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Primitive chain network simulations for comb-branched polymer under step shear deformations

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Abstract

The damping of the relaxation modulus under step shear deformation is weaker for multi-branched polymers such as comb polymers than for linear polymers. This weak damping has been related to the hierarchical relaxation, the branched arm relaxation occurring prior to the backbone relaxation and dilating the entanglement network for the backbone relaxation/contraction. A corresponding model has been proposed and favorably compared with the data for the damping function. However, the enhancement of dilation due to large deformation, known to occur for linear polymers to affect the chain contraction rate, was not considered in the model. Thus, in this paper, we investigated the dilation for a comb polymer under deformation with the aid of a 3D multichain sliplink simulation that naturally accounts for the dilation due to the constraint release through the many chain dynamics. The simulation was confirmed, to the first time, to reproduce the linear and nonlinear viscoelastic data for a comb polyisoprene (Kirkwood et al., Macromolecules 42:9592–9608, 2009). A magnitude of dilation under deformation was examined for the survival probability of the sliplinks. It turned out that the dilation for the comb backbone activated by the arm relaxation is enhanced by the deformation at short times but not at long times where the backbone relaxes and the damping function is defined. This result lends support to the conventional model.

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Acknowledgement

This study was supported by Grant-in-Aid for Scientific Research (B) No 20340111.

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Authors and Affiliations

  1. Institute for Chemical Research, Kyoto University, Gokasyo, Uji, Kyoto, 611-0011, Japan

    Yuichi Masubuchi, Yumi Matsumiya & Hiroshi Watanabe

  2. Sumitomo Chemical Co., Ltd., 2-1, Kitasode, Sodegaura, Chiba, 299-0295, Japan

    Seiji Shiromoto, Masaaki Tsutsubuchi & Yoshiaki Togawa

Authors
  1. Yuichi Masubuchi
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  2. Yumi Matsumiya
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  3. Hiroshi Watanabe
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  4. Seiji Shiromoto
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  5. Masaaki Tsutsubuchi
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  6. Yoshiaki Togawa
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Correspondence to Yuichi Masubuchi.

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Masubuchi, Y., Matsumiya, Y., Watanabe, H. et al. Primitive chain network simulations for comb-branched polymer under step shear deformations. Rheol Acta 51, 193–200 (2012). https://doi.org/10.1007/s00397-011-0574-x

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  • DOI: https://doi.org/10.1007/s00397-011-0574-x

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