Demulsification of Pickering emulsions: advances in understanding mechanisms to applications

Pickering emulsions are ultra-stable dispersions of two immiscible fluids stabilized by solid or microgel particles rather than molecular surfactants. Although their ultra-stability is a signature performance indicator, often such high stability hinders their demulsification, i.e., prevents the droplet coalescence that is needed for phase separation on demand, or release of the active ingredients encapsulated within droplets and/or to recover the particles themselves, which may be catalysts, for example. This review aims to provide theoretical and experimental insights on demulsification of Pickering emulsions, in particular identifying the mechanisms of particle dislodgment from the interface in biological and non-biological applications. Even though the adhesion of particles to the interface can appear irreversible, it is possible to detach particles via (1) alteration of particle wettability, and/or (2) particle dissolution, affecting the particle radius by introducing a range of physical conditions: pH, temperature, heat, shear, or magnetic fields; or via treatment with chemical/biochemical additives, including surfactants, enzymes, salts, or bacteria. Many of these changes ultimately influence the interfacial rheology of the particle-laden interface, which is sometimes underestimated. There is increasing momentum to create responsive Pickering particles such that they offer switchable wettability (demulsification and re-emulsification) when these conditions are changed. Demulsification via wettability alteration seems like the modus operandi whilst particle dissolution remains only partially explored, largely dominated by food digestion-related studies where Pickering particles are digested using gastrointestinal enzymes. Overall, this review aims to stimulate new thinking about the control of demulsification of Pickering emulsions for release of active ingredients associated with these ultra-stable emulsions.