Effect of interacting nanoparticles on the ordered morphology of block copolymer/nanoparticle mixtures

We investigated the effect of hard additives, that is, magnetic nanoparticles (NPs) and metal NPs, on the ordered morphology of block copolymers by varying the NP concentration. To characterize the structural changes of a block copolymer associated with different NP loadings, small-angle X-ray scattering and transmission electron microscopy were performed. Monodisperse maghemite (γ-Fe₂O₃) NPs (7 nm in diameter) and silver (Ag) NPs (6 nm in diameter) with surfaces modified with oleic acids were synthesized, and a cylinder-forming poly(styrene-block-isoprene) diblock copolymer was used as a structure-directing matrix for the NPs. As the NP concentration increased, domains of NP aggregates were observed for both magnetic and metal NPs. In the case of mixtures of cylinder-forming poly(styrene-block-isoprene) and Ag NPs with weak particle–particle interactions, random aggregates of Ag NPs were observed, and the ordered morphology of the block copolymer lost its long-range order with an increase in the NP concentration. However, regular, latticelike aggregates obtained with γ-Fe₂O₃ NPs, because of the strong interparticle interactions, induced an intriguing morphological transformation from hexagonal cylinders to body-centered-cubic spheres via undulated cylinders, whereas the neat block copolymer did not show such a morphological transition over a wide range of temperatures. The interplay between magnetic NPs and the block copolymer was also tested with magnetic NPs of different sizes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3571–3579, 2006