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Stress Relaxation of Comb Polymer Melts

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Abstract

Branched polymers stress relaxation is at the center to their function as viscosity modifiers, though the fundamentals that underlie the correlation between the polymer topology and their impact on viscosity remains an open question. Here, the stress relaxation of short, branched polyethylene comb polymer melts is studied by molecular dynamics simulations. A coarse-grained model where four methylene groups constitute one bead is used, and the results are transposed to the atomistic level. For arms of length comparable to entanglement length ne of the linear polymer, we show that while increasing the number of branches with the same arm length decreases the plateau modulus, the terminal diffusive time does not change significantly. Increasing the arm length decreases the plateau modulus and increases the terminal time. As arms shorter than ne relax by the entanglement time, both the chain mobility and stress relaxation can be described by reptation of the backbone with an increased tube diameter and an increased friction coefficient; or in other words, the branches act as a solvent.

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Acknowledgement

We dedicate this paper to the memory of Mark O. Robbins, graduate advisor to two of us (TG and KMS), friend and colleague to all. D. Perahia kindly acknowledged NSF DMR 1905407 for partial support. T. Ge acknowledges start-up funds from the University of South Carolina. This research used resources of the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility operated under Contract No. DE-AC02-05CH11231. This work was performed, in part, at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science. Sandia National Laboratories is a multimission laboratory managed and operated by the National Technology and Engineering Solutions of Sandia, LC, a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract no. DE-NA-0003525. The views expressed in the article do not necessarily represent the views of the U.S. DOE or the United States Government.

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Authors and Affiliations

  1. Department of Chemistry, Clemson University, Clemson, SC, 29634, USA

    Sidath Wijesinghe & Dvora Perahia

  2. Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC, 29208, USA

    Ting Ge

  3. U. S. Army Research Laboratory, Aberdeen Proving Grounds, Aberdeen, MD, 21005, USA

    K. Michael Salerno

  4. Sandia National Laboratories, Albuquerque, NM, 87185, USA

    Gary S. Grest

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  1. Sidath Wijesinghe
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  2. Dvora Perahia
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  3. Ting Ge
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  4. K. Michael Salerno
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  5. Gary S. Grest
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Correspondence to Dvora Perahia or Gary S. Grest.

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Wijesinghe, S., Perahia, D., Ge, T. et al. Stress Relaxation of Comb Polymer Melts. Tribol Lett 69, 59 (2021). https://doi.org/10.1007/s11249-021-01432-y

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