Colloids with Continuously Tunable Surface Charge

In this paper, we present a robust way to tune the surface potential of polystyrene colloids without changing the pH, ionic strength, etc. The colloids are composed of a cross-linked polystyrene core and a cross-linked vinylbenzyl chloride layer. Besides the chlorine groups, the particle surface contains sulfate/sulfonate groups (arising from the polymerization initiators) that provide a negative surface potential. Performing a Menschutkin reaction on the surface chlorine groups with tertiary amines allows us to introduce quaternary, positively charged amines. The overall charge on the particles is then determined by the ratio between the sulfate/sulfonate moieties and the quaternary amines. Using this process, we were able to invert the charge in a continuous manner without losing colloidal stability upon passing the isoelectric point. The straightforward reaction mechanism together with the fact that the reaction could be quenched rapidly resulted in a colloidal system in which the ζ potential can be tuned between −80 and 45 mV. As proof of principle, the positively charged particles were used in heterocoagulation experiments with nanometer- and micrometer-sized negatively charged silica particles to create geometrically well-defined colloidal (nano) clusters.