Harnessing the advantages of hard and soft colloids by the use of core-shell particles as interfacial stabilizers.

The ability of colloidal particles to penetrate fluid interfaces is a crucial factor in the preparation of particle stabilized disperse systems such as foams and emulsions. For hard micron-sized particles the insertion into fluid interfaces requires substantial energy input, but soft particles are known to adsorb spontaneously. Particle hardness, however, may also affect foam and emulsion stability. The high compliance of soft particles may compromise their ability to withstand the lateral compression associated with disproportionation. Hence, particles which can spontaneously adsorb onto fluid interfaces, and yet depict low compliance may be ideal as interfacial stabilizers. In the present work, we prepared core-shell particles comprising a hard, polystyrene core and a soft poly(N-isopropylacrylamide) based shell. We found that such core-shell particles adsorb spontaneously onto various fluid interfaces. The absence of a pronounced energy barrier for interfacial adsorption allowed the facile preparation of particle-stabilized bubbles as well as emulsion droplets. For bubbles, the stability was better than that of bubbles stabilized by entirely soft particles, but disproportionation was not stopped completely. Emulsion droplets, in contrast, showed excellent stability against both coalescence and disproportionation. Lateral compression of core-shell particles due to disproportionation was clearly limited by the presence of the polystyrene core, leading to long-lasting stability. For emulsions, we even observed non-spherical droplets, indicating a negligible Laplace pressure. Our results indicate that core-shell particles comprising a hard core and a soft shell combine the advantageous properties of hard and soft particles, namely spontaneous adsorption and limited compliance, and can therefore be superior materials for the preparation of particle-stabilized dispersions.

Assembly of jammed colloidal shells onto micron-sized bubbles by ultrasound.

Stabilization of gas bubbles in water by applying solid particles is a promising technique to ensure long-term stability of the dispersion against coarsening. However, the production of large quantities of particle stabilized bubbles is challenging. The delivery of particles to the interface must occur rapidly compared to the typical time scale of coarsening during production. Furthermore, the production route must be able to overcome the energy barriers for interfacial adsorption of particles. Here we demonstrate that ultrasound can be applied to agitate a colloidal dispersion and supply sufficient energy to ensure particle adsorption onto the air-water interface. With this technique we are able to produce micron-sized bubbles, solely stabilized by particles. The interface of these bubbles is characterized by a colloidal shell, a monolayer of particles which adopt a hexagonal packing. The particles are anchored to the interface owing to partial wetting and experience lateral compression due to bubble shrinkage. The combination of both effects stops coarsening once the interface is jammed with particles. As a result, stable bubbles are formed. Individual particles can desorb from the interface upon surfactant addition, though. The latter fact confirms that the particle shell is not covalently linked due to thermal sintering, but is solely held together by capillary interaction. In summary, we show that our ultrasound approach allows for the straightforward creation of micron-sized particle stabilized bubbles with high stability towards coarsening.