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.

Although it has long been recognized that dynamics in supercooled liquids might be spatially heterogeneous, only in the past few years has clear evidence emerged to support this view. As a liquid is cooled far below its melting point, dynamics in some regions of the sample can be orders of magnitude faster than dynamics in other regions only a few nanometers away. In this review, the experimental work that characterizes this heterogeneity is described. In particular, the following questions are addressed: How large are the heterogeneities? How long do they last? How much do dynamics vary between the fastest and slowest regions? Why do these heterogeneities arise? The answers to these questions influence practical applications of glass-forming materials, including polymers, metallic glasses, and pharmaceuticals.

Spatially Heterogeneous Dynamics in Supercooled Liquids

The field of viscous liquid and glassy solid dynamics is reviewed by a process of posing the key questions that need to be answered, and then providing the best answers available to the authors and their advisors at this time. The subject is divided into four parts, three of them dealing with behavior in different domains of temperature with respect to the glass transition temperature, Tg , and a fourth dealing with ‘‘short time processes.’’ The first part tackles the high temperature regime T.Tg ,i n which the system is ergodic and the evolution of the viscous liquid toward the condition at Tg is in focus. The second part deals with the regime T;Tg , where the system is nonergodic except for very long annealing times, hence has time-dependent properties ~aging and annealing!. The third part discusses behavior when the system is completely frozen with respect to the primary relaxation process but in which secondary processes, particularly those responsible for ‘‘superionic’’ conductivity, and dopart mobility in amorphous silicon, remain active. In the fourth part we focus on the behavior of the system at the crossover between the low frequency vibrational components of the molecular motion and its high frequency relaxational components, paying particular attention to very recent developments in the short time dielectric response and the high Q mechanical response. © 2000 American Institute of Physics.@S0021-8979~00!02213-1#

https://lib.dr.iastate.edu/cgi/viewcontent.cgi?article=1065&context=mse_pubs

Relaxation in glassforming liquids and amorphous solids

Selected aspects of recent progress in the study of supercooled liquids and glasses are presented in this review. As an introduction for nonspecialists, several basic features of the dynamics and thermodynamics of supercooled liquids and glasses are described. Among these are nonexponential relaxation functions, non-Arrhenius temperature dependences, and the Kauzmann temperature. Various theoretical models which attempt to explain these basic features are presented next. These models are conveniently categorized according to the temperature regimes deemed important by their authors. The major portion of this review is given to a summary of current experimental and computational research. The utility of mode coupling theory is addressed. Evidence is discussed for new relaxation mechanisms and new time and length scales in supercooled liquids. Relaxations in the glassy state and significance of the “boson peak” are also addressed.

Supercooled Liquids and Glasses

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

Colloquium : The glass transition and elastic models of glass-forming liquids

We have measured the dielectric relaxation times of the α process of phenyl salicylate (salol) covering 11 decades in frequency. Being representative for the class of low molecular weight organic glass forming materials, the highly resolved temperature dependence of the dynamics in salol does not follow a particular function like the Vogel–Fulcher–Tammann (VFT) law over the entire accessible range of temperatures. In order to conduct a detailed and unambiguous analysis of the temperature dependence, we take advantage of the derivatives of the experimental log(fmax) values with respect to temperature, which allow us to either linearize the frequently used temperature laws or to resolve subtle changes in fmax(T) by decreasing the number of free parameters. In this manner we observe that none of the common routes for rationalizing the dynamics like Arrhenius, VFT, Souletie scaling, and idealized mode‐coupling theory account for the experimental findings properly. However, we do observe a VFT behavior within the limits 265 K≤T≤320 K, i.e., for temperatures ranging from significantly above the glass transition at Tg=220 K to far above the melting point.

Dynamics of glass-forming liquids. i: temperature-derivative analysis of dielectric relaxation data

We have studied the temperature dependence of dielectric relaxation times in terms of the peak frequency fmax(T) of dielectric loss e″(ω) and the dc‐conductivity σdc(T) of several glass‐forming liquids, covering 12 decades in the peak frequency fmax and 9 decades in σdc. Although dc‐conductivity samples the mobility of ionic tracers, its variation with temperature is similar to that of fmax(T). The fmax(T) and σdc(T) are analyzed using the temperature‐derivative method and compared to the viscosity data η−1(T). While most liquids reveal a common Vogel–Fulcher–Tammann (VFT) behavior for fmax, σdc and η−1 in an extended temperature range T≥Tm, some liquids deviate from this behavior by displaying a crossover at T=TA to an Arrhenius regime. In these cases the quantity fmax(T) decouples from the common curves for σdc(T) and η−1(T) and attains activation energies in excess (∼40% for alcohols) of those related to translational processes. For many samples a departure from the VFT behavior occurs at lower tempera...

Dynamics of glass-forming liquids. II. Detailed comparison of dielectric relaxation, dc-conductivity, and viscosity data

We have measured the dielectric relaxation of the glass-former 1-propanol for temperatures between 65 and 350 K in the frequency range 10−2 to 2⋅1010 Hz and the photon correlation spectro-scopy decays near Tg. Attributing the strong Debye-type process of 1-propanol to distinct -OH group effects leaves two faster processes related to the structural relaxation which can be identified as α-relaxation and Johari–Goldstein type β-relaxation characteristic of nonhydrogen-bonding supercooled liquids. From the temperature dependent relaxation times τ(T) regarding the three distinct loss peaks, we can specify an α-β-bifurcation temperature Tβ, which coincides with characteristic qualitative changes in the τ(T) behavior, as also observed for ortho-terphenyl and other glass-forming liquids. This assignment is confirmed by the correla-tion times derived from incoherent quasielastic light-scattering data obtained from the simultaneously measured photon-correlation spectroscopy.

Dynamics of glass-forming liquids. III. Comparing the dielectric α- and β-relaxation of 1-propanol and o-terphenyl

We have measured the dielectric relaxation of butylbenzene and of the glass-former propylbenzene in the frequency range 10−2 Hz to 2×1010 Hz in order to characterize the variation of relaxation times with temperature for these low loss liquids. Additionally, salol has been remeasured above 1 GHz with improved resolution. Using the sensitive data representation [−dlog10(fmaxHz)/d(1/T)]−1/2 vs 1/T we find demarcation temperatures TA, at which the temperature dependence changes from a Vogel–Fulcher type law within the limits TB⩽T⩽TA to Arrhenius behavior for T>TA, corresponding to a position of the loss peak fmax>2 GHz. The activation energies derived from dielectric relaxation data for T>TA are associated with the energy of vaporization, Eη∝ΔEvap. A comparison of dielectric relaxation times τD to viscosity data in this wide range of temperatures suggests the relation τD∝η/T rather than τD∝η.

F. Stickel

Papers

Dynamics of glass-forming liquids. i: temperature-derivative analysis of dielectric relaxation data

Dynamics of glass-forming liquids. II. Detailed comparison of dielectric relaxation, dc-conductivity, and viscosity data

Dynamics of glass-forming liquids. III. Comparing the dielectric α- and β-relaxation of 1-propanol and o-terphenyl

Dynamics of glass-forming liquids. IV. True activated behavior above 2 GHz in the dielectric α-relaxation of organic liquids

Solvation dynamics and the dielectric response in a glass-forming solvent: from picoseconds to seconds