Effect of Iron Oxide Nanocrystal Content on the Morphology and Magnetic Properties of Polystyrene-block-polymethyl methacrylate Diblock Copolymer Based Nanocomposites

Iron oxide nanocrystals, synthesized by surfactant-assisted thermal decomposition of Fe(CO)(5), were selectively incorporated into the microseparated PS block phase of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer to design novel nanostructured inorganic/organic materials with magnetic properties. The colloidal synthesis led to oleic acid- and oleylamine- capped magnetic gamma-Fe2O3 maghemite nanocrystals, which resulted well-dispersible in the block copolymer up to 60 wt % due to the affinity between PS block and organic surfactants. Atomic force and scanning electron microscopy confirmed that nanocomposites with nanocrystal loading lower than 40 wt % maintained cylindrical morphology, even without additional treatment applied to enhance their nanostructuration. Nanocrystals appeared well-dispersed in the nanocomposites at low contents, while nanocrystal clusters, with size depending on their loading, were observed at higher contents. At the highest nanocrystal content, the nanostructured area size decreased and nanocrystals covered the entire surface. Magnetic force microscopy measurements confirmed the magnetic behavior of gamma-Fe2O3 nanocrystals confined in PS block of PS-b-PMMA block copolymer after applying UV treatment to the samples. The results demonstrated that the incorporation of as-synthesized colloidal iron oxide nanocrystals (up to 40%) in self-assembled PS-b-PMMA block copolymer offers a simple and direct approach to successfully design and fabricate novel nanostructured magnetic composites.