Colloidal Depletion and Structural Force Synergism or Antagonism in Solutions of Mutually Repelling Polyelectrolytes and Ionic Surfactants.

Depletion and structural forces were measured between a silica sphere and plate in solutions containing sodium polyacrylate (Na-PAA) anionic polyelectrolyte and sodium dodecyl sulfate (SDS) anionic surfactant using colloidal probe atomic force microscopy, at high pH where the two species are electrostatically repelling from each other and from the silica surfaces. Measurements were performed for a range of SDS and Na-PAA concentrations to span conditions where only one of the species or both of the species would exert a detectable depletion or structural force when present in a single-component solution. In mixed solutions, conditions were identified (i) where depletion attraction was synergistically enhanced or antagonistically weakened relative to single component solutions; (ii) where the range of the depletion attraction was significantly extended and the repulsive structural force barrier was eliminated, due to simultaneous depletion of both species over different length scales; and (iii) where one species was the dominant depletant and forces in mixtures were indistinguishable from those in a single component solution of the dominant depletant. Force measurements were interpreted with the aid of pyrene solubilization assays of SDS micellization and dynamic light scattering investigation of the state of assembly of the polyelectrolyte or surfactant. The variety of colloidal force effects were attributed to ionic strength and excluded volume effects of Na-PAA on SDS micellization, ionic strength effects of SDS on Na-PAA chain clustering in solution, and ionic strength effects on the counterion contribution to polyelectrolyte osmotic pressure. While prior studies have shown that depletion force synergism occurs when polymers and surfactants form mixed complexes, this work shows that it can occur in noncomplexing mixtures as well, and it indicates the variety of effects that should be taken into account when attempting to predict forces in such mixtures.