Nano ellipsoids at the fluid-fluid interface: effect of surface charge on adsorption, buckling and emulsification

In this contribution, we discuss the role of surface charge on the adsorption of shape anisotropic particles to fluid-fluid interfaces in the context of their application in particle-stabilized emulsions. Starting with a pendent aqueous drop containing nano-ellipsoids of known surface charge density suspended in an oil medium, we study the kinetics of adsorption of the ellipsoids to the water-decane interface using pendant drop tensiometry. The interfacial tension of the drop is recorded as a function of time by analyzing the shape of the drop. We show that the particles that are weakly charged readily adsorb to the water-decane interface and the adsorption behavior is influenced by the particle surface charge density. Furthermore, as the area available for the particles deposited at the interface is reduced, the interface populated with self-assembled ellipsoids shows wrinkles indicating buckling of the particle-laden interface under compression. However, the buckling is not observed if nano-ellipsoids are highly charged confirming that the particles do not adsorb to the interface when they are highly charged. This suggests that in several examples where the particles at interfaces concept is exploited, the repulsive energy barrier due to the particle surface charge plays a key role in the adsorption of particles to the interfaces. However, once the particles are adsorbed, the interfacial properties of the monolayer depend on the particle-particle interactions. Thus a combination of these interactions determines the concentration of particles at the interface, their microstructure and interfacial properties. The effect of these interactions on the quantity and size of the emulsion drops stabilized by ellipsoidal particles is also explored.