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Selfdiffusion of polymer chains in solutions and melts

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Diffusion Processes: Experiment, Theory, Simulations

Part of the book series: Lecture Notes in Physics ((LNP,volume 438))

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Abstract

Anomalous diffusion of monomers of polymer chains, as well as motion of these chains as a whole, is discussed with an emphasis on Monte Carlo simulations and simple scaling concepts. While the behavior of isolated chains in good solvents or Theta-solvents without excluded volume interactions is fully accounted for by the Rouse model, the behavior is less clear both for isolated chains in bad solvents and for chains in dense melts. Collapsed chains are shown to diffuse as g 3(t) = <([rCM (t) -rCM(0)]2〉 ∝ tξ3 where the (effective?) exponent ξ3 simply seems to be linearly temperature-dependent for temperatures T lower than the Σ-temperature, ξ3 T/Θ. A relaxation time τ oc N 3 is found, and scaling scenarios which possibly can explain these results are developed.

Short (not entangled!) chains in dense melts also are found to exhibit anomalous center of mass-diffusion, g 3(t) ∝ t ξ3 with ξ3 ≈ 0.8-0.85, contrary to expectations from the Rouse model. Therefore also the crossover from the Rouse-like behavior for chain length N less than the entanglement chain length Ne to reptation-like behavior for long chains shows some unexpected features.

Finally we briefly discuss the motion of chains in constrained geometry, such as chains constrained in straight tubes and chains end-grafted on a wall in a polymer brush.

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Authors and Affiliations

  1. Institut für Physik, Johannes Gutenberg Universität Mainz, Staudinger Weg 7, D-55099, Mainz, Germany

    K. Binder

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  1. K. Binder
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Andrzej Pękalski

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© 1994 Springer-Verlag

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Binder, K. (1994). Selfdiffusion of polymer chains in solutions and melts. In: Pękalski, A. (eds) Diffusion Processes: Experiment, Theory, Simulations. Lecture Notes in Physics, vol 438. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0031115

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  • DOI: https://doi.org/10.1007/BFb0031115

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  • Print ISBN: 978-3-540-58653-1

  • Online ISBN: 978-3-540-49038-8

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