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Monte Carlo simulations of defect-free cross-linked gels in the presence of salt

Edgecombe, Samuel LU ; Schneider, Stefanie LU and Linse, Per LU (2004) In Macromolecules 37(26). p.10089-10100
Abstract
Properties of polyelectrolyte gels in equilibrium with a reservoir of salt solution described within the primitive model have been investigated using Monte Carlo simulations. The polyelectrolyte gel was modeled as a charged defect-free three-dimensional network of diamondlike topology with explicit simple ions. The deswelling upon addition of salt was investigated for gels with different charge density, cross-linking density, chain flexibility, and counterion valence. All polyelectrolyte gels underwent a deswelling upon addition of salt. In most systems, however, even at high salt concentration, the equilibrium volumes remained significantly larger than those of the corresponding uncharged gels, and the salt concentration in the gel... (More)
Properties of polyelectrolyte gels in equilibrium with a reservoir of salt solution described within the primitive model have been investigated using Monte Carlo simulations. The polyelectrolyte gel was modeled as a charged defect-free three-dimensional network of diamondlike topology with explicit simple ions. The deswelling upon addition of salt was investigated for gels with different charge density, cross-linking density, chain flexibility, and counterion valence. All polyelectrolyte gels underwent a deswelling upon addition of salt. In most systems, however, even at high salt concentration, the equilibrium volumes remained significantly larger than those of the corresponding uncharged gels, and the salt concentration in the gel remained smaller than that in the reservoir. The salt content in the gel was larger as compared to that predicted by an ideal Donnan equilibrium due to a more negative excess chemical potential of the salt in the gel as compared to that in the reservoir. The predictions of the Flory-Rehner-Donnan theory were qualitatively in agreement with our results, but they displayed significant quantitative disagreement, mainly due to an overestimated contribution from the counterions to the osmotic pressure. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Macromolecules
volume
37
issue
26
pages
10089 - 10100
publisher
The American Chemical Society
external identifiers
  • wos:000225932900064
  • scopus:11444252007
ISSN
0024-9297
DOI
10.1021/ma0486391
language
English
LU publication?
yes
id
001e42eb-0234-4870-8f87-4275827a1e90 (old id 153769)
date added to LUP
2007-07-11 10:35:01
date last changed
2017-09-10 03:41:51
@article{001e42eb-0234-4870-8f87-4275827a1e90,
  abstract     = {Properties of polyelectrolyte gels in equilibrium with a reservoir of salt solution described within the primitive model have been investigated using Monte Carlo simulations. The polyelectrolyte gel was modeled as a charged defect-free three-dimensional network of diamondlike topology with explicit simple ions. The deswelling upon addition of salt was investigated for gels with different charge density, cross-linking density, chain flexibility, and counterion valence. All polyelectrolyte gels underwent a deswelling upon addition of salt. In most systems, however, even at high salt concentration, the equilibrium volumes remained significantly larger than those of the corresponding uncharged gels, and the salt concentration in the gel remained smaller than that in the reservoir. The salt content in the gel was larger as compared to that predicted by an ideal Donnan equilibrium due to a more negative excess chemical potential of the salt in the gel as compared to that in the reservoir. The predictions of the Flory-Rehner-Donnan theory were qualitatively in agreement with our results, but they displayed significant quantitative disagreement, mainly due to an overestimated contribution from the counterions to the osmotic pressure.},
  author       = {Edgecombe, Samuel and Schneider, Stefanie and Linse, Per},
  issn         = {0024-9297},
  language     = {eng},
  number       = {26},
  pages        = {10089--10100},
  publisher    = {The American Chemical Society},
  series       = {Macromolecules},
  title        = {Monte Carlo simulations of defect-free cross-linked gels in the presence of salt},
  url          = {http://dx.doi.org/10.1021/ma0486391},
  volume       = {37},
  year         = {2004},
}