Qualitative analysis, dielectric relaxation

Figures 3-5 that the dielectric relaxation again reveals only a single a relaxation for the mixtures. These are, however, noticeably broader than the a relaxation of the pure polymers. The temperatures of the loss maxima, when plotted (Figure 7) as a function of wu the weight fraction of PPO in the mixtures, do not display the smooth monotonic increase in T0 vs. Wi that was shown by both the Vibron and the DSC results. Instead, there is a pronounced increase in Tg above = 0.5 to give a sigmoid curve for this relation. Some reservations should be attached to this observation inasmuch as data for only three polyblend compositions are available nevertheless a qualitatively similar phenomenon is observed in the analysis of the intensity of the y peak (below). Further, if only the stronger maxima in the dynamical mechanical data are considered— i.e.y if the secondary peaks and shoulders which led to the identification of two phases are omitted—then a similar sigmoid curve is found. The significance of this observation is discussed later.

The DISPA analysis described above is based on comparison of an experimental curve to a reference circle. Although that display is qualitatively useful in identifying the correct line-broadening mechanism, the analogous Cole-Cole plotS in dielectric relaxation continues as a popular display mode after nearly 40 years), a display in vyhich the same experimental DISPA data is compared to a straight line could better help to determine quantitatively the line-broaoen-ing parameter(s) of that mechanism. 

HBA. The T p values display minima, coincident with the temperatures of the y and p relaxations previously observed by dielectric and dynamic mechanical analysis. The Tjp - temperature data have been fitted to the Cole-Davidson distribution function, which indicates a broad distribution of correlation times. The activation energies obtained from the fitting are higher than from dielectric data, but, in a qualitative sense support the contention that the y relaxation is associated with the motion of HBA units, and the p relaxation with the motion of HNA units. 

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