Morphological Evolution of Hybrid Block Copolymer Particles: Toward Magnetic Responsive Particles

The co-assembly of block copolymers (BCPs) and inorganic nanoparticles (NPs) under emulsion confinement allows facile access to hybrid polymeric colloids with controlled hierarchical structures. Here, the effect of inorganic NPs on the structure of the hybrid BCP particles and the local distribution of NPs are studied, with a particular focus on comparing Au and Fe₃O₄ NPs. To focus on the effect of the NP core, Au and Fe₃O₄ NPs stabilized with oleyl ligands were synthesized, having a comparable diameter and grafting density. The confined co-assembly of symmetric polystyrene-b-poly(1,4-butadiene) (PS-b-PB) BCPs and NPs in evaporative emulsions resulted in particles with various morphologies including striped ellipsoids, onion-like particles, and their intermediates. The major difference in PS-b-PB/Au and PS-b-PB/Fe₃O₄ particles was found in the distribution of NPs inside the particles that affected the overall particle morphology. Au NPs were selectively localized inside PB domains with random distributions regardless of the particle morphology. Above the critical volume fraction, however, Au NPs induced the morphological transition of onion-like particles into ellipsoids by acting as an NP surfactant. For PS-b-PB/Fe₃O₄ ellipsoids, Fe₃O₄ NPs clustered and segregated to the particle/surrounding interface of the ellipsoids even at a low volume fraction, while Fe₃O₄ NPs were selectively localized in the middle of PB domains in a string-like pattern for PS-b-PB/Fe₃O₄ onion-like particles.