Relaxation, beta, dielectric

The volumetric, elastic and dynamic properties of internally and externally plasticised PVC were studied and compared with those of unplasticised PVC. The glass transition temperature for the plasticised samples was markedly lowered and this decrease was more important for the externally plasticised ones. The positions of the loss peaks from dielectric alpha-relaxation measurements confirmed the higher efficiency of the external plasticisation. However, the shape of the dielectric alpha-relaxation function was altered only for the internally plasticised samples. The plasticisation effect was linked with a decrease in the intensity of the beta-relaxation process but no important changes in the activation energy of this process were observed. The results were discussed. 47 refs. 

Figure 5.2. A schematic representation of typieal alpha and beta relaxations observed from mechanical and dielectric properties. The observed relaxation temperatures increase with increasing frequency.

In accordance to the data reported in the literature for bulk hyperbranched polyesters [34,35], three relaxation processes are also observed in thin POHOAc films, (Fig. 23) the alpha relaxation process, representing the dynamic glass transition, the beta process, attributed to the relaxation of the ester groups, and the gamma relaxation process, originating from fluctuations of the —OH end groups. The latter two, which are broad and not well-separated from one another, are only distinguishable in the temperature representation of the dielectric spectra (inset, Fig. 23). 

The assignment of the alpha relaxation was additionally confirmed by AC-calorimetric measurements on thin films of POHOAc [31], The effect of confinement on the overall dynamics of POHOAc is given in Fig. 24, showing the dielectric spectra for different film thicknesses, ranging from 310 nm down to 17 nm. While the beta and the gamma relaxations, as local processes, are not affected with decreasing film thickness (except a decrease of the dielectric... 

Figure 23. Dielectric loss e" versus frequency at different temperatures, as indicated, showing the alpha relaxation process for a thin film of hyperbranched polyesters of 17 nm. Inset. Dielectric loss e" versus temperature at 49 kHz, showing the beta and the gamma relaxation processes for the same sample. Dotted lines serve as a guide for the reader.

Cerveny investigated the development of the dynamic glass transition in styrene-butadiene copolymers by dielectric spectroscopy in the frequency range from 10 to 10 Hz. Two processes were detected and attributed to the alpha- and beta-relaxations. The alpha relaxation time has a non-Arrhenius temperature behavior that is highly dependent on styrene content... 

Cerveny, S. Bergman, R. Schwartz, G.A. Jacobsson, P. Dielectric alpha- and beta-relaxations in uncured styrene butadiene rubber. Macromole-cular 2002, 35, 337-342. 

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. 

Hoffman, J.D., Williams, G. and Passaglia, E. (1966) Analysis of alpha beta and gamma relaxations in polychlorotrifluoroethylene and polyethylene - dielectric and mechanical properties. /. Polym. Sci., C, 14, 173. 

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