Rheology of dilute polyelectrolyte solutions

Abstract

The flow properties of polyelectrolyte solutions have been studied using narrow molecular weight polystyrene sulphonate (PSS) samples of different molecular weight. In salt-free solutions the viscosity behaviour was characteristically dependent on the molecular weight of the polyelectrolyte. For low molecular weight samples the simple classical behaviour was observed, the reduced viscosity of the solution increasing sharply on dilution. The shear dependence of viscosity was low in general, but increased on dilution in parallel with the increase of reduced viscosity. For high molecular weights the reduced viscosity reached a maximum on dilution, followed by a rapid decrease on further dilution of the solutions. The viscosity was strongly shear-dependent and approached infinity at low shearing stresses. At low concentrations the reduced viscosity of HPSS solutions was markedly higher than that of NaPSS solutions, the difference vanishing at higher concentrations. These findings indicate that the viscosity behaviour of salt-free polyelectrolyte solutions is essentially determined by strong electrostatic interactions between highly expanded polyion chains, with the possible formation of ordered quasicrystalline structures in dilute solutions.