Search

This paper reviews the effect of organic and inorganic coatings on magnetic nanoparticles. The ferromagnetic-like behaviour observed in nanoparticles constituted by materials which are non-magnetic in bulk is analysed for two cases: (a) Pd and Pt nanoparticles, formed by substances close to the onset of ferromagnetism, and (b) Au and ZnO nanoparticles, which were found to be surprisingly magnetic at the nanoscale when coated by organic surfactants. An overview of theories accounting for this unexpected magnetism, induced by the nanosize influence, is presented. In addition, the effect of coating magnetic nanoparticles with biocompatible metals, oxides or organic molecules is also reviewed, focusing on their applications.

In this paper, the physical properties of half-doped manganite La0.5Ca0.5MnO3 with crystallite sizes ranging from 15 to 40 nm are investigated. As expected, ferromagnetic order strengthens at expense of antiferromagnetic one as crystallite size is reduced to 15 nm. However, contrary to previously reported works, an enhancement of saturation magnetization is observed as crystallite size increases from 15 to 22 nm. This unexpected behavior is accompanied by an unusual cell volume variation that seems to induce ferromagnetic-like behavior at expense of antiferromagnetic one. Besides, field cooled hysteresis loops show exchange bias field and coercivity enhancement for increasing cooling fields, which suggest a kind of core-shell structure with AFM-FM coupling for crystallite sizes as small as 15 nm. It is expected that inner core orders antiferromagnetically, whereas uncompensated surface spins behave as spin glass with ferromagnetic-like ordering. [ABSTRACT FROM AUTHOR]

In this work we present new results on spontaneous oxidation of disordered fcc FePt nanoparticles. The “as-made” oleic acid and oleylamine coated FePt nanoparticles of average size 4 nm synthesized by a high-boiling coordinating solvent method were exposed to air over a period of days and characterized structurally and magnetically by means of different techniques such as XANES, XPS, EXAFS, and SQUID magnetometry. The “as-made” FePt nanoparticles stabilize in the disordered fcc structure and have a very low magnetic saturation (Ms=11 emu/g) and a huge coercive field (Hc=1800 Oe) compared to the low temperature bulk values of the disordered fcc FePt. We observed that the coercive field and the magnetic saturation change with the time the sample is exposed to air and these changes are associated with the oxidation or passivation of the nanoparticle surface that gives place to a core-shell structure. Indeed, the study on the electronic properties of the nanoparticles confirms the magnetic results and indicates that when the nanoparticles are exposed to air, changes in the oxidation state of both Fe and Pt occur, the oxidation state of Fe coming close to hematite. The formation of hematite tends to soften the “as-made” FePt nanoparticles as observed by the reduction of the coercive field to almost one third of the original value. Although the hematite softens the FePt nanoparticles, there is an exchange coupling at the interface of the core-shell characterized by the increase of the coercive field from 300 to 900 Oe when the sample is cooled in an applied field of 50 kOe. [ABSTRACT FROM AUTHOR]

In this work the study of oleic acid and oleylamine-capped gold nanoparticles is presented. The structural characterization of the sample shows 6.7 nm gold nanoparticles with a narrow size distribution. The experimental optical absorption spectrum has a maximum at 2.35 eV. The calculated optical absorption spectrum is shifted and narrower than the experimental one, indicating that the oleic acid and oleylamine do not merely passivate the metallic nanoparticles but modify its electronic structure. These gold nanoparticles show in addition a kind of magnetic order similar to other organic passivated gold nanoparticles as thiol-capped gold nanoparticles. Although the magnetic interactions seem to be weaker than in thiol-capped ones, the magnetic behavior looks similar to that, i.e., an invariant temperature dependence of the magnetization from 5 to 300 K and a noticeable coercive field. We analyze the influence of the organic layer bonding the nanoparticles on the magnetic behavior. [ABSTRACT FROM AUTHOR]

Bare and coated TiO2 nanoparticles with particle sizes d<5 nm have been synthesized in a microwave plasma process. Structural properties of these materials have been investigated by transmission electron microscopy, x-ray diffraction, and perturbed angular correlation (PAC) measurements of the electric quadrupole interaction (QI) at the probe nucleus 181Ta on the metal site of TiO2 at temperatures 290<=T<=1450 K. The electron diffraction of the uncoated nanoparticles in the as-synthesized state reflects long range order in the Ti sublattice. Depending on the particles size, either the anatase or the rutile phase of TiO2 was found. Anatase appears to be the stable form of nanocrystalline TiO2 below d∼10 nm. The PAC spectra of these nanocrystalline oxides are characterized by a broad distribution of strong quadrupole interactions, indicating a strongly disordered oxygen environment of the metal sites. Upon annealing, the grain size grows from d<5 nm after synthesis to d>100 nm after 1300 K. PAC spectra taken in the same temperature range show that with increasing temperature, the initially disordered state transforms to well-ordered rutile TiO2. The data suggest a critical grain size of d∼10 nm for the onset of the ordering process. The spectra of coarse-grained TiO2 are reached at a particle size d>=30 nm. In n-TiO2 coated with Al2O3 and ZrO2 both the cores and the coatings were found to grow with increasing temperature; the cores of the coated particles, however, grow much less than those of the noncoated particles. The PAC method was used to investigate the QI in both TiO2 cores and in the ZrO2 coating of n-TiO2/ZrO2 at different temperatures. These data suggest that although the coated particles grow with temperature, the ordering process is obstructed, possibly by a solid state reaction between the TiO2 kernels and the coatings. [ABSTRACT FROM AUTHOR]

