57Fe Mössbauer spectroscopy and X-ray diffraction study of complex metamict minerals. Part II

The magnetic behaviour of the nanocrystalline Ni_0.5Cu_0.5Fe₂O₄, synthesized by the co-precipitation method has been studied. The X-ray diffraction patterns confirm the formation of cubic spinel structure. The dc magnetization measurements show that the samples are superparamagnetic above the blocking temperatures and the blocking temperature increases with particle size. The reduction in saturation magnetization in the case of nanoparticles as compared to their bulk counterpart has been explained on the basis that the magnetic moments in the surface layers of a nanoparticle are in a state of frozen disorder. The hump in ZFC curve progressively shift to a lower temperature with increasing field and broader curves at higher field, suggests the spin-glass nature of the system.     

Synthesis and functionalization of magnetite nanoparticles with different amino-functional alkoxysilanes

Superparamagnetic iron oxide (SPIO) nanoparticles show great promise for many biotechnological applications. This paper addresses the synthesis and characterization of SPIO nanoparticles grafted with three different alkoxysilanes: 3-aminopropyl-triethoxysilane (APTES), 3-aminopropyl-ethyl-diethoxysilane (APDES) and 3-aminopropyl-diethy-ethoxysilane (APES). SPIO nanoparticles with an average particle diameter of 10 nm were prepared by chemical sonoprecipitation. As confirmed by Fourier transform infrared (FTIR) spectroscopy, silylation of these nanoparticles occurs through a two-step process. Decreasing the number of alkoxide groups reduced the concentration of free amino groups on the SPIO surface ([SPIO-NH₂]—APTES>APDES>APES). This phenomenon results from steric contributions and the formation of H-bonded amines provided by the ethyl groups present in the APDES and APES molecules. A simulation of SPIO nanoparticles in a saline physiologic solution shows that the ethyl groups impart larger steric stability onto the ferrofluids, which reduces aggregation. The magnetization (M) versus magnetic field (H) curves show that the synthesized iron oxide nanoparticles display superparamagnetic behavior. The zero-field cooling (ZFC) and field cooling (FC) curves show that the changes in the blocking temperature depend on the alkoxysilane-functionalized particle surface.     

Magnetic properties of iron loaded MCM-48 molecular sieves

Mesoporous molecular sieves of MCM-48 type were loaded with iron by the wet impregnation method, using Fe(III) nitrate or Fe(II) sulfate aqueous solutions as Fe sources, to obtain a magnetic porous composite. The iron loaded materials were characterized by XRD, N₂ adsorption and DRUV-vis and compared with the Si-MCM-48 host. Their magnetic properties were studied by measuring the hysteresis loops up to 1.5 T at different temperatures (5-300 K) and by magnetization vs. temperature curves following the conventional zero field cooling (ZFC) and field cooling (FC) protocols. Materials with high structure regularity and surface area are obtained, which exhibit a mixed paramagnetic and superparamagnetic behavior, arising in isolated iron ions inserted in the host framework, and in small iron oxide clusters or nanoparticles forming inside the pores, respectively. Larger hematite particles (8-13 nm) grown on the external surface provide a quite small ferromagnetic contribution to the hysteresis loop.     

Magneto-optic Faraday effect in maghemite nanoparticles/silica matrix nanocomposites prepared by the Sol–Gel method

Bulk monolithic samples of γ-Fe₂O₃/SiO₂ composites with different iron oxide/silica ratios have been prepared by the sol–gel technique. Iron oxide nanoparticles are obtained in-situ during heat treatment of samples and silica matrix consolidation. Preparation method was previously optimized to minimize the percentage of antiferromagnetic α-Fe₂O₃ and parallelepipeds of roughly 2×5×12 mm³, with good mechanical stability, are obtained. RT magnetization curves show a non-hysteretic behavior. Thus, magnetization measurements have been well fitted to an expression that combines the Langevin equation with an additional linear term, indicating that some of the nanoparticles are still superparamagnetic as confirmed by X-ray diffraction and electron microscopy measurements. Zero field cooled /field cooled experiments show curves with slightly different shapes, depending on the size and shape distribution of nanoparticles for a given composition. Magneto-optical Faraday effect measurements show that the Faraday rotation is proportional to magnetization of the samples, as expected. As a demonstration of their sensing possibilities, the relative intensity of polarized light, measured at 5° from the extinction angle, was plotted versus applied magnetic field.     

