Abstract
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 CoxFe3−xO4@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.
Highlights
Polymer-based hybrid materials are opening the way for engineering new, multifunctional, flexible materials exhibiting novel properties due to the synergy between the two components, polymer and inorganic nanoparticles (NPs) [1]
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
We described the functionalization of 10 nm exchange-biased CoxFe3−xO4@CoO core@shell NPs by two different polymers, poly(methyl methacrylate) (PMMA) and polystyrene (PS), Figure 10: Scanning electron microscopy (SEM) images of various assemblies of Exchangebiased NPs (ENPs)-PMMA, obtained by drop casting from THF suspension with ENP/PMMA ratios of 1:1, 1:2 and 1:9
Summary
Well-characterized exchange-biased perfectly epitaxial CoxFe3−xO4@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 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 built various assemblies of NPs directly on a substrate or suspended in PMMA
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