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Polydisperse Polymer Brushes: Internal Structure, Critical Behavior, and Interaction with Flow

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Download Hi-Res ImageDownload to MS-PowerPointCite This:Macromolecules 2016, 49, 24, 9665-9683
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    Polydisperse Polymer Brushes: Internal Structure, Critical Behavior, and Interaction with Flow
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    Institut für Physik, Johannes Gutenberg-Universität Mainz, Staudingerweg 7, D-55099 Mainz, Germany
    Department of Physics, American University of Beirut, P.O. Box 11-0236, Beirut 1107 2020, Lebanon
    Chemical-Pharmaceutical Academy, Professora Popova 14, 197022 St. Petersburg, Russia
    Institut für Physik, Johannes Gutenberg-Universität Mainz, Staudingerweg 7, D-55099 Mainz, Germany
    *E-mail [email protected] (S.Q.).
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    Macromolecules

    Cite this: Macromolecules 2016, 49, 24, 9665–9683
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    https://doi.org/10.1021/acs.macromol.6b02026
    Published December 14, 2016
    Copyright © 2016 American Chemical Society
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    Abstract

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    We study the effect of polydispersity on the structure of polymer brushes by analytical theory, a numerical self-consistent field approach, and Monte Carlo simulations. The polydispersity is represented by the Schulz–Zimm chain-length distribution. We specifically focus on three different polydispersities representing sharp, moderate, and extremely wide chain length distributions and derive explicit analytical expressions for the chain end distributions in these brushes. The results are in very good agreement with numerical data obtained with self-consistent field calculations and Monte Carlo simulations. With increasing polydispersity, the brush density profile changes from convex to concave, and for given average chain length Nn and grafting density σ, the brush height H is found to scale as (H/Hmono – 1) ∝ (Nw/Nn – 1)1/2 over a wide range of polydispersity indices Nw/Nn (here Hmono is the height of the corresponding monodisperse brush). Chain end fluctuations are found to be strongly suppressed already at very small polydispersity. On the basis of this observation, we introduce the concept of the brush as a near-critical system with two parameters (scaling variables), (Nnσ2/3)−1 and (Nw/Nn – 1)1/2, controlling the distance from the critical point. This approach provides a good description of the simulation data. Finally, we study the hydrodynamic penetration length lp for brush-coated surfaces in flow. We find that it generally increases with polydispersity. The scaling behavior crosses over from lp ∼ Nn1/2σ–1/6 for monodisperse and weakly polydisperse brushes to lp ∼ Nn2/3 for strongly polydisperse brushes.

    Copyright © 2016 American Chemical Society

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    This article is cited by 44 publications.

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    Macromolecules

    Cite this: Macromolecules 2016, 49, 24, 9665–9683
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.macromol.6b02026
    Published December 14, 2016
    Copyright © 2016 American Chemical Society
    Request reuse permissions

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