Numerical calculation of free-energy barriers for entangled polymer nucleation

Abstract

The crystallisation of entangled polymers from their melt is investigated using computer simulation with a coarse-grained model. Using hybrid Monte Carlo simulations enables us to probe the behaviour of long polymer chains. We identify solid-like beads with a centrosymmetry local order parameter and compute the nucleation free-energy barrier at relatively high supercooling with adaptive-bias windowed umbrella sampling. Our results demonstrate that the critical nucleus sizes and the heights of free-energy barriers do not significantly depend on the molecular weight of the polymer; however, the nucleation rate decreases with increasing molecular weight. Moreover, an analysis of the composition of the critical nucleus suggests that intramolecular growth of the nucleated cluster does not contribute significantly to crystallisation for this system.

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