In this work, we present the magnetic properties of gold-coated FePt nanoparticles and the study of stable aqueous dispersions of FePt@Au and FePt synthesized after ligand exchange with mercaptoundecanoic acid. The particle size determined from transmission electron microscopy (TEM) micrographs goes from 4 nm for the uncoated nanoparticles to a maximum of 10 nm for the gold-coated ones indicating that the thickness of the shell ranges from 1 to 3 nm. The magnetic characterization consists in hysteresis cycles at 10 and 300 K. The results show that, at low field and room temperature, the magnetic behavior of uncoated and coated nanoparticles are surprisingly quite similar. Because the gold-coated nanoparticles keep the magnetic properties of FePt and the presence of gold improves the functionalization of nanoparticles, the system is suitable for biological application. Mercaptoundecanoic ligand transfer was used to render water stable nanoparticles in a wide pH range. Transmission electron microscopy and dynamic light scattering (DLS) results show the nanoparticles slightly agglomerate after ligand exchange. Fourier transform infrared spectroscopy results suggest that thiol binds to the gold atoms of the surface. [ABSTRACT FROM AUTHOR]

Abstract: In the past few years ferromagnetic-like behavior has been reported in metal gold nanoparticles coated with diverse organic surfactants. In this work we report on the effect of thermal annealing on the ferromagnetic-like behavior of oleic acid and oleylamine coated gold nanoparticles of about 7 nm size. The magnetic moment of the “as prepared” sample is about 3×10−2 emu/g and the coercive field is 200 Oe at 10 kOe and 5 K, after the annealing the behavior changes from ferromagnetic-like to paramagnetic and the magnetization at 10 kOe decreases at a factor of 10. These results are compared with those obtained for oleylamine coated gold nanoparticles, which are diamagnetic at room temperature. [Copyright &y& Elsevier]

Magnetite nanostructured powder samples were synthesized by aging chemical method. Phase, structural, and magnetic properties were characterized. X-ray diffraction patterns showed cubic magnetite pure phase, with average crystallite size, , equal to 40 nm. Susceptibility measurements showed the well-known Verwey transition at a temperature of 90 K. The decrease of Verwey transition temperature, with respect to the one reported in literature (125 K) was attributed to the low average crystallite size. Moreover, the spin-glass like transition was observed at 35 K. Activation energy calculated from susceptibility curves, with values ranging from 6.26 to 6.93 meV, showed a dependence of spin-glass transition on frequency. Finally, hysteresis loops showed that there is not an effect of Verwey transition on magnetic properties. On the other hand, a large increase of coercivity and remanent magnetization at a temperature between 5 and 50 K confirmed the presence of a magnetic transition at low temperatures. [ABSTRACT FROM AUTHOR]

Abstract: In this work, the structural and magnetic properties of the gold-coated FePt nanoparticles synthesized from high-temperature solution phase are presented. The amount of gold was optimized to obtain most of the FePt particles coated. The particle diameter increases from 4 to 10nm as observed by TEM. The magnetic properties are largely affected by the coating. At low temperature, the coercive field Hc of the coated nanoparticles decreases about three times respect to the uncoated and the blocking temperature reduces to the half. The changes of the magnetic behavior are discussed in terms of the effect of the gold atoms at the FePt core surface. [Copyright &y& Elsevier]

Recently, potential applications of the magnetic heating for heterogeneous catalysis or organic synthesis have been reported. As these new applications are not limited by biocompatibility requirements, a wide range of possibilities for non-aqueous colloidal nanoparticles with enhanced magnetic properties is open. In this work, manganese and cobalt ferrite nanoparticles are synthesized by co-precipitation method with average particle size around 12 nm. The particles are either coated with tetramethylammonium hydroxide (TMAOH) and dispersed in water or with oleic acid (OA) and dispersed in hexane to produce aggregated or disaggregated nanoparticles, respectively. It is observed that the particle disaggregation improves significantly the heating efficiency from 12 to 96 W/g in the case of cobalt ferrite, and from 120 to 413 W/g for the manganese ferrite. The main responsible for this improvement is the reduction of hydrodynamic volume that allows a faster Brownian relaxation. This work also discusses the relevance of the size distribution. [ABSTRACT FROM AUTHOR]

Abstract: We present a study on the magnetic properties of naked and silica-coated Fe3O4 nanoparticles with sizes between 5 and 110nm. 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 30nm, as expected for a Néel relaxation mechanism in single-domain particles. The SiO2 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 SiO2 functional coating as thin as possible. [Copyright &y& Elsevier]

Abstract: Nanocrystalline ZrO2 and TiO2 (n-ZrO2, n-TiO2), synthesized in a microwave plasma, have been investigated by X-ray and electron diffraction and by perturbed angular correlation (PAC) measurements of the nuclear electric quadrupole interaction (QI) of the probe nucleus 181Ta residing on the cation site. The microwave synthesis produces zirconia in the cubic/tetragonal phase, titania in the anatase structure. Grain growth and phase transformations have been studied in bare and Al2O3-coated zirconia particles. Coating the nanoparticles with an amorphous Al2O3 layer obstructs grain growth and may suppress the monoclinic phase. [Copyright &y& Elsevier]