Timescales of emulsion formation caused by anisotropic particles

Abstract: Particle stabilized emulsions have received an enormous interest in the recent past, but our understanding of the dynamics of emulsion formation is still limited. For simple spherical particles, the time dependent growth of fluid domains is dominated by the formation of droplets, particle adsorption and coalescence of droplets (Ostwald ripening), which eventually can be almost fully blocked due to the presence of the particles. Ellipsoidal particles are known to be more efficient stabilizers of fluid interfaces than spherical particles and their anisotropic shape and the related additional rotational degrees of freedom have an impact on the dynamics of emulsion formation. In this paper, we investigate this point by means of simple model systems consisting of a single ellipsoidal particle or a particle ensemble at a flat interface as well as a particle ensemble at a spherical interface. By applying combined multicomponent lattice Boltzmann and molecular dynamics simulations we demonstrate that the anisotropic shape of ellipsoidal particles causes two additional timescales to be of relevance in the dynamics of emulsion formation: a relatively short timescale can be attributed to the adsorption of single particles and the involved rotation of particles towards the interface. As soon as the interface is jammed, however, capillary interactions between the particles cause a local reordering on very long timescales leading to a continuous change in the interface configuration and increase of interfacial area. This effect can be utilized to counteract the thermodynamic instability of particle stabilized emulsions and thus offers the possibility to produce emulsions with exceptional stability.