Dielectric relaxation activation enthalpy

In measurements of the dielectric relaxation of water adsorbed on acetylated wood, a large change in the activation enthalpy and entropy of dielectric relaxation was found to occur at 6 % moisture content (Zhao etal., 1994), this presumably being attributable to the onset of formation of capillary water in the cell wall. 

Relevant dielectric results of type B glasses were already discussed in Section IV.C.2. The spectra below Tg exhibit a broad symmetric secondary relaxation peak that can be interpolated assuming a Gaussian distribution of activation enthalpies. Only recently it became clear that also NMR is able to identify secondary relaxation processes in glasses, moreover providing information on the mechanisms of molecular reorientation that is not easily accessible to most of the other methods. For detailed reports the reader is referred to the reviews by Bohmer et al. [11] and Vogel et al. [15]. Here, we summarize the major results. 

Analysis of the enthalpy relaxation the enthalpy relaxation time and the activation energy were calculated by KWW in accordance with the previous work (Kawai et al., 2004). The KWW theory was originally proposed in dielectric relaxation study by Williams and Watts (1970), then applied in the form of nonexponential function such as the enthalpy relaxation. In KWW theory, the enthalpy relaxation, AH eiax/ which corresponds to the peak area given from the enthalpy relaxation is expressed by the equation... 

Then the FDSE exponent 5 = / = 2.1/1.6 0.76. The same value can be found in Fig. 2 basing on logjo a vs. logjo r plot. Dividing further eq. (5) by its analog for dielectric relaxation time one can obtain the relation linking apparent activation enthalpies, MCT critical-like exponent and FDSE exponent ... 

In Figure 11.17 we show Arrhenius plots of the isobaric [t (7)]/> (F = 0.1 MPa) and isochoric [t (7)] v/ (vy = 20 to 30 mm /g) dielectric relaxation times of PMPhS, where the free volume Vf was obtained from the S-S equation of state. The slopes at the intersection of the isochoric and isobaric curves yield the respective activation enthalpies for ambient pressure. 

Relaxation Phenomena Hilczer et al. [2002] studied the relaxation behavior of nanoceramic-polymer composites. The smdy focused on a PVDF/PZT composite with 30-nm particles. The dielectric relaxation time of PVDF as well as that of the low-temperature component followed VFTH [Eq. (13.2)]. By contrast, the relaxation time of the high-temperature component obeyed the Arrhenius equation. It is interesting to note that the activation enthalpy increased strongly in composites. The effect was ascribed to the wide-angle oscillation of dipolar groups of PVDF. 

Based on the dielectric and dynamic mechanical data, it appears that water and small polar molecules contribute to three dispersions in this poly(amide-imide). One is the low temperature relaxation between -100 and 0°C. This may be a hydrogen bonded relaxation since the activation enthalpy was 30 kJ/mol. This occurs at concentrations of water ranging between 0 to 4 weight percent. Two, the dielectric relaxation between 0 and 70 C can probably be attributed to conductive contaminants whose mobility is dependent upon a minimum amount of water. Three, at high water concentrations, greater than 2 weight percent, the water/NMP contributes to the beta relaxations observed between 50 and 150 C. 

Sato, T., Chiba, A., and Nozaki, R. (1999). Dynamical aspects of mixing schemes in ethanol-water mixtures in terms of the excess partial molar activation free energy, enthalpy, and entropy of the dielectric relaxation process. J. Chem. Phys., 110, 2508-2521. 

Since the subject of SCP is an extremely broad one, it is necessary to limit its scope for the present discussion. First, no further consideration will be given to ordinary dielectric response, although electrical behavior arising from the presence of electric dipoles may often be confused with SCP behavior and vice versa, especially in blocking electrode situations and especially when a distribution of relaxation times is invoked to explain putative dielectric response behavior. Incidentally, it is worth mentioning that the expressions frequently used to describe a distribution of thermally activated relaxation times are inappropriate when applied over a range of temperatures and when the enthalpy involved in the thermally activated dipole behavior is itself distributed. ... 

The invariance of relaxation frequency with molecular wei t may not be apparent at finite concentrations of polymer, because cofl — c< interactions can effect the relaxation of internal modes as well as the first order, rotational mode. There have been a number of studies of the concentration dependence of dielectric loss processes some of which show weU the continuous trend in behawour from dilute solution to the bulk state. Temperature variation can provide useful information on the enthalpies of activation of local mode motions. Finally, since such local modes are very structure sensitive, differences in chain tacticity would be expected, and do cause changes in loss behaviour. This prediction has been authenticated for such polymers as poly(methyl methacrylate) and poly(ethyl acrylate). ... 

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