Magnetic properties of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> surface

The magnetic properties of the magnetite Fe₃O₄(110) surface have been studied by spin resolved Auger electron spectroscopy (SRAES). Experimental spin resolved Auger spectra are presented. The results of calculation of Auger lines polarization carried out on the basis of electronic state density are presented. Problems related to magnetic moments of bivalent (Fe²⁺) and trivalent (Fe³⁺) ions on the Fe₃O₄(110) surface are discussed. It is established that the deposition of a thin bismuth film on the surface results in significant growth of polarization of iron Auger peaks, which is due to additional spin-orbit scattering of electrons by bismuth atoms.     

Magnetic properties and local configurations of <Superscript>57</Superscript>Fe atoms in CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> powders and CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/PVA nanocomposites

The composition and magnetic properties of the powders extracted from CoFe₂O₄ aqueous suspensions and the CoFe₂O₄/PVA (PVA is polyvinyl alcohol) nanocomposites with a cobalt ferrite content of 10–30 wt % have been investigated using Mössbauer spectroscopy, transmission electron microscopy, and vibration magnetometry. The cationic formulas of the cobalt ferrites synthesized have been determined. The differences between samples synthesized at temperatures of 72.5 and 82.5°C have been revealed. The specific features of the observed changes in the agglomeration of CoFe₂O₄ particles after introducing into the PVA matrix have been studied. It has been shown that the iron ion distribution determined by Mössbauer spectroscopy in octahedral and tetrahedral lattice sites correlates with vibration magnetometry data.     

Synthesis and studies of trisubstituted biphthalonitrile/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> magnetic hybrid microspheres

New trisubstituted biphthalonitrile/magnetite (TSB/Fe₃O₄) magnetic hybrid microspheres were synthesized from TSB and FeCl₃ · 6H₂O using the method of one-stage thermal temperature crystallization of solvents. The morphology and structure of magnetic hybrid microspheres were inspected using a scanning electron microscope, IR Fourier spectroscopy, and X-ray diffraction. It was found that the grown TSB/Fe₃O₄ magnetic hybrid microspheres represent spherical particles with an average size of ~137 nm and a small size spread. The size and size distribution of magnetic hybrid microspheres can be controlled by a small change in the ratio of TSB and Fe³⁺ ion contents in the microsphere. TSB/Fe₃O₄ hybrid microspheres exhibit a rather high saturation magnetization (58.16 emu g^–1) and new microwave electromagnetic properties, i.e., lower (in comparison with published) dielectric losses at low frequencies; magnetic losses are increased obviously due to an increase in the TSB content. Furthermore, it is detected that magnetic hybrid microspheres absorb microwaves, and strong reflection losses in a wide frequency range are established. The effective reflection loss of–31 dB is obtained in the microwave range from 2 to 16 GHz due to TSB content variations. Wide absorption properties of microwaves along with regular spherical shape and excellent magnetic properties offer wide opportunities for various applications of TSB/Fe₃O₄ magnetic hybrid microspheres as functional materials.     

Fabrication,structure, and properties of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@C encapsulated with YVO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript> composites

The use of carbon shells offers many advantages in surface coating or surface modification due to their surface with activated carboxyl and carbonyl groups. In this study, the Fe₃O₄@C@YVO₄:Eu³⁺ composites were prepared through a simple sol–gel process. Reactive carbon interlayer was introduced as a key component, which separates lanthanide-based luminescent component from the magnetite, more importantly, it effectively prevent oxidation of the Fe₃O₄ core during the whole preparation process. The morphology, structure, magnetic, and luminescent properties of the composites were characterized by transmission electron microscopy (TEM), high-resolution TEM, X-ray diffraction, X-ray photoelectron spectra, VSM, and photoluminescent spectrophotometer. As a result, the Fe₃O₄@C/YVO₄:Eu³⁺ composites with well-crystallized and core–shell structure were prepared and the YVO₄:Eu³⁺ luminescent layer decorating the Fe₃O₄@C core–shell microspheres are about 10 nm. In addition, the Fe₃O₄@C@YVO₄:Eu³⁺ composites have the excellent magnetic and luminescent properties, which allow them great potential for bioapplications such as magnetic bioseparation, magnetic resonance imaging, and drug/gene delivery.     

