Plateau Moduli of Several Single-Chain Slip-Link and Slip-Spring Models

preprint2021arXivOpen access

Abstract

We calculate the plateau moduli of several single-chain slip-link and slip-spring models for entangled polymers. In these models, the entanglement effects are phenomenologically modeled by introducing topological constraints such as slip-links and slip-springs. The average number of segments between two neighboring slip-links or slip-springs, N0N_{0}, is an input parameter in these models. To analyze experimental data, the characteristic number of segments in entangled polymers NeN_{e} estimated from the plateau modulus is used instead. Both N0N_{0} and NeN_{e} characterize the topological constraints in entangled polymers, and naively N0N_{0} is considered to be the same as NeN_{e}. However, earlier studies showed that N0N_{0} and NeN_{e} (or the plateau modulus) should be considered as independent parameters. In this work, we show that due to the fluctuations at the short time scale, NeN_{e} deviates from N0N_{0}. This means that the relation between N0N_{0} and the plateau modulus is not simple as naively expected. The plateau modulus (or NeN_{e}) depends on the subchain-scale details of the employed model, as well as the average number of segments N0N_{0}. This is due to the fact that the subchain-scale fluctuation mechanisms depend on the model rather strongly. We theoretically calculate the plateau moduli for several single-chain slip-link and slip-spring models. Our results explicitly show that the relation between N0N_{0} and NeN_{e} is model-dependent. We compare theoretical results with various simulation data in the literature, and show that our theoretical expressions reasonably explain the simulation results.

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