Theory of melt polyelectrolyte blends and block copolymers: Phase behavior, surface tension, and microphase periodicity

Charles E. Sing, Jos W. Zwanikken, Monica Olvera De La Cruz

Research output: Contribution to journalArticle

Abstract

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.

Original languageEnglish (US)
Article number034902
JournalJournal of Chemical Physics
Volume142
Issue number3
DOIs
StatePublished - Jan 21 2015

Fingerprint

Phase behavior
Polyelectrolytes
block copolymers
Block copolymers
self consistent fields
Surface tension
periodic variations
copolymers
interfacial tension
Liquids
liquids
Polymers
spacing
Functional materials
polymers
Chain length
Integral equations
Phase diagrams
integral equations
Electrostatics

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Theory of melt polyelectrolyte blends and block copolymers : Phase behavior, surface tension, and microphase periodicity. / Sing, Charles E.; Zwanikken, Jos W.; De La Cruz, Monica Olvera.

In: Journal of Chemical Physics, Vol. 142, No. 3, 034902, 21.01.2015.

Research output: Contribution to journalArticle

@article{e3d1fbeba0b14aaf8141a9651ef4f536,
title = "Theory of melt polyelectrolyte blends and block copolymers: Phase behavior, surface tension, and microphase periodicity",
abstract = "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.",
author = "Sing, {Charles E.} and Zwanikken, {Jos W.} and {De La Cruz}, {Monica Olvera}",
year = "2015",
month = "1",
day = "21",
doi = "10.1063/1.4905830",
language = "English (US)",
volume = "142",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "3",

}

TY - JOUR

T1 - Theory of melt polyelectrolyte blends and block copolymers

T2 - Phase behavior, surface tension, and microphase periodicity

AU - Sing, Charles E.

AU - Zwanikken, Jos W.

AU - De La Cruz, Monica Olvera

PY - 2015/1/21

Y1 - 2015/1/21

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84923796495&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84923796495&partnerID=8YFLogxK

U2 - 10.1063/1.4905830

DO - 10.1063/1.4905830

M3 - Article

AN - SCOPUS:84923796495

VL - 142

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 3

M1 - 034902

ER -