Adsorption of Polyelectrolyte–Nanoparticle Systems on Silica: Influence on Interaction Forces

In this work, we have studied the interfacial properties of cationic polyelectrolyte (PE) and silica nanoparticle (NP) systems at macroscopic silica surfaces by means of ellipsometry. The influence of adsorbed layers on the interactions between silica surfaces was also investigated using the bimorph surface force apparatus. Added nanoparticles were observed to strongly swell the interfacial polyelectrolyte layers, an effect partly related to neutralization of charged polyelectrolyte groups. The effect was more pronounced for low charged than for highly charged polyelectrolytes. Overall, the presence of nanoparticles seemed to increase the repulsive interaction measured between silica surfaces. The force measured on approach was long range and quite strongly repulsive. On separation, an attractive bridging interaction was measured for polyelectrolyte-covered surfaces. For the low charged polyelectrolyte used in the study, the force turned repulsive on addition of nanoparticles. For the highly charged polyelectrolyte used, a change from a very strong attraction (involving a jump of the surfaces out of contact) to a very long-range elastic attractive force was observed on adding nanoparticles. The long-range elastic force indicates that polymer chains and nanoparticles form a transient network in the gap between the surfaces. The observed difference in the outward force curves may explain why the addition of nanoparticles appears to improve, e.g., shear-resistance and reflocculation characteristics of polymeric flocculants.