Tuning Solvent Quality Induces Morphological Phase Transitions in Miktoarm Star Polymer Films

The ordering and kinetics of self-assembly of miktoarm star polymers of the form (An)k–C–(Bn)k in solution and confined between two surfaces are investigated using a coarse-grained molecular dynamics simulation, with the ultimate goal of developing predictive capabilities for these systems. By systematically changing the relative solvent-block interaction for one block, combined with the effect of confining substrate on one side and vapor on the other side, we observed a number of interesting morphologies for an inherently lamellar miktoarm star polymers in the absence of solvent. Furthermore, we also found that in solution the self-assembly kinetics of miktoarm star polymers into cylindrical and lamellar morphologies is completely different from the self-assembly kinetics of linear block copolymers. The findings from the present study can be used to tailor the film morphology of miktoarm star polymers, playing a leading role in guiding the experimentalists for designing this class of materials for different types of applications.