phase and its excitations, phase diagrams in which spin glass order and ferromagnetism or antiferromagnetism compete, the Ne\'el model of superparamagnetism and related approaches, and possible connections between spin glasses and other topics in the theory of disordered condensed-matter systems.

Spin glasses: Experimental facts, theoretical concepts, and open questions

We have derived, by using simple considerations, a relation between the diffusion constant D in a liquid of hard spheres and the ``free volume'' vf. This derivation is based on the concept that statistical redistribution of the free volume occasionally opens up voids large enough for diffusive displacement. The relation is D=A exp[−γv*/vf], where v* is the minimum required volume of the void and A and γ are constants. This equation is of the same form as Doolittle's [J. Appl. Phys. 22, 1471 (1951)] empirical relation between the fluidity φ of simple hydrocarbons and their free volume. It has been shown [Williams, Landel, and Ferry, J. Am. Chem. Soc. 77, 3701 (1955)] that the Doolittle equation also can be adapted to describe the abrupt decrease in molecular kinetic constants with decreasing temperature that accompanies the glass transition in certain liquids. Our result predicts that even the simplest liquids would go through this glass transition if sufficiently undercooled and crystallization did not oc...

Molecular Transport in Liquids and Glasses

Summary Generally substances are more stable in a crystalline than in a glassy state. Therefore, to form a glass, crystallization must be bypassed. Under certain conditions, the melts of many substances can be cooled to the glass state. Whether or not the melt of a given material forms a glass is determined principally by a set of factors which can be specified to some extent in the laboratory, namely, the cooling rate, - T, the liquid volume, v], and the seed density, ps and upon a set of materials constants: the reduced crystal–liquid interfacial tension, α the fraction, f, of acceptor sites in the crystal surface, and the reduced glass temperature, Trg . The glass-forming tendency will be greater the larger are - T and Trg and the smaller are v]. ps, and f. The number and variety of substances which have been prepared in a glassy or ‘amorphous solid’ form have been greatly increased with techniques in which the material is condensed from solution on to a surface held well below its glass temperature. T...

Under what conditions can a glass be formed

The known facts about nucleation phenomena in liquid metals are interpreted satisfactorily on the basis of the critical size and interfacial energy concepts. In large continuous masses nucleation is almost always catalyzed by extraneous interfaces. However, in very small droplets the probability that a catalytic inclusion is present is so much less that their minimum nucleation frequencies are reproducible and form a consistent set of values.Interfacial energies, σ, between crystal nuclei and the corresponding liquids have been calculated from nucleation frequencies of small droplets on the basis of the theory of homogeneous nucleation. Energies of interfaces, σg, one atom thick and containing N atoms were calculated from the σ's. The ratio of σg to the gram atomic heat of fusion, ΔHf, was approximately 0.45 for most metals but ∼0.32 for H2O, Bi, Sb, and Ge.The effect of relative complexity of crystal structure upon the supercooling behavior of pure metals apparently is a reflection of its effect upon ΔHf.

Formation of Crystal Nuclei in Liquid Metals

Free volume vf is defined as that part of the thermal expansion, or excess volume Δv which can be redistributed without energy change. Assuming a Lennard‐Jones potential function for a molecule within its cage in the condensed phase, it can be shown that at small Δv considerable energy is required to redistribute the excess volume; however, at Δv considerably greater than some value δvg (corresponding to potentials within the linear region), most of the volume added can be redistributed freely. The transition from glass to liquid may be associated with the introduction of appreciable free volume into the system. Free volume will be distributed at random within the amorphous phase and there is a contribution to the entropy from this randomness which is not present in the entropy of the crystalline phase. According to our model all liquids would become glasses at sufficiently low temperature if crystallization did not intervene. Therefore whether or not a glass forms is determined by the crystallization kinetic constants and the cooling rate of the liquid. The experience on the glass formation is consistent with the generalization: at a given level of cohesive energy the glass‐forming tendency of a substance in a particular class is greater the less is the ratio of the energy to the entropy of crystallization.

Free‐Volume Model of the Amorphous Phase: Glass Transition

We have improved the free‐volume model for molecular transport in dense fluids, as developed in earlier papers, by taking account of the variable magnitude of the diffusive displacement. The development is carried through in a way which may display more clearly the relation between the free‐volume model and the Enskog theory. Implicit in the free‐volume development is the association, on the average, of a correlation factor f(a) with each magnitude, a, of the displacement. It is assumed that f(a) is a step function which is zero, because of the predominance of back scattering, for a   a.* This corresponds to dividing the displacements sharply into two categories, one “gaslike” and the other “solidlike.” Molecular dynamics computations have shown that the self‐diffusion coefficient in the hard‐sphere fluid at the highest densities is falling precipitously, with increasing density, away from the Enskog values. It appears that this density trend, which was attributed to back scattering, ...

David Turnbull

Papers

Molecular Transport in Liquids and Glasses

Under what conditions can a glass be formed

Formation of Crystal Nuclei in Liquid Metals

Free‐Volume Model of the Amorphous Phase: Glass Transition

On the free-volume model of the liquid-glass transition.