One-Step Bulk Fabrication of Polymer-Based Microcapsules with Hard–Soft Bilayer Thick Shells

Microcapsules are important for the protection, transport, and delivery of cargo in a variety of fields but are often too weak to withstand the high mechanical stresses that arise during the preparation and formulation of products. Although thick-shell strong capsules have been developed to circumvent this issue, the microfluidic or multistep methods utilized thus far limit the ease of fabrication and encapsulation throughput. Here, we exploit the phase separation of ternary liquid mixtures to achieve a high-throughput fabrication of strong bilayer microcapsules using a one-step bulk emulsification process. Phase separation is induced by the diffusion of water from the continuous phase into droplets that initially contain a mixture of monomers, cross-linkers, an initiator, and cosolvent γ-butyrolactone. The double emulsions generated via such a phase separation are converted into microcapsules through a polymerization reaction triggered by UV illumination. Surprisingly, the shells of the consolidated capsules exhibit a hard–soft bilayer structure that can be designed to show a resilient eggshell-like fracture behavior. Our method allows for the production of large volumes of microcapsules with such a strong bilayer shell within a time scale of only a few minutes, thus offering an enticing pathway toward the high-throughput fabrication of mechanically robust encapsulation systems