Assembly of Colloidal Silica Crystals Inside Double Emulsion Drops

We investigated the assembly of colloidal silica crystals inside double emulsion drops generated in microcapillary microfluidic devices. The double emulsions are composed of an aqueous suspension of monodisperse silica particles in the inner drop surrounded by a PDMS oil drop that acts as a semipermeable membrane for the diffusion of water into or out of the inner drop in the presence of an osmotic gradient. Imposing a high osmotic pressure in the continuous phase induces water diffusion out of the inner drop, increasing the silica volume fraction (ϕ_silica) and leading to the formation of a spherical colloidal silica crystal. Silica suspensions with no salt or low salt concentration (<10^–3 M) formed colloidal crystals with ϕ_silica up to 0.68. Monodisperse spherical colloidal silica crystals with sizes ranging from 16 to 133 μm were generated by varying the device geometry, flow-rate ratios, and initial silica fraction. At salt concentrations > 10^–3 M, the electrostatic repulsion is reduced, and crystallization is suppressed. Crystals were preserved in a hydrogel matrix or inside a silicone rubber shell. This study demonstrates a robust path for controlled colloidal assembly inside double emulsion drops