The dynamics of glass is of importance in materials science but its nature has not yet been fully understood. Here we report that a verification of the temperature dependencies of the primary relaxation time or viscosity in the ultraslowing/ultraviscous domain of glass-forming systems can be carried out via the analysis of the inverse of the Dyre-Olsen temperature index. The subsequent analysis of experimental data indicates the possibility of the self-consistent description of glass-forming low-molecular-weight liquids, polymers, liquid crystals, orientationally disordered crystals and Ising spin-glass-like systems, as well as the prevalence of equations associated with the 'finite temperature divergence'. All these lead to a new formula for the configurational entropy in glass-forming systems. Furthermore, a link to the dominated local symmetry for a given glass former is identified here. Results obtained show a new relationship between the glass transition and critical phenomena.

Glass transition constitutes one of main problems of condensed matter physics and material engineering that remains unsolved. The common acceptance of the Vogel-Fulcher-Tammann (VFT) equation for portraying the primary relaxation time or shear viscosity indicated a possible phase transition, hidden below the glass transition temperature (Tg). Recently Hecksher et al. [Nat. Phys. 4, 737 (2008)] delivered strong empirical arguments that VFT description lacks a direct experimental basis and thus theories not predicting a dynamic divergence should be focused on. We present clear evidence for a superiority of critical-like divergent equation $\tau${}(T)=$\tau${}0(T$-${}TC)$-${}$\phi${} and TC<Tg for liquid crystalline (LC) glass formers and orientationally disordered crystals (ODIC). Such dependence was already known for spin-glasslike systems and the dynamical scaling model, although the latter was hardly explored so far. The pressure-related behavior is also discussed. Results obtained support arguments for the suggested direct link between critical phenomena and vitrification [Tanaka et al., Nat. Mater. 9, 324 (2010)]. LCs and ODICs may be considered as simple experimental model systems for the structural glass formers group.

Results of studies of the static and dynamic dielectric properties in rod-like 4-n-octyloxy-4'-cyanobiphenyl (8OCB) with isotropic (I)-nematic (N)-smectic A (SmA)-crystal (Cr) mesomorphism, combined with measurements of the low-frequency nonlinear dielectric effect and heat capacity are presented. The analysis is supported by the derivative-based and distortion-sensitive transformation of experimental data. Evidence for the I-N and N-SmA pretransitional anomalies, indicating the influence of tricritical behavior, is shown. It has also been found that neither the N phase nor the SmA phase are uniform and hallmarks of fluid-fluid crossovers can be detected. The dynamics, tested via the evolution of the primary relaxation time, is clearly non-Arrhenius and described via τ(T) = τ(c)(T-T(C))(-φ). In the immediate vicinity of the I-N transition a novel anomaly has been found: Δτ is proportional to 1/(T - T*), where T* is the temperature of the virtual continuous transition and Δτ is the excess over the 'background behavior'. Experimental results are confronted with the comprehensive Landau-de Gennes theory based modeling.

In the last decade the challenging analysis of previtreous behavior of relaxation time (τ(T)) in ultraviscous low molecular weight liquids led to the conceptual shift of the glass transition physics toward theories not predicting a “finite-temperature” divergence. This “breakthrough” experimental finding was strengthened by the discovery that “dynamic” (i.e. from τ(T) fitting) and “thermodynamic” estimations of the “ideal glass” (Kauzmann) temperature do not match, what in fact questioned its existence. In this report, due to the novel way of analysis based on the transformation of τ(T) experimental data to the activation energy temperature index form, the clear prevalence of the “finite-temperature” divergence is proved. The obtained “dynamic” singular temperatures clearly coincide with “thermodynamic” estimations of the Kauzmann temperature, thus solving also the second mystery. The comprehensive picture was obtained due to the analysis of 55 experimental data-sets, ranging from low molecular weight liquids and polymers to liquid crystal and plastic crystals.

One of the most intriguing phenomena in glass forming systems is the dynamic crossover (TB), occurring well above the glass temperature (Tg). So far, it was estimated mainly from the linearized derivative analysis of the primary relaxation time τ(T) or viscosity η(T) experimental data, originally proposed by Stickel et al. [J. Chem. Phys. 104, 2043 (1996)10.1063/1.470961; Stickel et al. J. Chem. Phys. 107, 1086 (1997)]10.1063/1.474456. However, this formal procedure is based on the general validity of the Vogel-Fulcher-Tammann equation, which has been strongly questioned recently [T. Hecksher et al. Nature Phys. 4, 737 (2008)10.1038/nphys1033; P. Lunkenheimer et al. Phys. Rev. E 81, 051504 (2010)10.1103/PhysRevE.81.051504; J. C. Martinez-Garcia et al. J. Chem. Phys. 134, 024512 (2011)]10.1063/1.3514589. We present a qualitatively new way to identify the dynamic crossover based on the apparent enthalpy space ($H_a^\prime = {{d\ln \tau }/{d({1/T})}}$Ha′=dlnτ/d(1/T)) analysis via a new plot $\ln H_a^\prime $lnHa′ vs. 1/T supported by the Savitzky-Golay filtering procedure for getting an insight into the noise-distorted high order derivatives. It is shown that depending on the ratio between the “virtual” fragility in the high temperature dynamic domain (mhigh) and the “real” fragility at Tg (the low temperature dynamic domain, m = mlow) glass formers can be splitted into two groups related to f < 1 and f > 1, (f = mhigh/mlow). The link of this phenomenon to the ratio between the apparent enthalpy and activation energy as well as the behavior of the configurational entropy is indicated.