Polymer mixtures such as blends or block copolymers are of great interest in energy applications and functional materials, and often, one or more of these species contain charges. The traditional fashion in which such materials are studied uses Self-Consistent Field Theory (SCFT) methods that incorporate electrostatics using Poisson-Boltzmann (PB) theory. We adapt a new and rigorous approach that does not rely on the mean-field assumptions inherent in the PB theory and instead uses Liquid State (LS) integral equation theory to articulate charge correlations that are completely neglected in PB. We use this theory to calculate phase diagrams for both blends and block copolyelectrolytes using SCFT-LS and demonstrate how their phase behavior is highly dependent on chain length, charge fraction, charge size, and the strength of Coulombic interactions. Beyond providing phase behavior of blends and block copolyelectrolytes, we can use this theory to investigate the interfacial properties such as surface tension and block copolyelectrolyte lamellar spacing. Lamellar spacing provides a way to directly compare the SCFT-LS theory to the results of experiments. SCFT-LS will provide conceptual and mathematical clarification of the role of charge correlations in these systems and aid in the design of materials based on charge polymers.
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21 January 2015
Research Article|
January 16 2015
Theory of melt polyelectrolyte blends and block copolymers: Phase behavior, surface tension, and microphase periodicity Available to Purchase
Charles E. Sing;
Charles E. Sing
1Department of Materials Science and Engineering,
Northwestern University
, Evanston, Illinois 60208, USA
2Department of Chemical and Biomolecular Engineering,
University of Illinois at Urbana-Champaign
, Urbana, Illinois 61801, USA
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Jos W. Zwanikken;
Jos W. Zwanikken
1Department of Materials Science and Engineering,
Northwestern University
, Evanston, Illinois 60208, USA
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Monica Olvera de la Cruz
Monica Olvera de la Cruz
1Department of Materials Science and Engineering,
Northwestern University
, Evanston, Illinois 60208, USA
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Charles E. Sing
1,2
Jos W. Zwanikken
1
Monica Olvera de la Cruz
1
1Department of Materials Science and Engineering,
Northwestern University
, Evanston, Illinois 60208, USA
2Department of Chemical and Biomolecular Engineering,
University of Illinois at Urbana-Champaign
, Urbana, Illinois 61801, USA
J. Chem. Phys. 142, 034902 (2015)
Article history
Received:
September 03 2014
Accepted:
December 30 2014
Citation
Charles E. Sing, Jos W. Zwanikken, Monica Olvera de la Cruz; Theory of melt polyelectrolyte blends and block copolymers: Phase behavior, surface tension, and microphase periodicity. J. Chem. Phys. 21 January 2015; 142 (3): 034902. https://doi.org/10.1063/1.4905830
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