Zero—field—cooled and field—cooled magnetizations and magnetic susceptibility of itinerant ferromagnet SrRuO3

Zero-field-cooled(ZFC) magnetization,field-cooled(FC) magnetization,ac magnetic susceptibility and major hysteresis loops of itinerant ferromagnet SrRuO3 have been measured at magnetic ordering temperatures ranging from 5 to 160K.An empirical model is proposed to calculate the measured ZFC magnetization.The result indicates that the calculated ZFC magnetization compares well with the measured one.Based on the generalized Preisach model.both the ZFC and FC curves are reproduced by numerical simulations.The critical temperature and critical exponents are determined by measuring the ac magnetic susceptibility in different bias magnetic fields at temperatures in the vicinity of the point of phase transition.     

Mössbauer study of Cu1−xZnxFe2O4 catalytic materials

In the present work, we have synthesized and characterized magnetic nanoparticles of maghemite γ-Fe₂O₃ to study their structural and magnetic properties. For the preparation, magnetite precursor, were oxidized by adjusting the pH = 3.5 at about 80 °C in an acid medium, The mean size of the maghemite particles calculated from the X-ray diffractogram was around 5.7 nm. Mössbauer spectroscopy measurements at room temperature show their superparamagnetic behavior. Furhermore, Mössbauer measurements were carried out at 77 K and 4.2 K in order to find the typical hyperfine fields of the maghemite. Magnetite phase was not found. FC and ZFC magnetization curves measured at 500 Oe indicate a blocking temperature of 105.3 K. The magnetization measurements also show almost zero coercivity at RT. TEM images show nanoparticles with diameter smaller than 10 nm, which are in good agreement with the X-ray pattern and the fitting of the magnetization data.     

Temperature behavior of magnetization of DyCo2 compound

Zero field cooled (ZFC) and field cooled (FC) magnetization measurements were performed on the binary DyCo₂ cubic compound. Maxima for this compound were observed under ZFC magnetization. Below the broad maximum, irreversibility is observed. The magnetization curves for ZFC and FC regimes are split and magnetic moments for FC are higher than for ZFC. The dependence of the maxima upon the magnetic field and the time dependence of remanence is similar to the case of spin-glass-like systems.     

EPR and Magnetization Studies of Polymer-Derived Fe-Doped SiCN Nanoceramics Annealed at Various Temperatures: Blocking Temperature,Superparamagnetism and Size Distributions

X-band EPR spectra on SiCN ceramics, doped with Fe(III) ions, annealed at 800 °C, 1000 °C, 1100 °C, 1285 °C, and 1400 °C have been simulated to understand better their magnetic properties, accompanied by new magnetization measurements in the temperature range of 5–400 K for zero-field cooling (ZFC) and field cooling (FC) at 100C. The EPR spectra reveal the presence of several kinds of Fe-containing nanoparticles with different magnetic properties. The maxima of the temperature variation of ZFC magnetization were exploited to estimate (i) the blocking temperature, which decreased with annealing temperature of the samples and (ii) the distribution of the size of Fe-containing nanoparticles in the various samples, which was found to become more uniform with increasing annealing temperature, implying that more homogenous magnetic SiCN/Fe composites can be fabricated by annealing at even higher temperatures than 1400 °C to be used as sensors. The hysteresis curves showed different behaviors above (superparamagnetic), below (ferromagnetic), and about (butterfly shape) the respective average blocking temperatures, 〈T_B〉. An analysis of the coercive field dependence upon temperature reveals that it follows Stoner–Wohlfarth model for the SiCN/Fe samples annealed above 1100 °C, from which the blocking temperatures was also deduced.     

Comparative study of core–shell iron/iron oxide gold covered magnetic nanoparticles obtained in different conditions

In this study, we report the synthesis and characterization of the core–shell Fe covered with Au shells nanoparticles with mean diameters between 5 and 8 nm. The inverse micelles method was utilized to produce the samples. X-ray diffraction studies show that both core–shell systems have the expected crystalline structure. High resolution transmission electron microscopy and atomic emission spectroscopy techniques give additional information concerning the structure and composition of nanoparticles. An intermediate shell of amorphous oxidized iron was found between the magnetic Fe core and the external gold shell. The magnetic behavior of different core–shell samples shows no hysteresis loop indicating the superparamagnetic behavior of Fe@Au systems. The superparamagnetic behavior is also evidenced from FC and ZFC dependences of the magnetization versus temperature. By using the temperature dependence of the thermoremanent magnetization combined with magnetization versus applied magnetic field, the effective anisotropy constant was determined. The Fe/Au interface contribution to the effective anisotropy constant was calculated and discussed in relation with the combined shape and stress anisotropies.     

