Universal critical-like scaling of dynamics in plastic crystals

Many theoretical models for the glassy dynamics have been proposed so far describing the changes in molecular dynamics along the extraordinary slowing down in the vitrification process of a disordered phase on cooling. Many of these theories share the concept of cooperative rearranging regions firstly proposed by Adam and Gibbs. Among them, the dynamical scaling model (DSM) is based on the random diffusion of free volume which creates random walking clusters formed by cooperatively rearranging entities.Within this framework a critical phenomenon relating a hidden phase transition at T_C (below T_g) implies the divergence of the relaxation time (τ) or viscosity (η) τ, η ∝ (T − T_C) ^− ? with a universal scaling exponent φ → 9. In this work we apply the DSM model to orientational glasses, obtained from the quenching of orientationally disordered phases (plastic crystals) via the application of the linearized derivative-based transformation of dielectric spectroscopy τ(T) data.     

The new insight into dynamic crossover in glass forming liquids from the apparent enthalpy analysis

One of the most intriguing phenomena in glass forming systems is the dynamic crossover (T(B)), occurring well above the glass temperature (T(g)). 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); J. Chem. Phys. 107, 1086 (1997)]. 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); P. Lunkenheimer et al. Phys. Rev. E 81, 051504 (2010); J. C. Martinez-Garcia et al. J. Chem. Phys. 134, 024512 (2011)]. We present a qualitatively new way to identify the dynamic crossover based on the apparent enthalpy space (H(a) (')=dlnτ/d(1/T)) analysis via a new plot lnH(a) (') 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 (m(high)) and the "real" fragility at T(g) (the low temperature dynamic domain, m = m(low)) glass formers can be splitted into two groups related to f < 1 and f > 1, (f = m(high)∕m(low)). 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.     

Test of the Einstein-Debye relation in supercooled dibutylphthalate at pressures up to 1.4 GPa

Broadband dielectric measurements were carried out on di-n-butyl phthalate (DBP) under isothermal conditions at hydrostatic pressures up to 1.6 GPa. A comparison of the dielectric relaxation times with the viscosity revealed that no breakdown of the Einstein-Debye relation is induced by high compression. This absence of any decoupling is attributed to the weak intermolecular cooperativity of DBP and its negligible change with pressure. Because of the latter, the dielectric spectra conform to time-pressure superpositioning.     

Long-Range Static and Dynamic Previtreous Effects in Supercooled Squalene—Impact of Strong Electric Field

This article presents evidence for the long-range previtreous changes of two static properties: the dielectric constant (ε) and its strong electric field related counterpart, the nonlinear dielectric effect (NDE). Important evidence is provided for the functional characterizations of ε(T) temperature changes by the ‘Mossotti Catastrophe’ formula, as well as for the NDE vs. T evolution by the relations resembling those developed for critical liquids. The analysis of the dynamic properties, based on the activation energy index, excluded the Vogel–Fulcher–Tammann (VFT) relation as a validated tool for portraying the evolution of the primary relaxation time. This result questions the commonly applied ‘Stickel operator’ routine as the most reliable tool for determining the dynamic crossover temperature. In particular, the strong electric field radically affects the distribution of the relaxation times, the form of the evolution of the primary relaxation time, and the fragility. The results obtained in this paper support the concept of a possible semi-continuous phase transition hidden below T_g. The studies were carried out in supercooled squalene, a material with an extremely low electric conductivity, a strongly elongated molecule, and which is vitally important for biology and medicine related issues.     

Pretransitional behavior in the isotropic phase of a nematic liquid crystal with the transverse permanent dipole moment

The results presented give the evidence for the quasicritical, pretransitional behavior of dielectric properties in the isotropic phase of a rodlike nematic liquid crystal with the transverse permanent dipole moment. Studies were conducted in 2-cyano-4-pentylbiphenyl 4-(trans-4-pentylcyclohexyl) benzoate, focusing on the static-and ionic-dominated low-frequency (LF) regions. For the static dielectric permittivity [epsilon(')(T)] the application of the derivative analysis revealed the pretransitional anomaly associated with the specific heat exponent alpha approximately 0.5. For the LF domain the contribution to epsilon(')(T) from residual ionic impurities follows a linear temperature dependence on approaching the isotropic-nematic (I-N) transition. This dependence and pretransitional anomalies of electric conductivity and dielectric modulus can be associated with the influence of prenematic fluctuations. "Linear" dielectric studies were supported by the static nonlinear dielectric effect measurements, which delivered reliable estimations of the temperature of the hypothetical continuous phase transition T(*) and the discontinuity of the I-N transition DeltaT approximately 1.7 K.     

Effect of pressure on dynamic heterogeneity in dendrimeric alkyd resin

Broadband dielectric spectroscopy is employed to investigate the non-Debye relaxation behavior in a dendrimeric alkyd resin. From temperature-dependent measurements at ambient pressure, we found a very broad distribution of relaxation times. This is attributed to the complex geometrical topology of the molecule. However, compression significantly reduces the non-Debye character of the dielectric response; thus, pressure induces dynamic homogeneity in the dendrimeric alkyd resin.     

Dynamics of critical fluctuations in a binary mixture of limited miscibility under a strong electric field

Experimental investigations of relaxation after switching off the strong electric field in a nitrobenzene-dodecane mixture are presented. Studies were conducted for mixtures of critical and noncritical concentrations using the time-resolved nonlinear dielectric effect. The decays obtained can be portrayed by means of the stretched exponential function with the value of the exponent in agreement with the dynamic droplet model predictions. It has been shown that experimental decays exhibit a universal scaling behavior. The relaxation time (scaling factor) shows a power behavior with the exponent y approximately 1.2 for the critical mixture and y-->1 for the noncritical one. These values are much smaller than theoretically predicted y=1.8-1.9. Based on the assumption that a strong electric field induces in the mixture a quasinematic structure with semiclassical critical properties, a quantitative explanation of this difference is proposed.