Vogel-Fulcher-Tammann-Hesse segmental relaxation

Fig. 19. Temperature dependence of the shift factors of the viscosity (T), terminal dispersion ( ), and softening dispersion (0) of app from Ref. 73. The temperature dependence of the local segmental relaxation time determined by dynamic light scattering ( ) (30) and by dynamic mechanical relaxation (o) (74). The two solid lines are separate fits to the terminal shift factor and local segmental relaxation by the Vogel-Fulcher-Tammann-Hesse equation. The uppermost dashed line is the global relaxation time tr, deduced from nmr relaxation data (75). The dashed curve in the middle is tr after a vertical shift indicated by the arrow to line up with the shift factor of viscosity (73). The lowest dashed curve is the local segmental relaxation time tgeg deduced from nmr relaxation data (75).

Segmental relaxation is a non-Arrhenius process having a time scale with a temperature dependence that follows the Vogel-Fulcher-Tammann-Hesse (VFTH) equation (27) ... 

Figure 6.5. Schematic of an Arrhenius plot for mechanisms commonly observed in polymers. The lines correspond to Arrhenius [Eq. (6.8) for y, p, and Maxwell-Wagner-Sillars (MWS) relaxations] and Vogel-Tammann-Fulcher-Hesse [VTFH Eq. (6.10)], for a and normal-mode (n-) relaxation] temperature dependences for the relaxation time t(T). Relaxations ascribed to small, highly mobile, dipolar units appear in the upper right side of the plot, while those originating from bulky dipolar segments, slowly moving ions, and MWS mechanisms are located in the lower-left part of the plot.

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