Surface Forces between Highly Charged Cationic Polyelectrolytes Adsorbed to Silica: How Control of pH and the Adsorbed Amount Determines the Net Surface Charge

Atomic force microscopy (AFM) and quartz crystal microbalance with dissipation (QCM-D) were employed to investigate the pH-dependent adsorption of poly(diallyldimethylammonium chloride) (polyDADMAC) to silica surfaces as well as the surface forces between these layers. It was found that polyDADMAC adopted a relatively flat conformation when adsorbed to a silica surface and that the adsorbed amount increased with increasing pH. From the surface force measurements it is evident that the surface undergoes a charge reversal upon saturation with polyDADMAC, at the three different investigated pH values, and that some degree of charge regulation of the silica surface takes place during the adsorption process. Finally, the overcharging phenomenon is discussed in terms of a geometrical mismatch due to the different average spacing between the surface charges on the silica surface and the size of the DADMAC monomer.