Chemical engineering of cationic distribution in spinel ferrite nanoparticles: the effect on the magnetic properties.

A set of ∼9 nm CoFe2O4 nanoparticles substituted with Zn2+ and Ni2+ was prepared by thermal decomposition of metallic acetylacetonate precursors to correlate the effects of replacement of Co2+ with the resulting magnetic properties. Due to the distinct selectivity of these cations for the spinel ferrite crystal sites, we show that it is possible to tailor the magnetic anisotropy, saturation magnetization, and interparticle interactions of the nanoparticles during the synthesis stage. This approach unlocks new possibilities for enhancing the performance of spinel ferrite nanoparticles in specific applications. Particularly, our study shows that the replacement of Co2+ by 48% of Zn2+ ions led to an increase in saturation magnetization of approximately 40% from ∼103 A m2 kg-1 to ∼143 A m2 kg-1, whereas the addition of Ni2+ at a similar percentage led to an ∼30% decrease in saturation magnetization to 68-72 A m2 kg-1. The results of calculations based on the two-sublattice Néel model of magnetization match the experimental findings, demonstrating the model's effectiveness in the strategic design of spinel ferrite nanoparticles with targeted magnetic properties through doping/inversion degree engineering.

Unraveling Exchange Coupling in Ferrites Nano-Heterostructures.

The magnetic coupling of a set of SrFe12 O19 /CoFe2 O4 nanocomposites is investigated. Advanced electron microscopy evidences the structural coherence and texture at the interfaces of the nanostructures. The fraction of the lower anisotropy phase (CoFe2 O4 ) is tuned to assess the limits that define magnetically exchange-coupled interfaces by performing magnetic remanence, first-order reversal curves (FORCs), and relaxation measurements. By combining these magnetometry techniques and the structural and morphological information from X-ray diffraction, electron microscopy, and Mössbauer spectrometry, the exchange intergranular interaction is evidenced, and the critical thickness within which coupled interfaces have a uniform reversal unraveled.

Tunable particle-agglomeration and magnetic coupling in bi-magnetic nanocomposites.

A set of non-stoichiometric Zn-Co-ferrite nanoparticles (NPs) was prepared by thermal decomposition of metallic complexes, in the presence of oleic acid, and, after a ligand-exchange process, was coated by a hydrophilic surfactant: these NPs were used as seeds in a sol-gel self-combustion synthesis to prepare nanocomposites (NCs) with a fixed weight ratio. Our focus here is the development of an efficient synthetic approach to control the magnetic coupling between a hard-magnetic matrix (Sr-ferrite) and NPs. The physico-chemical synthetic conditions (temperature, pH, colloidal stability) were optimized in order to tune their effect on the final particles' agglomeration in the matrix. We demonstrate that our synthetic approach is a novel way to produce strongly magnetically coupled NCs, where the final extrinsic properties could be tuned by controlling (i) the agglomeration of seeds in the matrix and (ii) their elemental doping.

Enhanced adsorption performance of magnetic Ni0.5Zn0.5Fe2O4/Zn0.95Co0.05O nanocomposites for the removal of malachite green dye.

This investigation reports the synthesis and characterization of (1-x)Ni0.5Zn0.5Fe2O4/(x)Zn0.95Co0.05O nanocomposites, with 0.0 ≤ × ≤ 0.5. Fourier transform infrared (FTIR) and Raman spectroscopies confirmed the purity of the samples and the presence of bands corresponding to octahedral and tetrahedral iron occupancies for Ni0.5Zn0.5Fe2O4 nanoparticles. A shift in peak positions of these bands was detected upon the addition of Zn0.95Co0.05O nanoparticles. The magnetic properties of the nanocomposites were examined using Mössbauer spectrometry at both room temperature and 77 K. Room temperature analysis showed the existence of both ferromagnetic and superparamagnetic behaviors, while at 77 K, all nanocomposites showed ferromagnetic behavior. The adsorption performance of the nanocomposite on the removal of malachite green (MG) dye solution was investigated by varying the contact time, adsorbent concentration, and reaction temperature. The adsorption reaction followed the second-order kinetics and the sample with x = 0.3 showed the highest adsorption rate. The adsorption rate showed an increase with the increase in the reaction temperature. The adsorption isotherm was determined by applying different adsorption isotherms (Langmuir, Freundlich, and Temkin isotherms), and the results are well-fitted with the Langmuir theoretical model.

Hardening of Cobalt Ferrite Nanoparticles by Local Crystal Strain Release: Implications for Rare Earth Free Magnets.

