The viscoelastic behavior of polymer/oligomer blends

The viscoelastic properties of poly(α-methyl styrene), its hexamer, and their athermal blends at various concentrations are studied. Master curves for the dynamic shear responses, G′ and G″, are successfully constructed for both the pure materials and the blends, indicating the validity of the time–temperature superposition principle for these systems. The temperature dependence of the shift factor follows the Vogel–Fulcher behavior over the temperature range studied, and the temperature dependence is slightly weaker for the blends. The rubbery plateau modulus scales with the polymer concentration as G N 0 ∝ ϕ 2 . 04 ± 0 . 32 ; the terminal relaxation time scales with the polymer concentration as τ d ∝ ϕ 1 . 35 ± 0 . 33 . The shape of the segmental dispersion appears unchanged by concentration, which differs from our calorimetric studies where mixtures show obviously temperature-broadened glass transitions and depressed enthalpy overshoots. The TNM (Tool-Narayanaswamy-Moynihan) model indicates that the change in the temperature dependence is not sufficient to account for the observed calorimetric broadening. We conclude that the temperature broadening of the glass transition for our blends is not due to a broadening of the dynamic spectrum or to changes in its temperature dependence. The possibility that the broadening is due to changes in the non-linearity parameter x in the TNM model is also considered. While the broadening could be due to a decreasing value of x, we found that this same decrease would lead to increasing enthalpy overshoots on heating, contrary to the experimental observations. The combination of the calorimetric results with the rheological measurements further indicates that the fundamental basis of the TNM-type of model of structural kinetics in glasses is potentially wrong.