Pickering stabilization mechanism revealed through direct imaging of particles with tuneable contact angle in a phase-separated binary solvent.

Pickering emulsions have attracted increasing attention from multiple fields, including food, cosmetics, healthcare, pharmaceutical, and agriculture. Their stability relies on the presence of colloidal particles instead of surfactant at the droplet interface, providing steric stabilization. Here, we demonstrate the microscopic attachment and detachment of particles with tunable contact angle at the interface underlying the Pickering emulsion stability. We vary the interfacial tension continuously by varying the temperature offset of a phase-separated binary liquid from its critical point, and employ confocal microscopy to directly observe the particles at the interface to determine their coverage and contact angle as a function of the varying interfacial tension. When the interfacial tension decreases upon approaching the binary liquid's critical point, the contact angle and detachment energy (ΔE) drop, and the particles move out of the interface. Microscopic imaging suggests necking and capillary interactions lead to clustering of the particles, before they eventually desorb from the interface. Macroscopic measurements show that concomitantly, coalescence takes place, and the emulsion loses its stability. These results reveal the interplay of interfacial energies, contact angle and surface coverage that underlies the Pickering emulsion stability, opening up ways to manipulate and design the stability through the microscopic behavior of the adsorbed particles.