Large influence of the synthesis conditions on the physico-chemical properties of nanostructured Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>

Magnetite synthesized via three different synthesis routes (coprecipitation process in aqueous media, electrochemical synthesis in presence of complexing agents and solid state reaction at high temperature) has been characterized by X-Ray diffraction, scanning electron microscopy, thermal analysis (TGA), FT-IR and Mössbauer spectroscopies. Although each procedure gave homogeneous magnetite powders, many differences could be seen in the physico-chemical properties of the samples mostly depending on the synthesis conditions. For instance, at least two factors seem to have a huge impact onto the Fe₃O₄ behaviour: the presence of hydration water molecules and the particle size of the powders since a superparamagnetic behaviour was observed with the thinnest particles, at room temperature, on the Mössbauer spectra via the appearance of line broadening and a pronounced central doublet.     

Synthesis of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles with tunable magnetism by the modified hydrothermal method

Cobalt ferrite (CoFe₂O₄) nanoparticles were synthesized by using the hydrothermal route with the addition of trisodium citrate dihydrate (Na₃CA·2H₂O). The formation of CoFe₂O₄ nanoparticles with size ranging from 13 to 19 nm was confirmed by X-ray diffraction, energy dispersive X-ray analysis, and Fourier transform infrared spectroscopy; the clear-cut sharp of the nanoparticles was observed by transmission electron microscopy. By these characterization methods, the evolution of lattice constant and morphologies of the nanoparticles with the addition of Na₃CA·2H₂O is observed. Furthermore, the magnetic hysteresis loops measured at room temperature indicate that the magnetic properties of the products also show clear relationship with the masses of Na₃CA·2H₂O. For example, coercivity and high-field paramagnetic susceptibility increase with the increasing masses of Na₃CA·2H₂O, whereas the saturation magnetization and the effective magnetic anisotropy constant have the maximum values as the mass of Na₃CA·2H₂O is 1 g. This change of magnetic properties is related with the expanded lattice and the varied size and shape because of the addition of Na₃CA·2H₂O.     

Microemulsion-mediated in-situ synthesis and magnetic characterization of polyaniline/Zn<Subscript>0.5</Subscript>Cu<Subscript>0.5</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanocomposite

Polyaniline/Zn_0.5Cu_0.5Fe₂O₄ nanocomposite was synthesized by a simple, general and inexpensive in-situ polymerization method in w/o microemulsion. The effects of polyaniline coating on the magnetic properties of Zn_0.5Cu_0.5Fe₂O₄ nanoparticles were investigated. The structural, morphological and magnetic properties of as-prepared samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectra, scanning electron microscopy (SEM) and magnetic measurements. The morphology analysis confirmed that polyaniline was deposited on the porous surface of magnetic Zn_0.5Cu_0.5Fe₂O₄. It was shown that the saturation magnetization and coercivity of Zn_0.5Cu_0.5Fe₂O₄ decreased after polyaniline coating, which can be interpreted by the interparticle dipole–dipole interactions that contributed to magnetic anisotropy and changed the magnetic properties of the nanoparticles. PACS  74.25.Ha; 81.05.-t; 81.05.Lg     

Polymethylmethacrylate/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> composite nanofiber membranes with ultra-low dielectric permittivity

Ultra-low dielectric permittivity poly (methyl methacrylate)/Fe₃O₄ composite fiber membranes have been successfully prepared using electrospinning. The composite membranes were characterized by SEM (scanning electron microscopy), TEM (transmission electron microscopy), FT-IR (Fourier transform infrared), XRD (X-ray diffraction) and a radio frequency (RF) impedance/capacitance material analyzer. The magnetic measurement showed that the composite membranes displayed the super-paramagnetic property. The results showed that the dielectric permittivity of the composite fiber membranes was decreasing with increasing Fe₃O₄ nanoparticle content.     

