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Simulation of nonlinear shear rheology of dilute salt-free polyelectrolyte solutions

J. Chem. Phys. 126, 124906 (2007); doi:10.1063/1.2712182

Published 26 March 2007

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Christopher Stoltz, Juan J. de Pablo, and Michael D. Graham
Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706-1691
Brownian dynamics simulations are used to conduct a systematic analysis of the nonlinear shear rheology of dilute polyelectrolyte solutions, exploring its relationship to shear rate, Bjerrum length, and concentration. A simple coarse-grained bead-spring chain model that incorporates explicit counterions is used. It is found that the polyelectrolyte chains exhibit a shear thinning behavior at high shear rate (as characterized by bead Peclet number Pe) that is independent of the electrostatic strength due to the stripping of ions from close proximity to the chain caused by the flow. In contrast, at low values of Pe, the viscosity increases monotonically with increasing Bjerrum length over the range studied here, in contrast to the nonmonotonic trend displayed by the chain size. Furthermore, at fixed Bjerrum length, the reduced viscosity increases monotonically with concentration. The mechanism underlying these observations is essentially the primary electroviscous effect; the ion cloud surrounding a polyelectrolyte chain deforms in flow, causing a significant increase in viscosity as concentration increases. Finally, the authors have also considered the role of hydrodynamic interactions in these simulations, finding that for low concentration studies in shear flow, these do not qualitatively affect the results. ©2007 American Institute of Physics
History: Received 16 May 2006; accepted 2 February 2007; published 26 March 2007
Permalink: http://link.aip.org/link/?JCPSA6/126/124906/1
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KEYWORDS and PACS

Keywords
PACS
  • 83.80.Rs
    Polymer solutions (rheology)
  • 83.60.Fg
    Shear rate dependent viscosity
  • 83.10.Mj
    Molecular dynamics, Brownian dynamics in rheology
  • 83.50.Ax
    Steady shear flows, viscometric flow
  • 82.45.Gj
    Electrolytes (electrochemistry)
  • 82.45.Wx
    Polymers and organic materials in electrochemistry
  • YEAR: 2007

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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