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.

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

Complex dielectric constants have been measured at frequencies from below 20 c/s to 5 mc/s over the temperature range −40° to −75°C in glycerol, −45° to −90° in propylene glycol, and −80° to −140° in n‐propanol. The results for n‐propanol are described by the Debye equation, but the values for the other two require a modified equation corresponding to a broader range of dispersion at higher frequencies. In all three liquids, evidence is found for a second dispersion region at still higher frequencies, which accounts for much of the difference between the radio frequency and optical dielectric constant. The relaxation times are quantitatively described over wide ranges by an empirical rate equation of a form which also fits viscosity data. The significance of the various results is discussed.

Dielectric Relaxation in Glycerol, Propylene Glycol, and n-Propanol

Recent attempts have been made to assess the relative merits of the free volume and entropy theories of viscous flow in glass‐forming liquids by accurate measurement of viscosity over wide temperature ranges, and subsequent comparison with the equations derived from these theories. In the author's view, this effort is misguided. The theories are crude and qualitative, and such tests are too stringent. It is better to make qualitative or semiquantitative comparison of a wide variety of physical phenomena; judged by this criterion, the entropy theory appears more successful. It is conjectured that further progress can be made by accepting the crude, naive character of any model we are likely to find tractable for the foreseeable future, and recognizing both the values and limitations of such models. A picture of the flow process in viscous liquids is proposed, in an attempt to answer certain questions about the molecular steps in flow either answered unsuccessfully or ignored by present theories, in the hop...

/pdf/viscous-liquids-and-the-glass-transition-a-potential-energy-47wz1nu6jb.pdf

Viscous Liquids and the Glass Transition: A Potential Energy Barrier Picture

Basic characteristics of the liquid-glass transition are reviewed, emphasizing its universality and briefly summarizing the most popular phenomenological models. Discussion is focused on a number of alternative models which one way or the other connect the fast and slow degrees of freedom of viscous liquids. It is shown that all these ``elastic'' models are equivalent in the simplest approximation.

/pdf/colloquium-the-glass-transition-and-elastic-models-of-glass-zkla9ibwsp.pdf

G. Tammann

Papers

Die Abhängigkeit der Viscosität von der Temperatur bie unterkühlten Flüssigkeiten