A B S T R A C TThe applications of exchange coupled bi-magnetic hard/soft and soft/hard ferromagnetic core/shell nanoparticles are reviewed. After a brief description of the main synthesis approaches and the core/shell structural-morphological characterization, the basic static and dynamic magnetic properties are presented. Five different types of prospective applications, based on diverse patents and research articles, are described: permanent magnets, recording media, microwave absorption, biomedical applications and other applications. Both the advantages of the core/shell morphology and some of the remaining challenges are discussed.

We present for the first time an in-depth magnetic characterization of a family of monodisperse cobalt-ferrite nanoparticles (NPs) with average size covering a broad range of particles sizes (from 4 to 60 nm), synthesized by thermal decomposition of metal–organic precursors. Metal precursors, surfactants, and synthetic parameters were settled in order to fine-tune the particle size, which preserves a narrow particle size distribution. The morphology of the family of cobalt-ferrite NPs shows a size-dependent behavior, evolving from sphere to octahedrons for size larger than 20 nm and passing through a cubic habit for intermediate sizes. The evolution of the magnetic properties was studied as a function of the particle size and shape, particularly focusing on those determining the best performance as permanent magnet. Although saturation and remnant magnetization increase monotonously with size, reaching a constant value above 20 nm, the coercive field exhibits a nonmonotonic behavior with two distinct maxima values for low and room temperature, respectively. In addition, we evaluated the (BH)max product, the figure of merit of permanent magnets, obtaining the highest value ever reported in the literature for cobalt-ferrite NPs (i.e., 2.1 MGOe (18 kJ/m–3) for 40 nm NPs). This study allowed us to establish, at least on the basis of the (BH)max product, the potentiality of cobalt-ferrite nanoparticles in current permanent magnet technology.

The growing miniaturization demand of magnetic devices is fuelling the recent interest in bi-magnetic nanoparticles as ultimate small components. One of the main goals has been to reproduce practical magnetic properties observed so far in layered systems. In this context, although useful effects such as exchange bias or spring magnets have been demonstrated in core/shell nanoparticles, other interesting key properties for devices remain elusive. Here we show a robust antiferromagnetic (AFM) coupling in core/shell nanoparticles which, in turn, leads to the foremost elucidation of positive exchange bias in bi-magnetic hard-soft systems and the remarkable regulation of the resonance field and amplitude. The AFM coupling in iron oxide-manganese oxide based, soft/hard and hard/soft, core/shell nanoparticles is demonstrated by magnetometry, ferromagnetic resonance and X-ray magnetic circular dichroism. Monte Carlo simulations prove the consistency of the AFM coupling. This unique coupling could give rise to more advanced applications of bi-magnetic core/shell nanoparticles.

The intimate relationship between stoichiometry and physicochemical properties in transition-metal oxides makes them appealing as tunable materials. These features become exacerbated when dealing with nanostructures. However, due to the complexity of nanoscale materials, establishing a distinct relationship between structure-morphology and functionalities is often complicated. In this regard, in the FexO/Fe3O4 system a largely unexplained broad dispersion of magnetic properties has been observed. Here we show, thanks to a comprehensive multi-technique approach, a clear correlation between the magneto-structural properties in large (45 nm) and small (9 nm) FexO/Fe3O4 core/shell nanoparticles that can explain the spread of magnetic behaviors. The results reveal that while the FexO core in the large nanoparticles is antiferromagnetic and has bulk-like stoichiometry and unit-cell parameters, the FexO core in the small particles is highly non-stoichiometric and strained, displaying no significant antiferromagnetism. These results highlight the importance of ample characterization to fully understand the properties of nanostructured metal oxides.

