Background: Magnetic nanoparticles (NPs) must not only be well-defined in composition, shape and size to exhibit the desired properties (e.g., exchange-bias for thermal stability of the magnetization) but also judiciously functionalized to ensure their stability in air and their compatibility with a polymer matrix, in order to avoid aggregation which may seriously affect their physical properties. Dipolar interactions between NPs too close to each other favour a collective magnetic glass state with lower magnetization and coercivity because of inhomogeneous and frustrated macrospin cluster freezing. Consequently, tailoring chemically (through surface functionalization) and magnetically stable NPs for technological applications is of primary importance. Results: In this work, well-characterized exchange-biased perfectly epitaxial Co x Fe3-x O4@CoO core@shell NPs, which were isotropic in shape and of about 10 nm in diameter, were decorated by two different polymers, poly(methyl methacrylate) (PMMA) or polystyrene (PS), using radical-controlled polymerization under various processing conditions. We compared the influence of the synthesis parameters on the structural and microstructural properties of the resulting hybrid systems, with special emphasis on significantly reducing their mutual magnetic attraction. For this, we followed two routes: the first one consists of the direct grafting of bromopropionyl ester groups at the surface of the NPs, which were previously recovered and redispersed in a suitable solvent. The second route deals with an "all in solution" process, based on the decoration of NPs by oleic acid followed by ligand exchange with the desired bromopropionyl ester groups. We then built various assemblies of NPs directly on a substrate or suspended in PMMA. Conclusion: The alternative two-step strategy leads to better dispersed polymer-decorated magnetic particles, and the resulting nanohybrids can be considered as valuable building blocks for flexible, magnetic polymer-based devices.
Keywords: ATRP; assembly; exchange-bias; films; functionalization; magnetic nanoparticle; poly(methyl methacrylate); polymerization; polystyrene; seed-mediated growth; surface.