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Numerical calculation of free-energy barriers for entangled polymer nucleation.

Accepted version
Peer-reviewed

Type

Article

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Authors

Tang, Xiaoliang 
Tian, Fucheng 
Reinhardt, Aleks 

Abstract

The crystallization 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 behavior 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 the increase in molecular weight. Moreover, an analysis of the composition of the critical nucleus suggests that intra-molecular growth of the nucleated cluster does not contribute significantly to crystallization for this system.

Description

Keywords

cond-mat.soft, cond-mat.soft, cond-mat.mtrl-sci, physics.chem-ph

Journal Title

J Chem Phys

Conference Name

Journal ISSN

0021-9606
1089-7690

Volume Title

152

Publisher

AIP Publishing

Rights

All rights reserved
Sponsorship
National Key R&D Program of China (2016YFB0302500); National Natural Science Foundation of China (51633009); Royal Society Newton Mobility Grant (MBAG/240 RG82754)
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