Gerardo F. Goya

Static and dynamic magnetic properties of spherical magnetite nanoparticles

We present a detailed study of static and dynamic magnetic behavior of Fe3O4 nanoparticles with average particle sizes 〈d〉 ranging from 5 to 150 nm. Bulk-like properties such as saturation magnetization, hyperfine parameters, coercive field, and Verwey transition are observed in 150 nm particles. For decreasing particle size, the Verwey temperature, TV, shifts down to ∼20 K for 〈d〉=50 nm and is no longer observable for smaller particles. The smallest particles (〈d〉=5 nm) display superparamagnetic behavior at room temperature, with transition to a blocked state at TB∼45 K, which depends on the applied field. The existence of surface spin disorder can be inferred from the decrease of saturation magnetization MS at low temperatures, as the average particle size is reduced. This disordered surface did not show effects of exchange coupling to the particle core, as observed from hysteresis loops after field cooling in a 7 T magnetic field. For particles with 〈d〉=5 nm, dynamic ac susceptibility measurements show...

Magnetically triggered nanocomposite membranes: a versatile platform for triggered drug release.

Drug delivery devices based on nanocomposite membranes containing thermoresponsive nanogels and superparamagnetic nanoparticles have been demonstrated to provide reversible, on-off drug release upon application (and removal) of an oscillating magnetic field. We show that the dose of drug delivered across the membrane can be tuned by engineering the phase transition temperature of the nanogel, the loading density of nanogels in the membrane, and the membrane thickness, allowing for on-state delivery of model drugs over at least 2 orders of magnitude (0.1-10 μg/h). The zero-order kinetics of drug release across the membranes permit drug doses from a specific device to be tuned according to the duration of the magnetic field. Drugs over a broad range of molecular weights (500-40000 Da) can be delivered by the same membrane device. Membrane-to-membrane and cycle-to-cycle reproducibility is demonstrated, suggesting the general utility of these membranes for drug delivery.

Magnetic properties of nanostructured CuFe2O4

The structural evolution and magnetic properties of nanostructured copper ferrite, CuFe2O4, have been investigated by x-ray diffraction, Mossbauer spectroscopy, and magnetization measurements. Nanometre-sized CuFe2O4 particles with a partially inverted spinel structure were synthesized by high-energy ball milling in an open container with grain sizes ranging from 9 to 61 nm. Superparamagnetic relaxation effects have been observed in milled samples at room temperature by Mossbauer and magnetization measurements. At 15 K, the average hyperfine field of CuFe2O4 decreases with decreasing average grain size while the coercive force, shift of the hysteresis loop, magnetic hardness, and saturation magnetization at 4.2 K increase with decreasing average grain size. At 295 K the coercive-field dependence on the average grain size is described, with particles showing superparamagnetic relaxation effects. At 4.2 K the relationship between the coercive field and average grain size can be attributed to the change of the effective anisotropy constant of the particles. The interface anisotropy of nanostructured CuFe2O4 is found to be about 1.8(1) × 105 erg cm-3. Although spin canting was present, approximately 20% enhancement of the saturation magnetization in CuFe2O4 nanoparticles was observed, which could be explained by a cation redistribution induced by milling. The high-field magnetization irreversibility and shift of the hysteresis loop detected in our samples have been assigned to a spin-disordered phase, which has a spin-freezing temperature of approximately 50 K.

Uniform and water stable magnetite nanoparticles with diameters around the monodomain–multidomain limit

A direct method for the preparation of uniform magnetite nanoparticles with sizes around 30?nm and stable in aqueous media at pH 7 has been developed. This method is based on the precipitation of an iron (II) salt (FeSO4) in the presence of a base (NaOH) and a mild oxidant (KNO3). Reaction rate seems to be controlled by the iron salt concentration and the presence of ethanol in the media. Thus lower iron concentration and a water/ethanol ratio equal to one lead to the formation of the smallest particles, 30?nm in diameter. Colloidal suspensions of these particles were directly obtained by simple ultrasonic treatment of the powders leading to very stable ferrofluids at pH 7. Sulphate anions present at the particle surface seem to be responsible for the colloidal stability, providing a biocompatible character to the suspensions. The structural, morphological and magnetic characterization of the nanoparticles is also described and suggests that the smallest particles have a diameter close to the limit between monodomain?multidomain magnetic structure, which could account for the high powder absorption of magnetic fields. According to this calorimetric experiments resulted in specific power absorption rates of ca 80?95?W?g?1, which are among the highest values reported in the literature and make these nanoparticles very interesting for hyperthermia.

