Molecular dynamics study of the thermal and the density effects on the local and the large-scale motion of polymer melts: Scaling properties and dielectric relaxation

Results from a molecular dynamics simulation of a melt of unentangled polymers are presented. The translational motion, the large-scale and the local reorientation processes of the chains, as well as their relations with the so-called "normal" and "segmental" dielectric relaxation modes are thoroughly investigated in wide temperature and pressure ranges. The thermodynamic states are well fitted by the phenomenological Tait equation of state. A global time-temperature-pressure superposition principle of both the translational and the rotational dynamics is evidenced. The scaling is more robust than the usual Rouse model. The latter provides insight but accurate comparison with the simulation calls for modifications to account for both the local chain stiffness and the nonexponential relaxation. The study addresses the issue whether the temperature or the density is a dominant control parameter of the dynamics or the two quantities give rise to comparable effects. By examining the ratio \alpha(tau)\/alpha(P) between the isochronic and isobaric expansivities, one finds that the temperature is dominant when the dynamics is fast. If the relaxation slows down, the fluctuations of the free volume increase their role and become comparable to those of the thermal energy. Detectable cross-correlation between the "normal-mode" and the "segmental" dielectric relaxations is found and contrasted with the usual assumption of independent modes. (C) 2004 American Institute of Physics.