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J. Chem. Phys. 119, 4085 (2003); http://dx.doi.org/10.1063/1.1592496 (14 pages)

Polyelectrolyte chain dimensions and concentration fluctuations near phase boundaries

V. M. Prabhu1, M. Muthukumar1, G. D. Wignall2, and Y. B. Melnichenko2

1Department of Polymer Science and Engineering, Materials Research Science and Engineering Center, University of Massachusetts, Amherst, Massachusetts 01003
2Oak Ridge National Laboratory, Condensed Matter Sciences, Oak Ridge, Tennessee 37831-6393

(Received 20 March 2003; accepted 23 May 2003)

We have measured the temperature (T) dependence of the correlation length (ξ) for concentration fluctuations in aqueous solutions of sodium–poly(styrene sulfonate) with a fixed level of added barium chloride salt. Apparent critical behavior is observed upon lowering the temperature to precipitation phase boundaries that complements our earlier work on salt-dependent behavior. We interpret experimental deviations from ξ−2 versus T−1 as crossover from the mean field to the Ising universality class. We also measured the radius of gyration (Rg) of labeled chains and ξ for semidilute polyelectrolyte solutions at low ionic strengths. We recovered the familiar result of ξ scaling with polymer concentration (Cp) and degree of polymerization (N), such that ξ = (73±9) N0Cp−0.48±0.03 [Å], and using SANS high concentration labeling Rg = (400±28)Cp−0.24±0.01 [Å] (for N = 577) and Rg = (2.8±2.1)N0.6±0.1 [Å] (for Cp = 206 gL−1), respectively. The indices recovered are in agreement with theoretical predictions for low ionic strength semidilute solutions. Such experiments offer insight into relatively unexplored phase behavior in charged macromolecular solutions. © 2003 American Institute of Physics.

© 2003 American Institute of Physics

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KEYWORDS and PACS

PACS

  • 61.25.H-

    Macromolecular and polymers solutions; polymer melts

  • 64.60.F-

    Equilibrium properties near critical points, critical exponents

ARTICLE DATA

PUBLICATION DATA

ISSN

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

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