In this work, we demonstrate that the reduction of the local internal stress by a low-temperature solvent-mediated thermal treatment is an effective post-treatment tool for magnetic hardening of chemically synthesized nanoparticles. As a case study, we used nonstoichiometric cobalt ferrite particles of an average size of 32(8) nm synthesized by thermal decomposition, which were further subjected to solvent-mediated annealing at variable temperatures between 150 and 320 °C in an inert atmosphere. The postsynthesis treatment produces a 50% increase of the coercive field, without affecting neither the remanence ratio nor the spontaneous magnetization. As a consequence, the energy product and the magnetic energy storage capability, key features for applications as permanent magnets and magnetic hyperthermia, can be increased by ca. 70%. A deep structural, morphological, chemical, and magnetic characterization reveals that the mechanism governing the coercive field improvement is the reduction of the concomitant internal stresses induced by the low-temperature annealing postsynthesis treatment. Furthermore, we show that the medium where the mild annealing process occurs is essential to control the final properties of the nanoparticles because the classical annealing procedure (T > 350 °C) performed on a dried powder does not allow the release of the lattice stress, leading to the reduction of the initial coercive field. The strategy here proposed, therefore, constitutes a method to improve the magnetic properties of nanoparticles, which can be particularly appealing for those materials, as is the case of cobalt ferrite, currently investigated as building blocks for the development of rare-earth free permanent magnets.

The Boundary Between Volume and Surface-Driven Magnetic Properties in Spinel Iron Oxide Nanoparticles.

Despite modern preparation techniques offer the opportunity to tailor the composition, size, and shape of magnetic nanoparticles, understanding and hence controlling the magnetic properties of such entities remains a challenging task, due to the complex interplay between the volume-related properties and the phenomena occurring at the particle's surface. The present work investigates spinel iron oxide nanoparticles as a model system to quantitatively analyze the crossover between the bulk and the surface-dominated magnetic regimes. The magnetic properties of ensembles of nanoparticles with an average size in the range of 5-13 nm are compared. The role of surface anisotropy and the effect of oleic acid, one of the most common and versatile organic coatings, are discussed. The structural and morphological properties are investigated by X-ray diffraction and transmission electron microscopy. The size dependence of the surface contribution to the effective particle anisotropy and the magnetic structure are analyzed by magnetization measurements and in-field Mössbauer spectrometry. The structural data combined with magnetometry and Mössbauer spectrometry analysis are used to shed light on this complex scenario revealing a crossover between volume and surface-driven properties in the range of 5-7 nm.

Structural and magnetic properties of hard-soft BaFe12O19/(Zn0.5Co0.5)Fe2O4ferrites.

Hard-soft nanocomposites of (1 -x) BaFe12O19/x(Zn0.5Co0.5)Fe2O4, forx= 0.00, 0.25, 0.50, 0.75 and 1.00, were prepared via co-precipitation and high-speed ball milling techniques, respectively. The synthesized samples were characterized via x-ray diffraction, transmission electron microscope, Fourier transform infrared (FTIR), and vibrating sample magnetometer. XRD revealed the formation of hard-soft nanocomposites. TEM indicated that the two phases are well distributed and the particle size distribution is narrower for low content of soft phase, leading to better exchange coupling between the grains. Magnetic measurements were performed at 300 K and 77 K. The results showed a good single-phase magnetic behavior, verifying the good exchange coupling between hard and soft phases. For low (Zn0.5Co0.5)Fe2O4content, the dipolar interactions were dominated by the exchange-coupling interactions. Additionally, the optimum values of saturation and remanent magnetizations, coercivity, and squareness ratio were obtained forx= 0.5. This was attributed to the dominance of exchange-coupling interaction. The enhancement of magnetic properties and energy product (BH)maxfor nanocomposites at low temperature is skilled in the reduction of the thermal fluxes of magnetic moments at the surface. The maximum energy product (BH)maxwas observed in C2 at both temperatures with a smaller value than that of pure BaFe12O19.

On the first evidence of exchange-bias feature in magnetically contrasted consolidates made from CoFe2O4-CoO core-shell nanoparticles.

Hetero-nanostructures based on magnetic contrast oxides have been prepared as highly dense nanoconsolidates. Cobalt ferrite-cobalt oxide core-shell type nanoparticles (NPs) were synthesized by seed mediated growth in polyol and subsequently consolidated by Spark Plasma Sintering (SPS) at 500 °C for a few minutes while applying a uniaxial pressure of 100 MPa. It is interesting to note that the exchange bias feature observed in the core-shell NPs is reproduced in their ceramic counterparts, or even attenuated. A systematic structural characterization was then carried out to elucidate the decrease in the exchange magnetic field, involving mainly advanced X-ray diffraction, zero-field and in-field 57Fe Mössbauer spectrometry, magnetic measurements and electron microscopy.

