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Title: Enhanced scattering induced by electrostatic correlations in concentrated solutions of salt-free dipolar and ionic polymers

Abstract

Here, we present a generalized theory for studying the static monomer density-density correlation function (structure factor) in concentrated solutions and melts of dipolar as well as ionic polymers. The theory captures effects of electrostatic fluctuations on the structure factor and provides insights into the origin of experimentally observed enhanced scattering at ultralow wavevectors in salt-free ionic polymers. It is shown that the enhanced scattering can originate from a coupling between the fluctuations of electric polarization and monomer density. Local and non-local effects of the polarization resulting from finite sized permanent dipoles and ion-pairs in dipolar and charge regulating ionic polymers, respectively, are considered. Theoretical calculations reveal that, similar to the salt-free ionic polymers, the structure factor for dipolar polymers can also exhibit a peak at a finite wavevector and enhanced scattering at ultralow wavevectors. Although consideration of dipolar interactions leads to attractive interactions between monomers, the enhanced scattering at ultralow wavevectors is predicted solely on the basis of the electrostatics of weakly inhomogeneous dipolar and ionic polymers without considering the effects of any aggregates or phase separation. Thus, we conclude that neither aggregation nor phase separation is necessary for observing the enhanced scattering at ultralow wavevectors in salt-free dipolar andmore » ionic polymers. For charge regulating ionic polymers, it is shown that electrostatic interactions between charged monomers get screened with a screening length, which depends not only on the concentration of “free” counterions and coions, but also on the concentration of “adsorbed” ions on the polymer chains. Qualitative comparisons with the experimental scattering curves for ionic and dipolar polymer melts are presented using the theory developed in this work.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1]
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  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1479790
Alternate Identifier(s):
OSTI ID: 1479600
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 16; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Kumar, Rajeev, Lokitz, Bradley S., Long, Timothy E., and Sumpter, Bobby G. Enhanced scattering induced by electrostatic correlations in concentrated solutions of salt-free dipolar and ionic polymers. United States: N. p., 2018. Web. doi:10.1063/1.5044637.
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Kumar, Rajeev, Lokitz, Bradley S., Long, Timothy E., & Sumpter, Bobby G. Enhanced scattering induced by electrostatic correlations in concentrated solutions of salt-free dipolar and ionic polymers. United States. https://doi.org/10.1063/1.5044637
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Kumar, Rajeev, Lokitz, Bradley S., Long, Timothy E., and Sumpter, Bobby G. Sun . "Enhanced scattering induced by electrostatic correlations in concentrated solutions of salt-free dipolar and ionic polymers". United States. https://doi.org/10.1063/1.5044637. https://www.osti.gov/servlets/purl/1479790.
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@article{osti_1479790,
title = {Enhanced scattering induced by electrostatic correlations in concentrated solutions of salt-free dipolar and ionic polymers},
author = {Kumar, Rajeev and Lokitz, Bradley S. and Long, Timothy E. and Sumpter, Bobby G.},
abstractNote = {Here, we present a generalized theory for studying the static monomer density-density correlation function (structure factor) in concentrated solutions and melts of dipolar as well as ionic polymers. The theory captures effects of electrostatic fluctuations on the structure factor and provides insights into the origin of experimentally observed enhanced scattering at ultralow wavevectors in salt-free ionic polymers. It is shown that the enhanced scattering can originate from a coupling between the fluctuations of electric polarization and monomer density. Local and non-local effects of the polarization resulting from finite sized permanent dipoles and ion-pairs in dipolar and charge regulating ionic polymers, respectively, are considered. Theoretical calculations reveal that, similar to the salt-free ionic polymers, the structure factor for dipolar polymers can also exhibit a peak at a finite wavevector and enhanced scattering at ultralow wavevectors. Although consideration of dipolar interactions leads to attractive interactions between monomers, the enhanced scattering at ultralow wavevectors is predicted solely on the basis of the electrostatics of weakly inhomogeneous dipolar and ionic polymers without considering the effects of any aggregates or phase separation. Thus, we conclude that neither aggregation nor phase separation is necessary for observing the enhanced scattering at ultralow wavevectors in salt-free dipolar and ionic polymers. For charge regulating ionic polymers, it is shown that electrostatic interactions between charged monomers get screened with a screening length, which depends not only on the concentration of “free” counterions and coions, but also on the concentration of “adsorbed” ions on the polymer chains. Qualitative comparisons with the experimental scattering curves for ionic and dipolar polymer melts are presented using the theory developed in this work.},
doi = {10.1063/1.5044637},
journal = {Journal of Chemical Physics},
number = 16,
volume = 149,
place = {United States},
year = {Sun Oct 28 00:00:00 EDT 2018},
month = {Sun Oct 28 00:00:00 EDT 2018}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1063/1.5044637
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Cited by: 6 works
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Figures / Tables:

FIG. 1 FIG. 1: Effects of non-local effects of the electric polarization (characterized by $x$ = β0b 2/6ζ$^{2}_{d}$) on location of the local minimum in the scattering intensity for dipolar polymer melts. Plots presented here are obtained from Eq. 9. The right hand side of Eq. 9 becomes a complex number formore » higher values of $x$ when $y$ < 8.5. In contrast, the right hand side of Eq. 9 becomes negative for higher values of $x$ when $y$ > 8.5.« less
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