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Polymer brushes with reversibly tunable grafting density.

Leonid I Klushin1, Alexander M Skvortsov2, Alexey A Polotsky3

  • 1Department of Physics, American University of Beirut, P. O. Box 11-0236, Beirut 1107 2020, Lebanon and Institute of Macromolecular Compounds, Russian Academy of Sciences, 31 Bolshoy Pr, 199004 Saint Petersburg, Russia.

The Journal of Chemical Physics
|February 20, 2021
PubMed
Summary

We developed responsive polymer brushes with tunable grafting density using substrate-affinity chains. This innovation allows controlled, reversible changes in polymer brush properties via external stimuli.

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Area of Science:

  • Polymer Science
  • Surface Chemistry
  • Materials Science

Background:

  • Responsive polymer brushes are crucial for tunable surface properties.
  • Controlling grafting density is key to tailoring brush behavior.
  • Existing methods often lack precise external control over effective grafting density.

Purpose of the Study:

  • To introduce a novel class of responsive polymer brushes with externally controllable effective grafting density.
  • To investigate the mechanism of grafting density control via substrate affinity and microphase separation.
  • To determine the optimal conditions (chain length, grafting density) for pronounced responsive behavior.

Main Methods:

  • Utilizing end-grafted polymer chains with specific substrate affinity.
  • Employing numerical self-consistent field (SCF) calculations to model brush behavior.
  • Applying scaling arguments to analyze the observed phenomena.
  • Exploring the influence of adsorption strength and environmental parameters.

Main Results:

  • A fraction of polymer chains condenses into a near-surface layer, forming coexisting microphases with an outer brush.
  • The effective grafting density of the outer brush is reversibly controlled by adsorption strength.
  • SCF studies reveal large fluctuations in individual chains within the dense layer.
  • Overall brush behavior shows smooth variation in effective grafting density with control parameters.

Conclusions:

  • The proposed polymer brush architecture enables controlled, stimuli-responsive tuning of effective grafting density.
  • The phenomenon relies on microphase separation driven by strong surface interactions.
  • This offers a new pathway for designing smart surfaces with adaptable properties.