Investigation of a 31 Charged Cationic Polyelectrolyte Interacting with Sodium Dodecyl Sulfate in Bulk Solution and as a Preadsorbed Layer on Mica. Low Ionic Strength

The behavior of mixtures of a cationic polyelectrolyte of intermediate charge density (31%) and anionic surfactant both in bulk and at a negatively charged solid surface has been investigated. The polyelectrolyte employed was a random copolymer of the neutral acrylamide and cationic [3-(2-methylpropionamido)propyl]trimethylammonium chloride, and the surfactant was sodium dodecyl sulfate (SDS). Measurements of flocculation and electrophoretic mobility in bulk solution clearly showed a phase separation with a maximum in turbidity corresponding roughly to charge neutralization of the polyelectrolyte/surfactant complex. Conductivity measured at low SDS concentrations showed a strong uptake of ions by the polyelectrolyte at a critical SDS concentration. The interferometric surface force apparatus was used to measure forces between muscovite mica surfaces onto which the polyelectrolyte was adsorbed from a 20 ppm, 10 - 4 M KBr solution. After the polymer solution was replaced with polymer-free 10 - 4 M KBr solution, a weak long range double-layer repulsion was observed between approaching surfaces, with a bridging attraction dominating at smaller separations. A weak adhesion was observed upon separating the surfaces. Addition of 4.2 × 10 - 4 M SDS caused a large swelling of the preadsorbed polymer layer due to formation of an associative complex between the polymer and surfactant. Further increasing the SDS concentration decreased the force and layer thickness due to screening of the electrostatic repulsion within the layers and some desorption of polymer molecules. That a slight desorption did occur was supported by electron spectroscopy for chemical analysis measurements. The results broaden the understanding of the effect of polyelectrolyte charge density on the interaction of preadsorbed polyelectrolyte layers with oppositely charged surfactants.