The magnetic properties of bimagnetic core/shell nanoparticles consisting of an antiferromagnetic MnO core and a ferrimagnetic passivation shell have been investigated. It is found that the phase of the passivation shell (gamma-Mn(2)O(3) or Mn(3)O(4)) depends on the size of the nanoparticles. Structural and magnetic characterizations concur that while the smallest nanoparticles have a predominantly gamma-Mn(2)O(3) shell, larger ones have increasing amounts of Mn(3)O(4). A considerable enhancement of the Néel temperature, T(N), and the magnetic anisotropy of the MnO core for decreasing core sizes has been observed. The size reduction also leads to other phenomena such as persistent magnetic moment in MnO up to high temperatures and an unusual temperature behavior of the magnetic domains.

Antiferromagnetic­(AFM)|ferrimagnetic­(FiM) core|shell (CS) nanoparticles (NPs) of formula Co0.3Fe0.7O|Co0.6Fe2.4O4 with mean diameter from 6 to 18 nm have been synthesized through a one-pot thermal decomposition process. The CS structure has been generated by topotaxial oxidation of the core region, leading to the formation of a highly monodisperse single inverted AFM|FiM CS system with variable AFM-core diameter and constant FiM-shell thickness (∼2 nm). The sharp interface, the high structural matching between both phases, and the good crystallinity of the AFM material have been structurally demonstrated and are corroborated by the robust exchange-coupling between AFM and FiM phases, which gives rise to one among the largest exchange bias (H E) values ever reported for CS NPs (8.6 kOe) and to a strongly enhanced coercive field (H C). In addition, the investigation of the magnetic properties as a function of the AFM-core size (d AFM), revealed a nonmonotonous trend of both H C and H E, which display a maximum value for d AFM = 5 nm (19.3 and 8.6 kOe, respectively). These properties induce a huge improvement of the capability of storing energy of the material, a result which suggests that the combination of highly anisotropic AFM|FiM materials can be an efficient strategy toward the realization of novel rare-earth-free permanent magnets.

The physicochemical properties of spinel oxide magnetic nanoparticles depend critically on both their size and shape. In particular, spinel oxide nanocrystals with cubic morphology have shown superior properties in comparison to their spherical counterparts in a variety of fields, like, for example, biomedicine. Therefore, having an accurate control over the nanoparticle shape and size, while preserving the crystallinity, becomes crucial for many applications. However, despite the increasing interest in spinel oxide nanocubes there are relatively few studies on this morphology due to the difficulty to synthesize perfectly defined cubic nanostructures, especially below 20 nm. Here we present a rationally designed synthesis pathway based on the thermal decomposition of iron­(III) acetylacetonate to obtain high quality nanocubes over a wide range of sizes. This pathway enables the synthesis of monodisperse Fe3O4 nanocubes with edge length in the 9–80 nm range, with excellent cubic morphology and high crystallinity by only minor adjustments in the synthesis parameters. The accurate size control provides evidence that even 1–2 nm size variations can be critical in determining the functional properties, for example, for improved nuclear magnetic resonance T 2 contrast or enhanced magnetic hyperthermia. The rationale behind the changes introduced in the synthesis procedure (e.g., the use of three solvents or adding Na-oleate) is carefully discussed. The versatility of this synthesis route is demonstrated by expanding its capability to grow other spinel oxides such as Co-ferrites, Mn-ferrites, and Mn3O4 of different sizes. The simplicity and adaptability of this synthesis scheme may ease the development of complex oxide nanocubes for a wide variety of applications.

A study of ''inverted'' core-shell, MnO=-Mn 2 O 3 , nanoparticles is presented. Crystal and magnetic structures and characteristic sizes have been determined by neutron diffraction for the antiferromagnetic core (MnO) and the ferrimagnetic shell (-Mn 2 O 3 ). Remarkably, while the MnO core is found to have a T N not far from its bulk value, the magnetic order of the -Mn 2 O 3 shell is stable far above T C , exhibiting two characteristic temperatures, at T $ 40 K [T C ð-Mn 2 O 3 Þ] and at T $ 120 K [$T N ðMnOÞ]. Magnetization measurements are consistent with these results. The stabilization of the shell moment up to T N of the core can be tentatively attributed to core-shell exchange interactions, hinting at a possible magnetic proximity effect.