Kinetically Controlled Self-Assembly of Block Copolymers into Segmented Worm-Like Micelles in Microfluidic Chips.

Kinetically controlled self-assembly of block copolymers (BCPs) in solution is an efficient route to fabricate complex hierarchical colloids which are of great importance for nanoencapsulation, microreactors, and biomimics. Herein, segmented worm-like micelles (SWMs) with controllable size are generated by self-assembly of polystyrene-block-poly(4-vinyl pyridine) (PS-b-P4VP) in microfluidic channel. Different from the assembly of BCPs off-chip at the same solution properties, it is found that the fabricated SWMs are kinetically controlled assemblies with thermodynamic metastable structures, which are formed by orderly aggregation of preformed spherical micelles due to fast mixing process in microfluidic channels. Moreover, by manipulating the total flow velocity of water and BCPs solution or their flow velocity ratio, both the percentage of SWMs among the whole assemblies and their sizes can be effectively tuned. Based on electron microscopy and dynamic light scatting investigations, a product diagram of micellar morphologies associated to initial polymer concentration and flow velocity ratio of water/BCPs solution was constructed, which is important for rational design and fabrication of complex hierarchical BCP colloids.