Viscosity of Semidilute and Concentrated Nonentangled Flexible Polyelectrolytes in Salt-Free Solution

We report viscosity data of nonentangled sodium polystyrene sulfonate (NaPSS) in salt-free aqueous solution as a function of polymer concentration ( c) and degree of polymerization ( N). Different empirical equations are examined and found not to describe the semidilute solution viscosity over a wide concentration range and/or to yield values of [η] that do not match dilute solution measurements. Deviations from the scaling prediction of η_sp ∝ c^1/2 (Fuoss' law) are observed at high concentrations. Specifically, we find η_sp ≈ N^1.26 c^1/2 e^{1.4 c} in the semidilute regime, which agrees with the scaling prediction only for c ≲ 0.02 M. The viscosity data presented in this study and in earlier reports show a high degree of consistency. A comparison with diffusion measurements for NaPSS in salt-free solution by Oostwal and co-workers suggests that the disagreement between the scaling theory and experiments does not arise solely from the concentration dependence of the monomeric friction coefficient.