Viscoelastic Properties of Semidilute Polyelectrolyte Solutions
Zero-shear viscosity η° and steady-state complinance Jc of poly(N-methyl-2-vinylpyridinium chloride) solutions were measured in the absence and presence of added-salt over a wide range of polymer concentration. The polymer concentration dependence of η° in semidilute regions increases with increasing added-salt concentrations Cs and almost agrees with that for non-ionic polymers in good solvents at high added-salt concentrations. JC in dilute regions depends on molecular weight M, polymer concentration C and Cs more strongly than that of non-ionic polymer solutions, as given by Jo ∝ M-2Cs. In entangled regions, on the other hand, Jc depends on polymer concentration only in the same manner as that of non-ionic polymer solutions, but its concentration dependence is weaker than that of non-ionic polymer solutions, as given by Je∝C-1.3. Moreover, the polymer concentration dependence of the weight-average relaxation time tw increases with increasing added-salt concentration in the semidilute region for η° and the entangled region for Jc. These viscoelastic properties of entangled-polyelectrolyte solutions can be well explained by the reptation model assuming that the correlation lengths related to entanglements are determined by the electrostatic interactions evaluated from the Donnan equilibrium.
KeywordsAnisotropy Titration Pyridine Macromolecule Dimethylformamide
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