Counterion condensation and phase separation in solutions of hydrophobic polyelectrolytes

Citation
Av. Dobrynin et M. Rubinstein, Counterion condensation and phase separation in solutions of hydrophobic polyelectrolytes, MACROMOLEC, 34(6), 2001, pp. 1964-1972
Citations number
38
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
MACROMOLECULES
ISSN journal
00249297 → ACNP
Volume
34
Issue
6
Year of publication
2001
Pages
1964 - 1972
Database
ISI
SICI code
0024-9297(20010313)34:6<1964:CCAPSI>2.0.ZU;2-6
Abstract
We have developed a theory of counterion condensation in solutions of hydro phobic polyelectrolytes. In the framework of Oosawa's two-zone model we dem onstrate that solutions of necklaces can be unstable with respect to phase separation. This phase separation is triggered by the concentration-induced counterion condensation. For the range of parameters at which the polyelec trolyte solution is stable, we predict nonmonotonic dependence of the chain size on polymer concentration. This nonmonotonicity in the chain size mani fests itself in the dramatic increase in solution viscosity at the crossove r to concentrated polyelectrolyte solution. There is also a possibility of two peaks in the scattering function of qualitatively different physical na ture observed in different concentration regimes. The scattering intensity at the peak position increases with polymer concentration in low concentrat ion (necklace) regime and decreases with concentration in concentrated poly electrolyte solutions.