Surface photovoltage properties and photocatalytic activities of nanocrystalline CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> particles with porous superstructure fabricated by a modified chemical coprecipitation method

In this study, nanocrystalline CoFe₂O₄ particles with porous timber-like superstructure were synthesized by a modified chemical co-precipitation route with calcination temperatures of 573, 673, 773, 873, and 973 K, respectively. The structural properties of the samples were systematically investigated by X-ray powder diffraction, scanning electronic microscopy, energy-dispersive X-ray spectra, UV–Vis diffuse reflectance spectroscopy, and Fourier transform infrared spectroscopy techniques. The photo-induced charge separation in the samples was demonstrated by surface photovoltage (SPV) measurement. The photocatalytic performances of the CoFe₂O₄ samples were comparatively studied by the degradation of 4-chlorophenol under Xe lamp irradiation. The results indicated that the sample calcined at 673 K exhibited the highest photocatalytic efficiency among the five samples.     

Magnetic properties of Pb<Subscript>2</Subscript>Fe<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>9</Subscript> single crystals

Single crystals of Pb₂Fe₂Ge₂O₉ have been grown. They were subjected to X-ray diffraction, magnetic, neutron diffraction, Mössbauer and spin resonance studies. It has been established that Pb₂Fe₂Ge₂O₉ is a weak ferromagnet with a Néel temperature T _N = 46 K, and the exchange and spin-flop transition fields have been estimated. It has been demonstrated that the weak ferromagnetic moment is actually the result of the single-ion anisotropy axes for the magnetic moments of different magnetic sublattices being not collinear.     

Magnetoreflection and Magnetostriction in Ferrimagnetic Spinels CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>

It is shown that magnetoreflectance of natural light up to +4% exists in magnetostrictive ferrimagnetic spinel CoFe₂O₄ single crystal; this effect is associated with a change of the fundamental absorption edge, the impurity absorption band, and the phonon spectrum under the action of a magnetic field. The correlation between the field dependences of magnetoreflectance and magnetostriction has been established. The physical mechanisms responsible for the spectral and field peculiarities of magnetoreflection have been explained. It is shown that the magnetorefractive effect in CoFe₂O₄, which is associated with magnetoelastic properties of the spinel, amounts to +1.5 × 10^–3 in magnetic fields exceeding the saturation field. Analysis of magnetooptical and magnetoelastic data has made it possible to estimate deformation potential as Ξ _u = 20 eV for the valence band of the spinel.     

Growth of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> films on the Si(111) surface covered by a thin SiO<Subscript>2</Subscript> layer

Magnetite polycrystalline films are grown by variously oxidizing a Fe film on the Si(111) surface covered by a thin (1.5 nm) SiO₂ layer. It is found that defects in the SiO₂ layer influence silicidation under heating of the Fe film. The high-temperature oxidation of the Fe film results in the formation of both Fe₃O₄ and iron monosilicide. However, the high-temperature deposition of Fe in an oxygen atmosphere leads to the growth of a compositionally uniform Fe₃O₄ film on the SiO₂ surface. It is found that such a synthesis method causes [311] texture to arise in the magnetite film, with the texture axis normal to the surface. The influence of the synthesis method on the magnetic properties of grown Fe₃O₄ films is studied. A high coercive force of Fe₃O₃ films grown by Fe film oxidation is related to their specific morphology and compositional nonuniformity.     

Electromagnetic wave absorption properties of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> octahedral nanocrystallines in gigahertz range

Large-scale octahedral Fe₃O₄ nanocrystallines with crystalline size of 100−500 nm were synthesized by a facile solvent-thermal method for electromagnetic wave application. The Fe₃O₄ nanocrystallines showed a higher saturation magnetization (M _s ) value of 86.8 emu/g and larger coercivity (H _cj ) value of 255 Oe than that of magnetite polycrystallines because of their good crystallization and dispersion. The epoxy resin composites with 40 vol% Fe₃O₄ powders provided good electromagnetic wave absorption performance (RL < −20 dB) in the range of 2.0–4.3 GHz over the absorber thicknesses of 3.5–6.8 mm. A minimum RL value of −47 dB was observed at 3.1 GHz with a thickness of 4.8 mm.     

