Self-Assembly of Linear Diblock Copolymers in Selective Solvents: From Single Micelles to Particles with Tri-continuous Inner Structure
Large-scale Dissipative Particle Dynamics (DPD) simulations have been performed to investigate the self-assembly of over 20,000 linear diblock copolymer chains in a selective solvent. Specifically, we found that the transition from spherical to cylindrical vesicles and in turn to disk-like, and onion-like vesicles, and finally to tri-continuous spherical particles is mainly due to the increase of aggregation number. In addition, the structures with large aggregation numbers are formed through fusion of smaller aggregates and the length of the corona block of the block copolymer plays a critical on the resulting morphology. Furthermore, our simulations indicate that the very larger amount of polymer in our simulation is the key to observation of a state of dynamic equilibrium between free chain and aggregates in solution, as well as formation of more complex structures from linear diblock copolymer in selective solvents. Overall, this study paves the way for future coordinated experimental/computational studies on formation nanoparticles with complex morphologies from diblock copolymers, an area of great scientific and industrial interest.