Polymer Films in the Normal-Liquid and Supercooled State: A Review of Recent Monte Carlo Simulation Results

Details Polymer Films in the Normal-Liquid and Supercooled State: A Review of Recent Monte Carlo Simulation Results Polymer Films in the Normal-Liquid and Supercooled State: A Review of Recent Monte Carlo Simulation Results

2000-12-15

arxiv.org/abs/cond-mat/0012277v1

Physics

Condensed Matter

Soft Condensed Matter

39 pages of REVTeX, 14 PostScript figures

Scientific paper

This paper reviews recent Monte Carlo simulation studies of the glassy behavior in thin polymer films. The simulations employ a version of the bond-fluctuation lattice model, in which the glass transition is driven by the competition between a stiffening of the polymers and their dense packing in the melt. The melt is geometrically confined between two impenetrable walls separated by distances ranging from once to about fifteen times the bulk radius of gyration. The confinement influences static and dynamic properties of the films: Chains close to the wall preferentially orient parallel to it. This orientation tendency propagates through the film and leads to a layer structure at low temperatures and small thicknesses. The layer structure strongly suppresses out-of-plane reorientations of the chains. In-plane reorientations have to take place in a high density environment which gives rise to an increase of the corresponding relaxation times. However, local density fluctuations are enhanced if film thickness and temperature decrease. This implies a reduction of the glass transition temperature with decreasing film thickness.

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