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Unexpected power-law stress relaxation of entangled ring polymers

Nature Materials volume 7, pages 997–1002 (2008)Cite this article

Abstract

After many years of intense research, most aspects of the motion of entangled polymers have been understood. Long linear and branched polymers have a characteristic entanglement plateau and their stress relaxes by chain reptation or branch retraction, respectively. In both mechanisms, the presence of chain ends is essential. But how do entangled polymers without ends relax their stress? Using properly purified high-molar-mass ring polymers, we demonstrate that these materials exhibit self-similar dynamics, yielding a power-law stress relaxation. However, trace amounts of linear chains at a concentration almost two decades below their overlap cause an enhanced mechanical response. An entanglement plateau is recovered at higher concentrations of linear chains. These results constitute an important step towards solving an outstanding problem of polymer science and are useful for manipulating properties of materials ranging from DNA to polycarbonate. They also provide possible directions for tuning the rheology of entangled polymers.

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Figure 1: Illustration of entangled polymer conformations and relaxation models.
Figure 2: Stress relaxation moduli G(t) of entangled polymers.
Figure 3: Effects of added linear chains on entangled purified ring polymer rheology.
Figure 4: Illustrations of conformations of mixtures involving ring and linear polymers.

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Acknowledgements

We are indebted to J. Roovers for providing the original ring polymers used in this work and for many insightful discussions. We are particularly grateful to S. T. Milner and T. C. B. McLeish for extended discussions that clarified the role of constraint release and significantly improved the quality of the paper. We thank S. Panyukov, S. P. Obukhov, N. Hadjichristidis, B. Loppinet, E. van Ruymbeke, G. Fytas, A.Y. Grosberg, C. Tsenoglou and M. Vamvakaki for helpful discussions. This work was supported by EU (NoE Softcomp NMP3-CT-2004-502235), NSF (CHE-0616925, CBET-0609087), NIH (1-R01-HL0775486A) and KOSEF (CIMS, R0A-2007-000-20125-0).

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Author notes

  1. M. Kapnistos & D. Cho

    Present address: Present addresses: DSM Research, Materials Science Centre, Geleen 6160 BD, The Netherlands (M.K.); Samsung Electro-Mechanics Co., Central R&D Institute, Suwon 443743, Korea (D.C.),

Authors and Affiliations

  1. FORTH, Institute of Electronic Structure and Laser, Heraklion, Crete 71110, Greece

    M. Kapnistos & D. Vlassopoulos

  2. Department of Chemical Engineering, University of California, Santa Barbara, California 93106, USA

    M. Kapnistos

  3. Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599-3290, USA

    M. Lang & M. Rubinstein

  4. Leibniz Institute for Polymer Research, Dresden 01005, Germany

    M. Lang

  5. Department of Materials Science and Technology, University of Crete, Heraklion 71003, Greece

    D. Vlassopoulos

  6. Forschungszentrum Jülich, Institute of Solid State Research, Jülich 52425, Germany

    W. Pyckhout-Hintzen & D. Richter

  7. Department of Chemistry, Pohang University of Science and Technology, Pohang 790784, Korea

    D. Cho & T. Chang

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Correspondence to D. Vlassopoulos or M. Rubinstein.

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Kapnistos, M., Lang, M., Vlassopoulos, D. et al. Unexpected power-law stress relaxation of entangled ring polymers. Nature Mater 7, 997–1002 (2008). https://doi.org/10.1038/nmat2292

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