Electric and magnetic properties of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/Pb(Zr<Subscript>0.52</Subscript>Ti<Subscript>0.48</Subscript>)O<Subscript>3</Subscript> bilayer thin films prepared by pulsed-laser deposition

CoFe₂O₄ (CFO) thin film with highly (111)-preferential orientation was first deposited on the silicon substrate by a pulsed-laser deposition, and then Pb(Zr_0.52Ti_0.48)O₃ (PZT) layers were deposited with different oxygen pressures to form the bilayer CFO/PZT nanocomposite thin films. X-ray diffraction showed that the PZT preferential orientation was strongly dependant on the oxygen pressure. The smooth film surface was obtained after depositing the CFO and PZT layers. The bilayer thin films exhibit good ferromagnetic and ferroelectric properties, and a low leakage current density of 0.004 μA/cm² at 50 kV/cm. The leakage current density curves show loops for the electric polarized field when the electric field reverses. PACS 77.84.Lf; 75.80+q; 81.05.Zx; 81.15.Fg     

Cluster formation in LiNi<Subscript>0.4</Subscript>Fe<Subscript>0.6</Subscript>O<Subscript>2</Subscript>

The structure of an LiNi_0.4Fe_0.6O₂ cubic solid solution is determined using magnetic measurements and electron diffraction. It is found that this solid solution has a microinhomogeneous structure due to the formation of superparamagnetic clusters. The electron diffraction analysis of LiNi_0.4Fe_0.6O₂ samples has revealed diffuse scattering characteristic of the substitutional short-range order in ordered solid solutions with a B1-type structure. It is shown that the short-range order is associated with the LiNiO₂-type rhombohedral superstructure (space group \(R\bar 3m\)), i.e., with the redistribution of lithium and nickel atoms in the (111)_B1 alternating planes. The short-range order is observed in regions with a nickel content higher than the mean nickel content corresponding to the macroscopic composition.     

Fe<Subscript>3</Subscript>P impurity phase in high-quality LiFePO<Subscript>4</Subscript>: X-ray diffraction and neutron-graphical studies

High discharge capacity and long life cycles of electrodes fabricated from various LiFePO₄ powders have been used to select samples for detailed structural studies. In some samples, the presence of ferromagnetic Fe₃P crystallites was revealed by the synchrotron X-ray diffraction analysis, with the integral intensity ratio of the peaks Fe₃P (231) and LiFePO₄ (112) equal to ～1/12. Small-angle polarized neutron scattering (SAPNS) detected the presence of magnetic nuclear contrasting regions with size of 17 ± 1 nm. The average diameter of LiFePO₄ crystallites is 230 nm, and Fe₃P crystallites were found as 17 × 54 nm² plates. The high quality of these samples was provided by their manufacturer via synthesis of the Fe₃P impurity phase. It can be stated that the set of studies, developed in the study, is helpful in a search for new effective impurity phases and in optimization of their parameters.     

ZnO-coated LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> cathode material for lithium-ion batteries synthesized by a combustion method

ZnO-coated LiMn₂O₄ cathode materials were prepared by a combustion method using glucose as fuel. The phase structures, size of particles, morphology, and electrochemical performance of pristine and ZnO-coated LiMn₂O₄ powders are studied in detail by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), galvanostatic charge-discharge test, and X-ray photoelectron spectroscopy (XPS). XRD patterns indicated that surface-modified ZnO have no obvious effect on the bulk structure of the LiMn₂O₄. TEM and XPS proved ZnO formation on the surface of the LiMn₂O₄ particles. Galvanostatic charge/discharge test and rate performance showed that the ZnO coating could improve the capacity and cycling performance of LiMn₂O₄. The 2 wt% ZnO-coated LiMn₂O₄ sample exhibited an initial discharge capacity of 112.8 mAh g^?1 with a capacity retention of 84.1 % after 500 cycles at 0.5 C. Besides, a good rate capability at different current densities from 0.5 to 5.0 C can be acquired. CV and EIS measurements showed that the ZnO coating effectively reduced the impacts of polarization and charge transfer resistance upon cycling.     

