Janus particles with two different compartments have enormous potential as building blocks of hierarchically multifunctional nanomaterials. One of the most versatile and powerful methods to fabricate Janus micelles is through the solution-state self-assembly of block copolymers. In this study, we applied the Monte Carlo simulation to study the self-assembly of a AB/BC diblock copolymer mixture in A- and C-selective solvents. Our simulations predicted a variety of novel Janus micelles, which include Janus-like cylinders, lamellas, vesicles, and rings, all of which were self-assembled from amphiphilic A4B6/B6C4 copolymers. The effects of control parameters, which include the solvent quality for solvophobic B blocks (εBS) and the incompatibility between the solvophilic A and C blocks (εAC), on the formation of Janus micelles were examined, and a generic phase diagram in εBS × εAC was constructed. The phase diagram demonstrates that the micellar shape mainly depends on εBS, whereas the formation of the Janus architecture is controlled by εAC. Moreover, the formation pathways of the Janus lamella, vesicle, and ring were investigated and their formation mechanisms were investigated.
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