Forces between Surfaces across Nanoparticle Solutions:  Role of Size, Shape, and Concentration

Using a surface force apparatus, we have measured the normal forces between mica surfaces across various types of nanoparticles consisting of ZnS cores coated with a monolayer of physisorbed surfactant, dispersed in organic solvents. We focused on the effects of nanoparticle size, shape, and concentration on the force−distance profiles. Forces were exponentially repulsive when the surfactant layers were strongly bound to the nanoparticles and were roughly linear when there was adhesion between the nanoparticle cores, i.e., when the surfactant layers detached from the nanoparticles. In both cases, the range and magnitude of the forces were dependent upon the particle size, shape, and solution concentration. Fine details in the otherwise smooth force−distance profiles indicate specific effects due to particle chemistry and geometry and the existence of first-order disorder−order phase transitions upon confinement. Small amounts of water in the (hydrophobic) organic solvents had dramatic effects on the measured forces. Understanding and controlling the effects of particle shape, size, and concentration and the presence of water (or other surface-active solutes) on particle−particle and particle−surface interactions are important for the processing of nanoparticles into ordered superstructured materials.