Controlled-synthesis,characterization, and magnetic properties of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanostructures

Fe₃O₄ nanostructures with different morphologies, including uniform nanoparticles, nanorods and nanowire bundles, have been successfully synthesized via a facile hydrothermal route. Based on the observation of TEM images, the growth mechanism of one-dimensional Fe₃O₄ nanostructures is in accordance with Ostwald ripening process. From the hysteresis loops of as-prepared Fe₃O₄ products, we found that the morphology has great influence on the magnetic properties. The uniform Fe₃O₄ nanoparticles have higher saturation magnetization and lower coercivity than that of Fe₃O₄ nanorods and nanowires bundles. These phenomena attribute to the high shape anisotropy of nanorods and nanowire bundles, which prevent them from magnetizing in directions other than along their easy magnetic axes. PACS 81.07.-b; 75.50.Bb; 75.30.Gw; 81.10.Dn; 81.16.Be     

Plasmachemical synthesis and basic properties of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> magnetic nanoparticles

Cobalt-ferrite (CoFe₂O₄) nanoparticles (CFNPs) are obtained using direct plasmachemical synthesis in the plasma of a low-pressure arc discharge. The formation of the CFNPs with an average size of 9 nm and a narrow granulometric composition is established employing the methods of X-ray structure analysis and transmission microscopy. The CFNP behavior upon high-temperature annealing is analyzed. The CFNP functional groups are determined using the infrared Fourier spectrum. The results of the X-ray energy dispersion confirm the correspondence of the ratio of the number of atoms of each material to the nominal stoichiometry. The basic magnetic properties of the obtained and annealed samples are investigated at room temperature using the vibrating spectrum magnetometry (VSM).     

The magnetization reversal in CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/CoFe<Subscript>2</Subscript> granular systems

The temperature-dependent field cooling (FC) and zero-field cooling (ZFC) magnetizations, i.e., M _FC and M _ZFC, measured under different magnetic fields from 500 Oe to 20 kOe have been investigated on two exchange–spring CoFe₂O₄/CoFe₂ composites with different relative content of CoFe₂. Two samples exhibit different magnetization reversal behaviors. With decreasing temperature, a progressive freezing of the moments in two composites occurs at a field-dependent irreversible temperature T _irr. For the sample with less CoFe₂, the curves of ?d(M _FC ? M _ZFC)/dT versus temperature T exhibit a broad peak at an intermediate temperature T ₂ below T _irr , and the moments are suggested not to fully freeze till the lowest measuring temperature 10 K. However, for the ?d(M _FC ? M _ZFC)/dT curves of the sample with more CoFe₂, besides a broad peat at an intermediate temperature T ₂, a rapid rise around the low temperature T ₁~15 K is observed, below which the moments are suggested to fully freeze. Increase of magnetic field from 2 kOe leads to the shift of T ₂ and T _irr towards a lower temperature, and the shift of T ₂ is attributable to the moment reversal of CoFe₂O₄.

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Graphical abstract CoFe₂O₄/CoFe₂ composites with different relative content of CoFe₂ were prepared by reducing CoFe₂O₄ in H₂ for 4 h (S4H) and 8 h (S8H). The temperature-dependent FC and ZFC magnetizations, i.e., M _FC and M _ZFC, under different magnetic fields from 500 Oe to 20 kOe have been investigated. Two samples exhibit different magnetization reversal behaviors. With decreasing temperature, a progressive freezing of the moments in two composites occurs at field-dependent irreversible temperature T _irr. For the S4H sample, the curves of ?d(M _FC ? M _ZFC)/dT versus temperature T exhibit a broad and field-dependent relaxing peak at T ₂ below T _irr (figure a), and the moments were suggested not to fully freeze till the lowest measuring temperature 10 K. However, for the S8H sample, it exhibits the reentrant spin-glass state around 50 K, as evidenced by a peak in the M _FC curve (inset in figure b) and as a result of the cooperative effects of the random anisotropy of CoFe₂O₄, exchange–spring occurring at the interface of CoFe₂O₄ and CoFe₂ together with the inter-particle dipolar interaction (figure c); in ?d(M _FC ? M _ZFC)/dT curves, besides a broad relaxing peat at T ₂, a rapid rise around the low-temperature T ₁~15 K is observed, below which the moments are suggested to fully freeze. Increase of magnetic field from 2 kOe leads to the shift of T ₂ and T _irr towards a lower temperature, and the shift of T ₂ is attributable to the moment reversal of CoFe₂O₄.