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Title: Charge segregation in weakly ionized microgels

Abstract

Here we investigate microgels synthesized from N-isopropylacrylamide (NIPAM) copolymerized with a large mol% of acrylic acid, finding that when the acid groups are partially ionized at high temperatures, competition between ion-induced swelling and hydrophobic deswelling of poly(NIPAM) chains results in microphase separation. In cross-linked microgels, this manifests as a dramatic decrease in the ratio between the radius of gyration and the hydrodynamic radius to ~0.2, indicating that almost all the mass of the microgel is concentrated near the particle center. We also observe a concurrent decrease of the polymer network length scale via small-angle neutron scattering, confirming the presence of a dense, deswollen core surrounded by a diffuse, charged periphery. We compare these results to those obtained for a system of charged ultralow-cross-linked microgels; the form factor shows a distinct peak at high q when the temperature exceeds a threshold value. Lastly, we successfully fit the form factor to theory developed to describe scattering from weakly charged gels in poor solvents, and we tie this behavior to charge segregation in the case of the cross-linked microgels.

Authors:
 [1];  [2];  [3];  [3];  [4];  [1]
  1. Georgia Inst. of Technology, Atlanta, GA (United States). School of Physics
  2. Georgia Inst. of Technology, Atlanta, GA (United States). Wallace H. Coulter Dept. of Biomedical Engineering
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Biology and Soft Matter Division, Neutron Sciences Directorate
  4. Univ. of Virginia, Charlottesville, VA (United States). Dept. of Biomedical Engineering
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division; National Science Foundation (NSF)
OSTI Identifier:
1422543
Alternate Identifier(s):
OSTI ID: 1341312
Grant/Contract Number:  
AC05-00OR22725; DMR-1609841
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review E
Additional Journal Information:
Journal Volume: 95; Journal Issue: 1; Journal ID: ISSN 2470-0045
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Hyatt, John S., Douglas, Alison M., Stanley, Chris, Do, Changwoo, Barker, Thomas H., and Fernández-Nieves, Alberto. Charge segregation in weakly ionized microgels. United States: N. p., 2017. Web. doi:10.1103/PhysRevE.95.012608.
Hyatt, John S., Douglas, Alison M., Stanley, Chris, Do, Changwoo, Barker, Thomas H., & Fernández-Nieves, Alberto. Charge segregation in weakly ionized microgels. United States. doi:10.1103/PhysRevE.95.012608.
Hyatt, John S., Douglas, Alison M., Stanley, Chris, Do, Changwoo, Barker, Thomas H., and Fernández-Nieves, Alberto. Thu . "Charge segregation in weakly ionized microgels". United States. doi:10.1103/PhysRevE.95.012608. https://www.osti.gov/servlets/purl/1422543.
@article{osti_1422543,
title = {Charge segregation in weakly ionized microgels},
author = {Hyatt, John S. and Douglas, Alison M. and Stanley, Chris and Do, Changwoo and Barker, Thomas H. and Fernández-Nieves, Alberto},
abstractNote = {Here we investigate microgels synthesized from N-isopropylacrylamide (NIPAM) copolymerized with a large mol% of acrylic acid, finding that when the acid groups are partially ionized at high temperatures, competition between ion-induced swelling and hydrophobic deswelling of poly(NIPAM) chains results in microphase separation. In cross-linked microgels, this manifests as a dramatic decrease in the ratio between the radius of gyration and the hydrodynamic radius to ~0.2, indicating that almost all the mass of the microgel is concentrated near the particle center. We also observe a concurrent decrease of the polymer network length scale via small-angle neutron scattering, confirming the presence of a dense, deswollen core surrounded by a diffuse, charged periphery. We compare these results to those obtained for a system of charged ultralow-cross-linked microgels; the form factor shows a distinct peak at high q when the temperature exceeds a threshold value. Lastly, we successfully fit the form factor to theory developed to describe scattering from weakly charged gels in poor solvents, and we tie this behavior to charge segregation in the case of the cross-linked microgels.},
doi = {10.1103/PhysRevE.95.012608},
journal = {Physical Review E},
number = 1,
volume = 95,
place = {United States},
year = {2017},
month = {1}
}

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