Understanding the multiple orientations of isolated superellipsoidal hematite particles at the oil–water interface

Abstract

Non-spherical particles have the potential to adopt multiple orientations once adhered to a liquid–liquid interface. In this work we combine simulations and experiments to investigate the behaviour of an isolated microscopic hematite particle of superellipsoidal shape. We show that this microparticle can adopt one of three orientations when adhered to a hexadecane–water interface. Two of the orientations, and estimates for their relative populations, could be assigned to two thermodynamic minima on the energy landscape as generated through both free-energy minimization and particle trajectory simulations. The third orientation was found to correspond to a kinetically trapped state, existing on certain particle trajectories in a region of a negligible gradient in free energy. To underpin the simulations the individual orientation of a set of 100 isolated particles was explored by means of scanning electron microscopy (SEM) using the gel trapping technique as a tool. Atomic force microscopy (AFM) was additionally used to support the experimental findings. This is the first example of such a kinetic metastable state being observed for particles at liquid–liquid interfaces.