Surfactant-free oil-in-water emulsions prepared with temperature and pH sensitive poly(N-isopropylacrylamide)(PNIPAM) microgel particles offer unprecedented control of emulsion stability.

Using stimulus-sensitive microgel particles as an emulsifier, we have prepared a new type of emulsion responsive to pH, ionic strength, and temperature changes. Each of these environmental changes can trigger a volume phase transition in poly(N-isopropylacrylamide) (PNIPAM) microgel particles containing some carboxylic groups. Depending on their hydrophobicity and charging state, such PNIPAM microgel particles can adsorb to the droplets of an octanol-in-water emulsion and provide excellent stability against coalescence and ripening. We have studied in detail the correlation between the particles' response to changes in the solution conditions and the corresponding response of particle-decorated emulsion droplets. In their swollen, hydrophilic state, the microgel particles consistently stabilize the octanol droplets, but inducing a microgel collapse usually results in a destabilization of the emulsion and eventually in phase separation. A notable exception was found at high pH where particles are highly charged: in this regime emulsions remain stable even upon a temperatureinduced collapse of the microgel particles and prove sensitive only to high levels of screening ions. Microscopy studies of toluene-in-water emulsions stabilized by compact polystyrene particles of variable surface charge further suggest an intimate connection between the charge and packing density of interfacial particles and hint at a charge-induced interparticle attraction.

The versatility of colloidal particles endows the particle stabilized or Pickering emulsions with unique features and can potentially enable the fabrication of a wide variety of derived materials. We review the evolution and breakthroughs in the research on the use of colloidal particles for the stabilization of Pickering emulsions in recent years for the particle categories of inorganic particles, polymer-based particles, and food-grade particles. Moreover, based on the latest works, several emulsions stabilized by the featured particles and their derived functional materials, including enzyme immobilized emulsifiers for interfacial catalysis, 2D colloidal materials stabilized emulsions as templates for porous materials, and Pickering emulsions as adjuvant formulations, are also summarized. Finally, we point out the gaps in the current research on the applications of Pickering emulsions and suggest future directions for the design of particulate stabilizers and preparation methods for Pickering emulsions and their derived materials.

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Understanding the adsorption behaviors of soft poly(N-isopropylacrylamide) (PNIPAM) microgels to the oil-water interface has become increasingly important both in terms of fundamental science and applications of microgels as multi-stimuli responsive emulsion stabilizers. In the present work, we used pendant drop tensiometry to trace the evolution of oil-water interfacial tensions. We investigated two PNIPAM microgels with different cross-link density as well as poly(styrene-co-NIPAM) particles. We found that the adsorption of microgels from the aqueous phase to the oil-water interface is dominated by two steps. Microgels first diffuse to the oil-water interface and this diffusion process depends on microgel concentration in the bulk phase. The second process involves the deformation and spreading of microgels at the interface. The second process depends strongly on microgel deformability. The behavior of the different microgel systems is compared with conventional Pickering stabilizers and proteins. Our results demonstrate that the softness of the microgels dominates their properties at the oil-water interface. The change of microgel shape at the interface resembles the unfolding transitions observed with proteins. On the other hand, microgels are distinctly different from conventional, rigid Pickering stabilizers.