Viscosity and Scaling of Semiflexible Polyelectrolyte NaCMC in Aqueous Salt Solutions

Abstract

We investigate the viscosity dependence on concentration and molecular weight of semiflexible polyelectrolyte sodium carboxymethylcellulose (NaCMC) in aqueous salt-free and NaCl solutions. Combining new measurements and extensive literature data, we establish relevant power laws and crossovers over a wide range of degree of polymerization (N) as well as polymer (c) and salt (cs) concentrations. In salt-free solution, the overlap concentration shows the expected c* ∝ N–2 dependence, and the entanglement crossover scales as ce ∝ N–0.6±0.3, in strong disagreement with scaling theory for which ce ∝ c* is expected, but matching the behavior found for flexible polyelectrolytes. A second crossover, to a steep concentration dependence for specific viscosity (ηsp ∝ c3.5±0.2), commonly assigned to the concentrated regime, is shown to follow c** ∝ N–0.6±0.2 (with c**/ce ≃ 6) which thus suggests instead a dynamic crossover, possibly related to entanglement. The scaling of c* and ce in 0.01 and 0.1 M NaCl shows neutra...