Interparticle forces arising from an adsorbed strong polyelectrolyte in colloidal dispersions: charged patch attraction

Abstract

Adsorbed polystyrene sulphonate (PSS) shifts the pH of the zero zeta potential, pH_ς = 0, of ZrO₂ to a lower pH. The positive charge density of ZrO₂ at pH = pH_ς=0 determined from the amount of PSS adsorbed was in excellent agreement with that obtained from charge titration. Polystyrene sulphonic acid shifts pH_ς=0 to a greater degree compared with polyacrylic acid because it is a much stronger acid. A patch is likely to just consist of one adsorbed molecule. The patch is negative when the charges of the molecule exceed the underlying positive surface charge. Attraction between the negative patch and the bare positive surface of a second particle is responsible for increasing the yield stress of concentrated ZrO₂ dispersions at pH_ς=0. Its magnitude is only of the order of the van der Waals attraction. Increasing ionic strength and patch misalignment diminish the attraction. The upper limit of the patch area was estimated from the radius of gyration of the molecule in solution. With a known patch area, the patch charged density can be calculated. With the selection of an appropriate patch area, the yield stress due to charged patch attraction increases linearly with the product of the negative and positive patch densities.