Effects of dipolar interactions on magnetic properties of granular solids

The magnetic behavior of superparamagnetic Co nanoparticles (2–4 nm in diameter) dispersed in an amorphous, insulating SiO₂ matrix was studied. Conventional fittings of magnetization curves present mean magnetic moments which diminish with decrease in temperature. In order to treat this anomalous behavior, we have applied the interacting superparamagnetic model (ISP). Mean diameters obtained from transmission electron microscopy (TEM) were compared with values obtained applying ISP model.     

Magnetite nanoparticles embedded in biodegradable porous silicon

Magnetite nanoparticles, which are coated with oleic acid in a hexane solution and exhibit an average diameter of 7.7 nm, were embedded in a porous silicon (PS) matrix by immersion under defined parameters (e.g. concentration, temperature, time). The porous silicon matrix is prepared by anodization of a highly n-doped silicon wafer in an aqueous HF-solution. Magnetic characterization of the samples has been performed by SQUID-magnetometry. The superparamagnetic behaviour of the magnetite nanoparticles is represented by temperature-dependent magnetization measurements. Zero field (ZFC)/field cooled (FC) experiments indicate magnetic interactions between the particles. For the infiltration into the PS-templates different concentrations of the magnetite nanoparticles are used and magnetization measurements are performed in respect with magnetic interactions between the particles. The achieved porous silicon/magnetite specimens are not only interesting due to their transition between superparamagnetic and ferromagnetic behaviour, and thus for magnetic applications but also because of the non-toxicity of both materials giving the opportunity to employ the system in medical applications as drug delivery or in medical diagnostics.     

Magnetic properties and the mechanism of formation of the uncompensated magnetic moment of antiferromagnetic ferrihydrite nanoparticles of a bacterial origin

The magnetic properties of the superparamagnetic ferrihydrite nanoparticles that form as a result of the vital activity of Klebsiella oxytoca bacteria are studied. Both an initial powder with an average number of iron atoms N _Fe ～ 2000–2500 in a particle and this powder after annealing at 140°C for 3 h in air are investigated. The following substantial modifications of the magnetic properties of the ferrihydrite nanoparticles are detected after annealing: the superparamagnetic blocking temperature increases from 23 to 49.5 K, and the average magnetic moment of a particle increases (as follows from the results of processing of magnetization curves). The particles have antiferromagnetic ordering, and the magnetic moment resulting in the superparamagnetism of the system appears due to random spin decompensation inside the particle. For this mechanism, the number of uncompensated spins is proportional to the number of magnetically active atoms raised to the one-half power, and this relation holds true for the samples under study at a good accuracy. The possible causes of the detected shift of magnetic hysteresis loops at low temperatures upon field cooling are discussed.     

Magnetic susceptibility curves of a nanoparticle assembly, I: Theoretical model and analytical expressions for a single magnetic anisotropy energy

We study a model system made of non-interacting monodomain ferromagnetic nanoparticles, considered as macrospins, with a randomly oriented uniaxial magnetic anisotropy. We derive a simple differential equation governing the magnetic moment evolution in an experimental magnetic susceptibility measurement, at low field and as a function of temperature, following the well-known Zero-Field Cooled/Field Cooled (ZFC/FC) protocol. Exact and approximate analytical solutions are obtained, together for the ZFC curve and the FC curve. The notion of blocking temperature is discussed and the influence of various parameters on the curves is investigated. A crossover temperature is defined and a comparison is made between our progressive crossover model (PCM) and the crude “two states” or abrupt transition model (ATM), where the particles are assumed to be either fully blocked or purely superparamagnetic. We consider here the case of a single magnetic anisotropy energy (MAE), which is a prerequisite before considering the more realistic and experimentally relevant case of an assembly of particles with a MAE distribution (cf. part II that follows).     

Non-equilibrium effects in the magnetic behavior of Co3O4 nanoparticles

We report detailed studies of the non-equilibrium magnetic behavior of antiferromagnetic Co₃O₄ nanoparticles. The temperature and field dependence of magnetization, wait time dependence of magnetic relaxation (aging), memory effects, and temperature dependence of specific heat have been investigated to understand the magnetic behavior of these particles. We find that the system shows some features that are characteristic of nanoparticle magnetism such as bifurcation of field-cooled (FC) and zero-field-cooled (ZFC) susceptibilities and a slow relaxation of magnetization. However, strangely, the temperature at which the ZFC magnetization peaks coincides with the bifurcation temperature and does not shift on application of magnetic fields up to 1 kOe, unlike most other nanoparticle systems. Aging effects in these particles are negligible in both FC and ZFC protocols, and memory effects are present only in the FC protocol. We show that Co₃O₄ nanoparticles constitute a unique antiferromagnetic system which enters into a blocked state above the average Néel temperature.     

