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

Glasses are disordered materials that lack the periodicity of crystals but behave mechanically like solids. The most common way of making a glass is by cooling a viscous liquid fast enough to avoid crystallization. Although this route to the vitreous state-supercooling-has been known for millennia, the molecular processes by which liquids acquire amorphous rigidity upon cooling are not fully understood. Here we discuss current theoretical knowledge of the manner in which intermolecular forces give rise to complex behaviour in supercooled liquids and glasses. An intriguing aspect of this behaviour is the apparent connection between dynamics and thermodynamics. The multidimensional potential energy surface as a function of particle coordinates (the energy landscape) offers a convenient viewpoint for the analysis and interpretation of supercooling and glass-formation phenomena. That much of this analysis is at present largely qualitative reflects the fact that precise computations of how viscous liquids sample their landscape have become possible only recently.

Supercooled liquids and the glass transition

Ionic liquids as electrolytes

Deviations from thermally activated and from exponential response are typical features of the vitrification phenomenon and previously have been studied using viscoelastic, dielectric, calorimetric, optical, and other techniques. Linear response data from literature on about 70 covalent glass formers, ionic melts, supercooled liquids, amorphous polymers, and glassy crystals are surveyed. Except for orientational glasses and monohydric aliphatic alcohols a distinct but broad correlation of non‐Debye behavior with non‐Arrhenius relaxations is found. Within the broad trend several groups of materials, distinguished by their respective molecular complexity, can be identified and are shown to exhibit narrow correlations. At a given degree of deviation from Arrhenius behavior externally imposed stresses are relaxed with a departure from exponential behavior which is stronger the more the molecular or atomic subunits of the glassforming material are interconnected with each other.

Nonexponential relaxations in strong and fragile glass formers

Viscosity of Simple Soda-Silicate Glasses, 500° to 1400°C
Comparison of the results given by English with those of Washburn, Shelton and Libman, indicates a discrepancy in the absolute values of log10 viscosity amounting to 0.6, those of Washburn et al., being relatively too high. If correction for this is made, the isothermal curves of log10 viscosity as a function of soda content are smooth up to 50% Na2O, showing no inflection. The observations as a function of temperature T are all represented within accidental error by an equation of the type log10η=−A+B× 103/ (T−T0) where all three constants vary regularly with the composition.

Change of Viscosity of Glass (6SiO2, 2Na2O) due to Molecular Substitution of CaO, MgO and Al2O3 for Na2O
The effect is clearly brought out by plotting (from the results of English) the change of log10n due to the substitution as a function of temperature. The curves each show a sharp bend at a temperature between 840° and 1050°C, which is designated the aggregation temperature Ta. If we divide these curves by the corresponding percentage substituted, we get curves for each oxide which are straight and parallel below the aggregation temperatures, the slopes (increase of change of log10n per 100°C) being −0.056 (CaO), −0.055 (MgO), −0.018 (Al2O3) per per cent oxide substituted. For substitution of 1/2 molecule the slopes are −0.325 (CaO), −0.23 (MgO) and −0.18 (Al2O3) per 100°. At the aggregation temperature the change of log10n per per cent is a minimum, 0.03 to 0.06 for CaO, 0.12 for MgO, 0.07 for Al2O3.

Evidence of Aggregation in Glasses, from Viscosity Measurements
. The sharp bends in the plots of change of log10n due to substitution of an oxide for Na2O, suggest the beginning of molecular aggregation at these temperatures. These aggregation temperatures are close to the devitrification temperatures, but the effect on the viscosity curves cannot be due to actual devitrification since it does not change with time. Taking the aggregation temperatures as equal to devitrification temperatures, additional isotherms are roughly sketched into the equilibrium triangle of the system Na2O─CaO─SiO2.

Change of Viscosity of Glass (4SiO2, 2Na2O) due to Substitution of B2O3 for SiO2
The change of log10n (from the results of English) is plotted as a function of temperature, and also the change of log10n per per cent B2O3. The curves are more complex than for the substitution for Na2O.

Gordon S. Fulcher

Papers

Analysis of recent measurements of the viscosity of glasses

Cast refractory article and method of making the same

Cast refractory product

Method of making solid cast refractory articles

Method of making composite refractory articles