The forces between colloidal particles at a decane-water interface, in the presence of low concentrations of a monovalent salt (NaCl) and of the surfactant sodium dodecylsulfate (SDS) in the aqueous subphase, have been studied using laser tweezers. In the absence of electrolyte and surfactant, particle interactions exhibit a long-range repulsion, yet the variation of the interaction for different particle pairs is found to be considerable. Averaging over several particle pairs was hence found to be necessary to obtain reliable assessment of the effects of salt and surfactant. It has previously been suggested that the repulsion is consistent with electrostatic interactions between a small number of dissociated charges in the oil phase, leading to a decay with distance to the power -4 and an absence of any effect of electrolyte concentration. However, the present work demonstrates that increasing the electrolyte concentration does yield, on average, a reduction of the magnitude of the interaction force with electrolyte concentration. This implies that charges on the water side also contribute significantly to the electrostatic interactions. An increase in the concentration of SDS leads to a similar decrease of the interaction force. Moreover the repulsion at fixed SDS concentrations decreases over longer times. Finally, measurements of threebody interactions provide insight into the anisotropic nature of the interactions. The unique time-dependent and anisotropic interactions between particles at the oil-water interface allow tailoring of the aggregation kinetics and structure of the suspension structure.2

We study the equilibrium orientation of nonspherical Janus particles at an oil-water interface. Two types of nonspherical Janus particles are considered: Janus ellipsoids and Janus dumbbells. To find their equilibrium orientation, we calculate and minimize the attachment energy of each Janus particle as a function of its orientation angle with respect to the oil-water interface. We find that the equilibrium orientation of the interface trapped Janus particles strongly depends on the particle characteristics, such as their size, aspect ratio, and surface properties. In general, nonspherical Janus particles adopt the upright orientation (i.e., the long axis of ellipsoids or dumbbells is perpendicular to the interface) if the difference in the wettability of the two sides is large or if the particle aspect ratio is close to 1. In contrast, Janus particles with a large aspect ratio or a small difference in the wettability of the two regions tend to have a tilted orientation at equilibrium. Moreover, we find that Janus ellipsoids, under appropriate conditions, can be kinetically trapped in a metastable state due to the presence of a secondary energy minimum. In contrast, Janus dumbbells possess only a primary energy minimum, indicating that these particles prefer to be in a single orientation. The absence of a secondary minimum is potentially advantageous for obtaining particle layers at fluid-fluid interfaces with uniform orientation. Our calculation provides a detailed guidance for synthesizing nonspherical Janus particles that can be used as effective solid surfactants for the stabilization of multiphasic fluid mixtures and the modification of the rheological properties of fluid interfaces.

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The electrostatic interaction of charged spherical colloids trapped at an interface between a nonpolar medium and water is analyzed. Complementary experiments provide consistent values for the dipole-dipole interaction potential over a wide range of interparticle distances. After accounting for the contribution from the compact inner double layer arising from the finite size of the counterions, we demonstrate quantitative agreement between experiments and nonlinear Poisson-Boltzmann theory. We find that the inner layer contribution dominates the electrostatic interaction in the far field for particles pinned at the interface. This result is fundamentally different from screened electrostatic interactions in the bulk and could contribute to the further understanding of the structure of the compact counterion layer in highly charged systems.