Formation of pickering emulsions using ion-specific responsive colloids.

The ability to control the dispersion, aggregation, and assembly of colloidal systems is important for a number of applications, for instance, Pickering emulsions, drug and gene delivery, control of fluid rheology, and the formation of colloidal crystal arrays. We generated a responsive colloidal system based on polymer-brush-grafted silica nanoparticles and demonstrated that such a colloidal system can be used to produce stable oil-in-water Pickering emulsions. Cationic poly(2-(methacryloyloxy)-ethyl-trimethyl-ammonium chloride) (PMETAC) brushes were grown from silica nanoparticles (diameter ∼320 nm) through surface-initiated atom-transfer radical polymerization (ATRP). PMETAC brushes are attractive coatings for controlling the behavior of colloidal systems, owing to their ion-specific collapse resulting in the switching of surface hydrophilicity. Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), transmission electron microscopy (TEM), dynamic light scattering (DLS), and zeta-potential measurements indicated the successful grafting of PMETAC brushes on nanoparticles. The resulting colloidal dispersion was shown to be responsive to perchlorate ions (ClO(4)(-)), which triggered particle aggregation and enabled the generation of Pickering emulsions. The onset of aggregation depended on the polymer chain length. Aggregation was not affected by the initiator density and brush conformational changes. Further studies suggested that particle aggregation and the formation of stable Pickering emulsions were not simply due to brush collapse but also were due to a gradual shielding of electrostatic repulsion. Finally, the stability and homogeneity of the resulting Pickering emulsions were studied.