Macromolecules, Vol.50, No.1, 332-338, 2017
Viscosity and Scaling of Semiflexible Polyelectrolyte NaCMC in Aqueous Salt Solutions
We investigate the viscosity dependence on concentration and molecular weight of semiflexible polyelectrolyte sodium carboxyrnethylcellulose (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 (c(s)) concentrations. In salt-free solution, the overlap concentration shows the expected c* proportional to N-2 dependence, and the entanglement crossover scales as c(e) proportional to N-0.6 +/- 0.3 in strong disagreement with scaling theory for which c(e) proportional to c* is expected, but matching the behavior found for flexible polyelectrolytes. A second crossover, to a steep concentration dependence for specific viscosity (eta(sp) proportional to c(3.5 +/- 0.2)), commonly assigned to the concentrated regime, is shown to follow c** proportional to N-0.6 +/- 0.2 (with c**/c(e) similar or equal to 6) which thus suggests instead a dynamic crossover, possibly related to entanglement. The scaling of c* and c(e) in 0.01 and 0.1 M NaCl shows neutral polymer in good solvent behavior, characteristic of highly screened polyelectrolyte solutions. This unified scaling picture enables the estimation of viscosity of ubiquitous NaCMC solutions as a function of N, c, and c(s) and establishes the behavior expected for a range of semiflexible polyelectrolyte solutions.