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Published on: August 20, 2014
Kinetic Selection of Chain Folds under Entanglement Constraint
Renkuan Cao1, Fan Peng1, Hao Sun1
1National Synchrotron Radiation Laboratory, State Key Laboratory of Advanced Glass Materials, Anhui Provincial Engineering Research Center for Advanced Functional Polymer Films, University of Science and Technology of China, Hefei, Anhui 230029, China.
Abstract:
How to fold long-chain molecules under entanglement topological constraints is a long-standing challenge in polymer crystallization. Using molecular dynamics simulations, we observe that polymer chains undergo directional reptation toward the growth front, demonstrating the existence of an along-chain force that drives disentanglement and facilitates tight-fold formation. Our results seminally reveal a linear scaling between the tight-fold fraction and the reciprocal of the entanglement length. This scaling originates from the regulation by entanglement and chain rigidity: the former limits the physical scale at which the segment can fold, whereas the latter determines the difficulty of bending the chain segment into a tight fold within confined space.
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