Recent MD Results on Supercooled Thin Polymer Films

Physics – Condensed Matter – Soft Condensed Matter

Scientific paper

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42 pages (with figures), 1 table, 16 figures

Scientific paper

The dynamic and static properties of a supercooled (non-entangled) polymer melt are investigated via molecular dynamics (MD) simulations. The system is confined between two completely smooth and purely repulsive walls. The wall-to-wall separation (film thickness), $D$, is varied from about 3 to about 14 times the bulk radius of gyration. Despite the geometric confinement, the supercooled films exhibit many qualitative features which were also observed in the bulk and could be analyzed in terms of mode-coupling theory (MCT). Examples are the two-step relaxation of the incoherent intermediate scattering function, the time-temperature superposition property of the late time $\alpha$-process and the space-time factorization of the scattering function on the intermediate time scale of the MCT $\beta$-process. An analysis of the temperature dependence of the $\alpha$-relaxation time suggests that the critical temperature, $\Tc$, of MCT decreases with $D$. If the confinement is not too strong ($D \ge 10 {monomer diameter}$) the static structure factor of the film coincides with that of the bulk when compared for the same distance, $T-\Tc(D)$, to the critical temperature. This suggests that $T-\Tc(D)$ is an important temperature scale of our model both in the bulk and in the films.

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