Template-Free Bottom-Up Method for Fabricating Diblock Copolymer Patchy Particles

Patchy particles are one of most important building blocks for hierarchical structures because of the discrete patches on their surface. We have demonstrated a convenient, simple, and scalable bottom-up method for fabricating diblock copolymer patchy particles through both experiments and dissipative particle dynamics (DPD) simulations. The experimental method simply involves reducing the solvent quality of the diblock copolymer solution by the slow addition of a nonsolvent. Specifically, the fabrication of diblock copolymer patchy particles begins with a crew-cut soft-core micelle, where the micelle core is significantly swelled by the solvent. With water addition at an extremely slow rate, the crew-cut soft-core micelles first form a larger crew-cut micelle. With further water addition, the corona-forming blocks of the crew-cut micelles begin to aggregate and eventually form well-defined patches. Both experiments and DPD simulations indicate that the number of patches has a very strong dependence on the diblock copolymer composition the particle has more patches on the surface with a lower volume fraction of patch-forming blocks. Furthermore, particles with more patches have a greater ability to assemble, and particles with fewer patches have a greater ability to merge once assembled.