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The non-linear viscoelastic response under interrupted shear flows is one of the interesting characteristics of entangled polymers. In particular, the stress overshoot in the resumed shear has been discussed concerning the recovery of the entanglement network in some studies. In this study, we performed multichain slip-link simulations to observe the molecular structure of an entangled polymer melt. After confirming the reasonable reproducibility of our simulation with the literature data, we analyzed the molecular characteristics following the decoupling approximation. We reasonably found that the segment orientation dominates the stress overshoot even under the resumed shear with minor contributions from the segment stretch and entanglement density. We defined the mitigation function for the recovery of the stress overshoot as a function of the rest time and compared it with the relaxation of the molecular quantities after the initial shear. As a result, we have found that the mitigation of the stress overshoot coincides with the relaxation of entanglement density., ファイル公開：2021/07/28

In the present paper, a new type of micro-mechanically motivated chain network model for rubber-like materials is proposed. The model captures topological constraints of polymer network chains, in particular, entanglements. The model demonstrates how the local molecular packing constraints modify under deformation and shows the impact of these changes on the macroscopic elasticity of the material. To this end, we combine concepts of a confining tube and a slip-link (reptation) model. In these models, entanglements of polymer chains play an important role. The nature of entanglements is discussed, and relationships governing entanglements are formulated in terms of molecular physics. In the context of nonlinear elasticity, we apply a non-affine concept which captures the liquid-like behavior of polymer networks at smaller scales in a more realistic way. Model predictions show good agreement with experimental results from uniaxial and biaxial tension tests.

Although lots of coarse-grained models have been proposed to trace the long-term behaviors of entangled polymers, compatibility among the different models has not been frequently discussed. In this study, some dynamical and static quantities, such as diffusion, relaxation modulus, chain dimension, and entanglement density, were examined for the multi-chain slip-link model (primitive chain network model) and the multi-chain slip-spring model, and the results were compared with those reported for the standard bead-spring model. For the diffusion, three models are compatible with scale-conversion parameters for units of length, time and bead (segment) number (or the molecular weight). The relaxation modulus is also compatible given that the model dependence can be accommodated by the entanglement density and the additional scale-conversion for the unit of modulus. The chain dimension is reasonably coincident with small deviations due to the weak non-Gaussianity of the models. Apart from these plausible compatibilities, significant discrepancies have been found for the inter-chain cross-correlations in the relaxation modulus., ファイル公開：2019/08/07