Magnetic properties of ZnFe2O4 nanoparticles produced by a low-temperature solid-state reaction method

ZnFe₂O₄ nanoparticles with average grain size ranging from 40 to 60 nm behaving superparamagnetic at room temperature have been produced using a low-temperature solid-state reaction (LTSSR) method without ball-milling process. Abnormal magnetic properties such as S-shape hysteresis loops and non-zero magnetic moments were observed. ZnFe₂O₄ nanoparticles were also synthesized using a NaOH coprecipitation method and a PVA sol-gel method to study the relationship between the preparation processes and the magnetic properties. Spin-glass behavior was observed in the low temperature solid-state reaction produced Zn ferrite in the zero-field cooled (ZFC) measurement. Our work proves that the various preparation methods will to some extent determine the properties of magnetic nanoparticles.     

Modeling of the blocking temperature of a system of core/shell nanoparticles

A theoretical study was conducted on the size dependence of the blocking temperature T_b of a system of interacting core/shell nanoparticles. A method for estimating the blocking temperature of interacting core/shell nanoparticles is presented, which allows T_b to be calculated more precisely than using the “Neel relation”. It was shown that with an increase in the intensity of the magnetostatic interaction (concentration of nanoparticles), the blocking temperature increases, while the growth of the external magnetic field leads to the opposite effect. Moreover, the T_b of large nanoparticles changes more significantly. Comparing different approaches, we identify a precise method for determining the blocking temperature from ZFC and FC magnetization curves.     

Effect of composition and thermal treatment on the properties and microstructure of Co–SiO<Subscript>2</Subscript> films

The effect of various physical factors (chemical composition, temperature, and thermal treatment) on the macroscopic properties of Co–SiO₂ film composites produced by ion-plasma sputtering of mosaic targets has been investigated. The microstructure parameters have been estimated indirectly by analyzing the magnetization curves and the temperature dependence of magnetization. It has been concluded that the model of homogeneous noninteracting superparamagnetic particles of hexagonal Co is applicable for describing the magnetic properties of the film composites under study over a rather wide range of compositions.     

Synthesis and characterization of superparamagnetic iron oxide nanoparticles for biomedical applications

Monodisperse iron oxide nanoparticles (NPs) of 4 nm were obtained through high-temperature solution phase reaction of iron (III) acetylacetonate with 1, 2-hexadecanediol in the presence of oleic acid and oleylamine. The as-synthesized iron oxide nanoparticles have been characterized by X-ray diffraction, transmission electron microscopy, Mössbauer spectroscopy and magnetic measurements. The species obtained were Fe₃O₄ and/or $\upgamma$ -Fe₂O₃. These NPs are superparamagnetic at room temperature and even though the reduced particle size they show a high saturation magnetization (MS ≈ 90 emu/g).     

Ferromagnetic properties of glucose coated Cu2O nanoparticles

Magnetic properties of glucose coated cuprous oxide nanoparticles of different sizes have been studied. Unlike bulk Cu₂O, which shows diamagnetic behavior, the nanoparticles show superparamagnetic behavior. A superparamagnetic blocking temperature of 21 K is observed for 5 nm particles. A magnetic hysteresis loop with a coercivity of 406 Oe is observed for these particles at 5 K. The magnetization and the coercivity increase with decreasing particle size. The superparamagnetic behavior, along with the increase in magnetization and coercivity with decreasing particle size, is due to the enhanced surface contributions to the magnetism.     

Magnetic properties of some opal-based nanocomposites

Nanoparticles of complex titanium, cobalt, and manganese oxides with ilmenite and spinel structure have been synthesized in pores of an opal. The particle composition has been determined by X-ray diffraction analysis. The magnetic properties of the obtained nanocomposites with different particles embedded in pores have been studied. The temperature dependences of the dc and ac magnetizations in the range from 2 to 300 K have been measured. It has been shown that the magnetic ordering in all the nanocomposites studied emerges at temperatures above 150 K, which not in all cases can be related directly to the properties of the materials identified by X-ray diffraction. The appearance of peaks in the ZFC susceptibility and ac magnetization curves below 50 K is assigned to disordering and frustration in nanoparticles of titanates of the type of CoTiO₃, NiTiO₃, and Co₂TiO₄.