Thermodynamic−Kinetic Correlations in Supercooled Liquids:  A Critical Survey of Experimental Data and Predictions of the Random First-Order Transition Theory of Glasses

Abstract

Thermodynamics and kinetics are thought to be linked in glass transitions. The quantitative predictions of alpha-relaxation activation barriers provided by the theory of glasses based on random first-order transitions are compared with the experimental results for 44 substances. The agreement found between the predicted activation energies near T(g) and experiment is excellent. These predictions depend on the configurational heat capacity change on vitrification and the entropy of melting the crystal which are experimental inputs.

On the strength of glasses

“…These regions become more fractal, resembling strings or percolation clusters (20) at higher temperatures where flow is no longer thermally activated (21) but rather dominantly collisional. The quantitative predictions of RFOT theory concerning the well-established thermodynamic/kinetic correlations in the viscous liquid state, dynamical heterogeneity in supercooled liquids (18), and the aging (22) and rejuvenating (19) properties of the glassy state proper agree quite well with observations (23). It is thus natural to enquire as to what the theory predicts for the material strength of glasses.…”

Comprehensive studies on physical and chemical stability in liquid and glassy states of telmisartan (TEL): solubility advantages given by cryomilled and quenched material

“…Here, it should be also pointed out that significant limitation of modified Adam-Gibbs method is that it predicts same molecular mobility for glasses prepared using various methods and having different thermal histories. However, as shown in the literature, the time scales of molecular motion below T g might strongly depend on the experimental conditions [ 53 ].…”

Electronic structure and the glass transition in pnictide and chalcogenide semiconductor alloys. II. The intrinsic electronic midgap states

“…13,38 The RFOT theory predicts that this coefficient should be equal to what one may call a "thermodynamically" determined fragility m thermo = 34.7 × ∆c p (T g ) where ∆c p (T g ) is the heat capacity jump at the glass transition per bead. 13,38 Using the measured ∆c p (T g ) per mole, and the bead size determination from the fusion enthalpy produces excellent agreement for dozens of substances, 38 however among the outliers are the chalcogenides. For instance, for As 2 Se 3 , the measured m ≃ 40, while the theoretically computed m thermo ≃ 7.5.…”