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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
(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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