Structural and magnetic properties of ball milled copper ferrite

The structural and magnetic evolution in copper ferrite (CuFe2O4) caused by high-energy ball milling are investigated by x-ray diffraction, Mossbauer spectroscopy, and magnetization measurements. Initially, the milling process reduces the average grain size of CuFe2O4 to about 6 nm and induces cation redistribution between A and B sites. These nanometer-sized particles show superparamagnetic relaxation effects at room temperature. It is found that the magnetization is not saturated even with an applied field of 9 T, possibly as the result of spin canting in the partially inverted CuFe2O4. The canted spin configuration is also suggested by the observed reduction in magnetization of particles in the blocked state. Upon increasing the milling time, nanometer-sized CuFe2O4 particles decompose, forming α-Fe2O3 and other phases, causing a further decrease of magnetization. After a milling time of 98 h, α-Fe2O3 is reduced to Fe3O4, and magnetization increases accordingly to the higher saturation magnetization va...

Spin disorder and magnetic anisotropy in Fe3O4 nanoparticles

We have studied the magnetic behavior of dextran-coated magnetite (Fe3O4) nanoparticles with median particle size ⟨d⟩=8nm. Magnetization curves and in-field Mossbauer spectroscopy measurements showed that the magnetic moment MS of the particles was much smaller than the bulk material. However, we found no evidence of magnetic irreversibility or nonsaturating behavior at high fields, usually associated to spin canting. The values of magnetic anisotropy Keff from different techniques indicate that surface or shape contributions are negligible. It is proposed that these particles have bulklike ferromagnetic structure with ordered A and B sublattices, but nearly compensated the magnetic moments. The dependence of the blocking temperature with frequency and applied fields, TB(H,ω), suggests that the observed nonmonotonic behavior is governed by the strength of interparticle interactions.

Magnetic nanoparticles for power absorption: Optimizing size, shape and magnetic properties

We present a study on the magnetic properties of naked and silica-coated Fe{sub 3}O{sub 4} nanoparticles with sizes between 5 and 110 nm. Their efficiency as heating agents was assessed through specific power absorption (SPA) measurements as a function of particle size and shape. The results show a strong dependence of the SPA with the particle size, with a maximum around 30 nm, as expected for a Neel relaxation mechanism in single-domain particles. The SiO{sub 2} shell thickness was found to play an important role in the SPA mechanism by hindering the heat outflow, thus decreasing the heating efficiency. It is concluded that a compromise between good heating efficiency and surface functionality for biomedical purposes can be attained by making the SiO{sub 2} functional coating as thin as possible. - Graphical Abstract: The magnetic properties of Fe{sub 3}O{sub 4} nanoparticles from 5 to 110 nm are presented, and their efficiency as heating agents discussed as a function of particle size, shape and surface functionalization.

The influence of colloidal parameters on the specific power absorption of PAA-coated magnetite nanoparticles

The suitability of magnetic nanoparticles (MNPs) to act as heat nano-sources by application of an alternating magnetic field has recently been studied due to their promising applications in biomedicine. The understanding of the magnetic relaxation mechanism in biocompatible nanoparticle systems is crucial in order to optimize the magnetic properties and maximize the specific absorption rate (SAR). With this aim, the SAR of magnetic dispersions containing superparamagnetic magnetite nanoparticles bio-coated with polyacrylic acid of an average particle size of ≈10 nm has been evaluated separately by changing colloidal parameters such as the MNP concentration and the viscosity of the solvent. A remarkable decrease of the SAR values with increasing particle concentration and solvent viscosity was found. These behaviours have been discussed on the basis of the magnetic relaxation mechanisms involved.PACS: 80; 87; 87.85jf

Magnetic hyperthermia in single-domain monodisperse FeCo nanoparticles: Evidences for Stoner–Wohlfarth behavior and large losses

We report on hyperthermia measurements on a colloidal solution of 14.2±1.5 nm monodisperse FeCo nanoparticles (NPs). Losses as a function of the magnetic field display a sharp increase followed by a plateau, which is what is expected for losses of ferromagnetic single-domain NPs. The frequency dependence of the coercive field is deduced from hyperthermia measurement and is in quantitative agreement with a simple model of noninteracting NPs. The measured losses (1.5 mJ/g) compare to the highest of the literature, although the saturation magnetization of the NPs is well below the bulk one.

Ionic disorder and Néel temperature in ZnFe2O4 nanoparticles

Abstract Magnetic properties of ultrafine ZnFe 2 O 4 particles obtained from mechanosynthesis of the precursor oxides are presented. The ordering temperature of as-milled sample is T N ≈ 115(10) K, and extends over a Δ T ≈ 60 K range. This behavior can be explained by oxygen vacancies and local disorder at Fe sites resulting from the milling process. Magnetic coupling between ordered and disordered phases is discussed.