Chemical Inhomogeneity in Iron Oxide@CoO Core-Shell Nanoparticles: A Local Probe Study Using Zero-Field and In-Field 57Fe Mössbauer Spectrometry.

Core-shell magnetic nanoparticles type Fe3-xO4 (≈10 nm)@CoO (≈3 nm) prepared by forced hydrolysis in polyol medium have been investigated through the combined use of dc magnetization measurements by SQUID and local analysis by 57Fe Mössbauer spectrometry. A shift of the hysteresis loop along the field axis was observed, which highlights the presence of exchange bias coupling in these nanoparticles. This exchange bias coupling is accompanied by an unexpected high value of coercive field in hysteresis loop in mode ZFC. A local probe study using both zero-field and in-field Mössbauer spectrometry reveals complex hyperfine structures. Great attention is paid to the fitting procedure: it is concluded that Fe3-xO4@CoO nanoparticles result from a mixture of magnetite and maghemite phases in addition to the formation of an interface-like layer close to a cobalt ferrite. Such a structure explains both the high coercive field value observed by SQUID and the presence of exchange bias coupling.

Enhancing the magnetic anisotropy of maghemite nanoparticles via the surface coordination of molecular complexes.

Superparamagnetic nanoparticles are promising objects for data storage or medical applications. In the smallest--and more attractive--systems, the properties are governed by the magnetic anisotropy. Here we report a molecule-based synthetic strategy to enhance this anisotropy in sub-10-nm nanoparticles. It consists of the fabrication of composite materials where anisotropic molecular complexes are coordinated to the surface of the nanoparticles. Reacting 5 nm γ-Fe2O3 nanoparticles with the [Co(II)(TPMA)Cl2] complex (TPMA: tris(2-pyridylmethyl)amine) leads to the desired composite materials and the characterization of the functionalized nanoparticles evidences the successful coordination--without nanoparticle aggregation and without complex dissociation--of the molecular complexes to the nanoparticles surface. Magnetic measurements indicate the significant enhancement of the anisotropy in the final objects. Indeed, the functionalized nanoparticles show a threefold increase of the blocking temperature and a coercive field increased by one order of magnitude.

On the use of amine-borane complexes to synthesize iron nanoparticles.

The effectiveness of amine-borane as reducing agent for the synthesis of iron nanoparticles has been investigated. Large (2-4 nm) Fe nanoparticles were obtained from [Fe{N(SiMe3)2}2]. Inclusion of boron in the nanoparticles is clearly evidenced by extended X-ray absorption fine structure spectroscopy and Mössbauer spectrometry. Furthermore, the reactivity of amine-borane and amino-borane complexes in the presence of pure Fe nanoparticles has been investigated. Dihydrogen evolution was observed in both cases, which suggests the potential of Fe nanoparticles to promote the release of dihydrogen from amine-borane and amino-borane moieties.

Size-dependent magnetic properties of CoFe2O4 nanoparticles prepared in polyol.

Highly crystalline CoFe(2)O(4) nanoparticles with different diameters ranging from 2.4 to 6.1 nm have been synthesized by forced hydrolysis in polyol. The size can be controlled through adjusting the nominal water/metal molar ratio. X-ray diffraction, transmission electron microscopy, x-ray absorption spectroscopy and (57)Fe Mössbauer spectrometry were employed to investigate the structure and the microstructure of the particles produced. Magnetic measurements performed on these particles show that they are superparamagnetic with a size-dependent blocking temperature. At 5 K, high saturation magnetization (~85 emu g(-1)) approaching that of the bulk was found for the larger particles, whereas a very large coercivity (14.5 kOe) is observed for the 3.5 nm sized particles.

Short period magnetic coupling oscillations in Co/Si multilayers: Theory versus experiment.

Today the magnetic properties of multilayers and nanostructures including a metal or an insulator as a nonmagnetic spacer layer are rather well understood. But they are much more controversial for semiconductor spacers. For instance, for Co/Si multilayers short period coupling oscillations are predicted by ab initio computations but have yet to be observed. Here we show in Co/Si multilayers prepared at low temperature (90 K) strong saturation field oscillations that are consistent with the predicted coupling oscillations. However, the decay length of the oscillations is much longer than the expected one and cannot be explained within the framework of available theories.