Ultrastrong Anchoring Yet Barrier-Free Adsorption of Composite Microgels at Liquid Interfaces

Microgel particles display an interesting duality with properties attributed typically both to polymeric and colloidal systems. When adsorbed at a liquid-liquid interface, this duality becomes particularly apparent as the various phenomena at play are governed by different aspects of these soft and responsive particles. The introduction of a solid, fluorescently labeled, polystyrene core into the microgels allows direct and accurate visualization without the necessity of potential perturbing sample preparation techniques. By combining in-situ imaging and tensiometry, we determine that composite microgels at a wide variety of oil-water interfaces anchor strongly, with adsorption energies of approximately 10(6) k(B)T, typical for particle adsorption, yet accumulate at the interface spontaneously without any energy barrier, which is more typical for polymers. The high adsorption energies allow the particle to spontaneously form very dense crystalline packings at the liquid interface in which the microgels are significantly compressed with respect to their swollen state in bulk solutions. Finally, we demonstrate the unique nature of these particles by producing highly stable and monodisperse microgel-stabilized droplets using microfluidics.