Responsive emulsions stabilized by stimuli-sensitive microgels: emulsions with special non-Pickering properties

Langmuir. 2012 Dec 18;28(50):17218-29. doi: 10.1021/la302331s. Epub 2012 Oct 17.

Abstract

Recent studies revealing the unique properties of microgel-stabilized responsive emulsions are discussed, and microgels are compared to classical rigid-particle Pickering stabilizers. Microgels are strongly swollen, lyophilic particles that become deformed at the oil-water interface and protrude only a little into the oil phase. Temperature- and pH-sensitive microgels allow us to prepare temperature- and pH-sensitive emulsions and thus enable us to prepare and break emulsions on demand. Although such emulsions are sensitive to pH, the stabilization of droplets is not due to electrostatic repulsion, instead the viscoelastic properties of the interface seem to dominate droplet stability. Being soft and porous, microgels behave distinctly differently from rigid particles at the interface: they are deformed and strongly flattened especially in the case of oil-in-water emulsions. The microgels are located mainly on the water side of the interface for both oil-in-water and water-in-oil emulsions. In contrast to rigid, solid particles, the behavior of microgels at oil-water interfaces does not depend only on the interfacial tension but also on the balance among the interfacial tension, swelling, elasticity, and deformability of the microgel, which needs to be considered. It is obvious that microgels as soft, porous particles are significantly different from classical rigid colloidal stabilizers in Pickering emulsions and we suggest avoiding the term Pickering emulsion when swollen microgels are employed. Microgel-stabilized emulsions require the development of new theoretical models to understand their properties. They open the door to new sophisticated applications.