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:
-
- Georgia Inst. of Technology, Atlanta, GA (United States). School of Physics
- Georgia Inst. of Technology, Atlanta, GA (United States). Wallace H. Coulter Dept. of Biomedical Engineering
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Biology and Soft Matter Division, Neutron Sciences Directorate
- 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). 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. https://doi.org/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. https://doi.org/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 = {Thu Jan 19 00:00:00 EST 2017},
month = {Thu Jan 19 00:00:00 EST 2017}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 11 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Temperature-sensitive poly(N-Isopropyl-Acrylamide) microgel particles: A light scattering study
journal, November 2008
- Reufer, M.; Dıaz-Leyva, P.; Lynch, I.
- The European Physical Journal E, Vol. 28, Issue 2
Predictions of Bound Water Content in Poly( N -isopropylacrylamide) Gel †
journal, January 1997
- Lele, A. K.; Hirve, M. M.; Badiger, M. V.
- Macromolecules, Vol. 30, Issue 1
Effect of Cross-Link Density on the Internal Structure of Poly( N -isopropylacrylamide) Microgels
journal, September 2001
- Varga, Imre; Gilányi, Tibor; Mészáros, Róbert
- The Journal of Physical Chemistry B, Vol. 105, Issue 38
Eine neue Bestimmung der Moleküldimensionen
journal, January 1906
- Einstein, A.
- Annalen der Physik, Vol. 324, Issue 2
Small-angle neutron scattering study of structural changes in temperature sensitive microgel colloids
journal, April 2004
- Stieger, Markus; Richtering, Walter; Pedersen, Jan Skov
- The Journal of Chemical Physics, Vol. 120, Issue 13
Responsive core-shell microgels: Synthesis, characterization, and possible applications
journal, May 2013
- Hellweg, Thomas
- Journal of Polymer Science Part B: Polymer Physics, Vol. 51, Issue 14
An Improved Representative Equation for the Dynamic Viscosity of Water Substance
journal, October 1980
- Watson, J. T. R.; Basu, R. S.; Sengers, J. V.
- Journal of Physical and Chemical Reference Data, Vol. 9, Issue 4
Surface grafting of thermoresponsive microgel nanoparticles
journal, January 2011
- Seeber, Michael; Zdyrko, Bogdan; Burtovvy, Ruslan
- Soft Matter, Vol. 7, Issue 21
Segregation of mass at the periphery of -isopropylacrylamide-co-acrylic-acid microgels at high temperatures
journal, September 2015
- Hyatt, John S.; Do, Changwoo; Hu, Xiaobo
- Physical Review E, Vol. 92, Issue 3
A statistical theory of weakly charged polyelectrolytes: fluctuations, equation of state and microphase separation
journal, November 1988
- Borue, V. Yu.; Erukhimovich, I. Ya.
- Macromolecules, Vol. 21, Issue 11
Influence of Reaction Conditions on the Synthesis of Self-Cross-Linked N -Isopropylacrylamide Microgels
journal, June 2003
- Gao, Jun; Frisken, Barbara J.
- Langmuir, Vol. 19, Issue 13
Small‐angle neutron scattering study on weakly charged temperature sensitive polymer gels
journal, November 1992
- Shibayama, Mitsuhiro; Tanaka, Toyoichi; Han, Charles C.
- The Journal of Chemical Physics, Vol. 97, Issue 9
Normal stresses in colloidal dispersions
journal, May 1995
- Brady, John F.; Vicic, Michael
- Journal of Rheology, Vol. 39, Issue 3
Small angle neutron scattering study on poly(N‐isopropyl acrylamide) gels near their volume‐phase transition temperature
journal, November 1992
- Shibayama, Mitsuhiro; Tanaka, Toyoichi; Han, Charles C.
- The Journal of Chemical Physics, Vol. 97, Issue 9
Cross-Linker-Free N -Isopropylacrylamide Gel Nanospheres
journal, June 2003
- Gao, Jun; Frisken, Barbara J.
- Langmuir, Vol. 19, Issue 13
Berichtigung zu meiner Arbeit: „Eine neue Bestimmung der Moleküldimensionen”
journal, January 1911
- Einstein, A.
- Annalen der Physik, Vol. 339, Issue 3
Ultrasoft, highly deformable microgels
journal, January 2015
- Bachman, Haylee; Brown, Ashley C.; Clarke, Kimberly C.
- Soft Matter, Vol. 11, Issue 10
The extended Q -range small-angle neutron scattering diffractometer at the SNS
journal, July 2010
- Zhao, J. K.; Gao, C. Y.; Liu, D.
- Journal of Applied Crystallography, Vol. 43, Issue 5
Kinetic Prediction of Functional Group Distributions in Thermosensitive Microgels
journal, October 2006
- Hoare, Todd; McLean, Daniel
- The Journal of Physical Chemistry B, Vol. 110, Issue 41
Colloidal nature of star polymer dilute and semidilute solutions
journal, May 1991
- Dozier, William D.; Huang, John S.; Fetters, Lewis J.
- Macromolecules, Vol. 24, Issue 10
Ultrasoft microgels displaying emergent platelet-like behaviours
journal, September 2014
- Brown, Ashley C.; Stabenfeldt, Sarah E.; Ahn, Byungwook
- Nature Materials, Vol. 13, Issue 12
Temperature-programmed synthesis of micron-sized multi-responsive microgels
journal, January 2009
- Meng, Zhiyong; Smith, Michael H.; Lyon, L. Andrew
- Colloid and Polymer Science, Vol. 287, Issue 3
The effect of Brownian motion on the bulk stress in a suspension of spherical particles
journal, November 1977
- Batchelor, G. K.
- Journal of Fluid Mechanics, Vol. 83, Issue 1
The kinetics of poly(N-isopropylacrylamide) microgel latex formation
journal, April 1994
- Wu, X.; Pelton, R. H.; Hamielec, A. E.
- Colloid & Polymer Science, Vol. 272, Issue 4
Works referencing / citing this record:
Synthesis of smart dual-responsive microgels: correlation between applied surfactants and obtained particle morphology
journal, January 2019
- Wiehemeier, Lars; Brändel, Timo; Hannappel, Yvonne
- Soft Matter, Vol. 15, Issue 28
Numerical insights on ionic microgels: structure and swelling behaviour
journal, January 2019
- Del Monte, Giovanni; Ninarello, Andrea; Camerin, Fabrizio
- Soft Matter, Vol. 15, Issue 40