Structural relaxation time pressure dependence

Free Volume Versus Configurational Entropy Descriptions of Glass Formation Isothermal Compressibility, Specific Volume, Shear Modulus, and Jamming Influence of Side Group Size on Glass Formation Temperature Dependence of Structural Relaxation Times Influence of Pressure on Glass Formation... 

We now discuss the impact of this general property on theories and models of the glass transition. The primary concern of most theories is to explain the temperature and pressure dependences of the structural relaxation time ra. The dispersion (n or >kww) °f the structural relaxation is either not addressed or... 

The general experimental fact of constant frequency dispersion (or time dependence of the correlation function) of the a-relaxation at constant Ta for different combinations of T and P has an immense impact on glass transition. Although the data were mostly obtained by dielectric relaxation, the same effect was found in some glass-formers by photon correlation spectroscopy. The primary concern of most theories, including those mentioned in the NY Times article, is to explain the temperature and pressure dependences of the structural relaxation time Tq.. In these theories, the dispersion of the structural relaxation is either not addressed, or else considered separately with additional input not involved in arriving at r . Consequently, the frequency dispersion is unrelated to the relaxation time of the structural a-relaxation in these theories, and they are unlikely to be consistent with the T, / -superpositioning property by happenstance. 

Figure 13 A modified Angell plot of the rescaled fragility displaying the dependence of the structural relaxation times to the scaling quantity r = f I/" for some typical van der Waals liquids and polymers. From Floudas, G. Paluch, M. Grzybowski, A. Ngai, K.L. Molecular Dynamics of Glass-Forming Systems Effects of Pressure Springer Heidelberg, 2011. ...

There is one important caveat to consider before one starts to interpret activation volumes in temis of changes of structure and solvation during the reaction the pressure dependence of the rate coefficient may also be caused by transport or dynamic effects, as solvent viscosity, diffiision coefficients and relaxation times may also change with pressure [2]. Examples will be given in subsequent sections. 

Interest in the pressure dependence of structural relaxation in fluids has been stimulated by recent applications [175, 176] of a simple pressure analogue of the VFTH equation for the relaxation time x at a constant pressure P to the analysis of experimental data at variable pressures. Specifically, x(P) for both polymer and small molecule fluids has been found to extrapolate to infinity at a critical pressure Pg, and this divergence takes the form of an essential singularity,... 

Abstract For three liquids, salol, propylene carbonate, and o-terphenyl, we show that the relaxation time or the viscosity at the onset of Arrhenius behavior is a material constant. Thus, while the temperature of this transition can be altered by the application of pressure, the time scale of the dynamics retains a characteristic, pressure-independent value. Since the onset of an Arrhenius temperature-dependence and the related Debye relaxation behavior signify the loss of intermolecular constraints on the dynamics, our result indicates that intermolecular cooperativity effects are governed by the time scale for structural relaxation. 

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