| The segmental and terminal dynamics of miscible polymer blends have been systematically investigated with pointed experiments to test dichotomous literature ideas on the origin of dynamic heterogeneity in these systems. Segmental dynamics have been studied by dielectric spectroscopy, while terminal dynamics have been studied by oscillatory shear rheology. It has been found that when composition fluctuations are suppressed, dynamic heterogeneities, such as the failure of time-temperature superposition (tTS), are also suppressed. This observation lends credence to the ideas of Fischer and Kumar that spontaneous composition fluctuations in miscible blends profoundly affect their segmental dynamics. In addition, data acquired in this study on two model weakly-interacting miscible polyolefin blends, were combined with literature data to show that breakdown of tTS worsens with increasing dynamic asymmetry (intrinsic differences in component dynamics) in weakly-interacting miscible blends. This observation is adduced as evidence for the role of dynamic asymmetry in miscible blend dynamics, in addition to the role of composition fluctuations. Finally, attempts were made to use information on component segmental dynamics, as obtained from the composition fluctuation model of Kumar, to predict terminal dynamics in miscible blends. In this regard, the composition fluctuation model was first used to model segmental dynamics in a model weakly-interacting blend. Then, experimental segmental and terminal dynamics data were used to identify a possible segmental time-scale which may control terminal relaxation of a chain in a blend. This timescale was found to lie on the long-time end of the distribution of segmental relaxation times for each component. It was calculated from the segmental relaxation time distribution for each component of a miscible blend as the average-longest segmental time experienced by the monomers of a given chain. Using the Doi-Edwards tube model, the terminal chain time was determined and fed as an input to the double reptation model of des Cloizeaux. The complex modulus of miscible blends was calculated by this simple approach, and the predictions were found to be only in qualitative agreement with experimental data. The drawbacks of the proposed approach have also been discussed, and issues which need further attention have been identified. |
