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The Polyelectrolyte Brush: Poor Solvent

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Abstract

We investigate the end grafted polyelectrolyte brush in the poor solvent regime of the corresponding neutral polymer system. Using Poisson-Boltzmann theory for the electrostatics and Flory-Huggins-mean-field theory for the excluded volume and Van-der-Waals-like monomer interactions, we find the existence of a first order phase transition to a collapsed state for moderate to highly charged polyelectrolytes in the poor solvent regime. Irreversibilities in the disjoining pressure between planar grafted surfaces are predicted. For polyelectrolytes grafted to spherical and cylindrical surfaces with small radii of curvature, the phase transition is predicted to become second order in the infinite molecular weight limit. A phase diagram for the entire poor solvent regime is given.

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Acknowledgements

The authors express their sincere thanks to E.B. Zhulina, J.-F. Argillier, M. Tirrell, J. Klein and J. Isrealachvilli for many helpful discussions. This work was supported in part by a SURS grant #0357(800612) from IBM and the U.S. DOE grant #DE-FG03-87ER45288.

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Authors and Affiliations

  1. Department of Physics, University of California, Santa Barbara, CA, 93106, USA

    Richard S. Ross & Phil Pincus

  2. Materials Department, University of California, Santa Barbara, CA, 93106, USA

    Phil Pincus

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  1. Richard S. Ross
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  2. Phil Pincus
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Ross, R.S., Pincus, P. The Polyelectrolyte Brush: Poor Solvent. MRS Online Proceedings Library 248, 431–436 (1991). https://doi.org/10.1557/PROC-248-431

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