Macromolecules, Vol.28, No.16, 5450-5457, 1995
Component Dynamics in Polystyrene bis(2-Ethylhexyl) Phthalate Solutions by Polarized and Depolarized Light-Scattering and Dielectric-Spectroscopy
Depolarized Rayleigh, polarized Rayleigh-Brillouin scattering, and dielectric spectroscopy have been used to resolve the dynamics of the two components in concentrated solutions of polystyrene (PS) in bis(2-ethylhexyl)phthalate (DOP) close to and above the glass transition temperature. Two distinct time scales of motion exist in the macroscopically homogeneous PS/DOP solutions which are associated with the faster solvent (DOP) and slower polymer (PS) dynamics with different temperature shift factors. The width and the degree of asymmetry of the distribution of relaxation times determined as a function of temperature for both components increase as temperature decreases, and also as the PS concentration increases, indicating that the contribution at a lower frequency has a larger temperature shift factor, alpha(T). The temperature dependencies of the most probable relaxation times, tau(iota) with iota = 1, 2, of both processes conform to the Vogel-Fulcher-Tammann (VFT) equation. These VFT dependencies for the two components, iota = 1, 2, in the mixture when replotted respectively against T-g iota/T, where T-g iota is the temperature at which tau(iota)(T-g iota) = 10(o) s, show a trend that can be expected from the enhancement (mitigation) of constraint dynamics of DOP (PS) with further addition of PS (DOP) to the mixture. There is an exact analogy between the current experimental findings in the mixture of polymer and small-molecule diluent and what we have found in the component dynamics in binary miscible polymer blends. Thus the physics in these two systems are similar. The Rayleigh-Brillouin experiment revealed the existence of an additional faster process associated with a localized motion of the phenyl group of the DOP molecule in the concentrated solutions in agreement with a previously reported study.
Keywords:SEGMENTAL RELAXATION;AROCLOR SOLUTIONS;MOLECULAR-DYNAMICS;POLYMER-SOLUTIONS;SOLVENT MOBILITY;BLENDS;DIFFUSION;MOTION