Intrinsic structure and dynamics of monolayer ring polymer melts

J Kim and JM Kim and C Baig, SOFT MATTER, 17, 10703-10715 (2021).

DOI: 10.1039/d1sm01192h

We present the general structural and dynamical characteristics of flexible ring polymers in narrowly confined two-dimensional (2D) melt systems using atomistic molecular dynamics simulations. The results are further analyzed via direct comparison with the 2D linear analogue as well as the three-dimensional (3D) ring and linear melt systems. It is observed that dimensional restriction in 2D confined systems results in an increase in the intrinsic chain stiffness of the ring polymer. Fundamentally, this arises from an entropic penalty on polymer chains along with a reduction in the available chain configuration states in phase space and spatial choices for individual segmental walks. This feature in combination with the intermolecular interactions between neighboring ring chains leads to an overall extended interpenetrated chain configuration for the 2D ring melt. In contrast to the generally large differences in structural and dynamical properties between ring and linear polymers in 3D melt systems, relatively similar local-to- global chain structures and dynamics are observed for the 2D ring and linear melts. This is attributed to the general structural similarity (i.e., extended double-stranded chain conformations), the less effective role of the chain ends, and the absence of complex topological constraints between chains (i.e., interchain entanglement and mutual ring threading) in the 2D confined systems compared with the corresponding 3D bulk systems.

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