Ferromagnetic resonance observation of a phase transition in magnetic field-aligned Fe2O3 nanoparticles

Fe₂O₃ hematite (alpha) nanoparticles suspended in the liquid phase of the liquid crystal 4,4-azoxyanlsole (PAA) are cooled below the freezing temperature (397 K) in a 4000 G dc magnetic field. The in field solidification locks the direction of maximum magnetization of the particles parallel to the direction of the applied dc magnetic field removing the effects of dynamical fluctuations of the nanoparticles on the magnetic properties allowing a study of the intrinsic magnetic properties of the nanoparticles as well as the anisotropic behavior of the ferromagnetic resonance (FMR) signal. Freezing in PAA allows temperature-dependent measurements to be made at much higher temperature than previous measurements. The field position, line width and intensity of the FMR signal as a function of temperature as well as the magnetization show anomalies in the vicinity of 200 K indicative of a magnetic transition, likely the previously observed Morin transition shifted to lower temperature due to the small particle size. Weak ferromagnetism is observed below T_c in contrast to the bulk material where it is antiferromagnetic below T_c. The Raman spectrum above and below 200 K shows no evidence of a change in lattice symmetry associated with the magnetic transition.     

Ferromagnetism and spin reorientation in Sm12Fe14Al5

The single crystal of the new ternary compound Sm₁₂Fe₁₄Al₅ was grown and its crystallographic and magnetic properties were investigated. Sm₁₂Fe₁₄Al₅ has a hexagonal structure of the space group p-3m1 and shows ferromagnetism with a Curie temperature of 245 K. The easy direction of magnetization is parallel to the c-axis at temperatures between 245 and 85 K; however, it changes to the c-plane below 85 K through a first-order-like phase transition. No saturation is observed in the magnetization curve even under the applied field of 55 kOe at 5 K. Sm₁₂Fe₁₄Al₅ seems to have a large coercive field at very low temperatures. The anisotropy field was estimated at 5 and 120 K and the saturation magnetization of low temperature phase is explained assuming a ferromagnetic coupling between Fe and Sm sublattices.     

Magnetic,electrical transport and electron spin resonance studies of Fe-doped manganite LaMn0.7Fe0.3O3+δ

We have investigated the magnetic, electrical transport and electron spin resonance (ESR) properties of polycrystalline Fe-doped manganite LaMn_0.7Fe_0.3O_3+δ prepared by sol–gel method. A typical cluster-glass feature is presented by DC magnetization and AC susceptibility measurements and a sharp but shallow memory effect was observed. Symmetrical Lorentzian lines of the Mn/Fe spectra were detected above 120 K, where the sample is a paramagnetic (PM) insulator. When the temperature decreases from 120 K, magnetic clusters contributed from ferromagnetic (FM) interaction between Mn³⁺ and Mn³⁺/Fe³⁺ ions develop and coexist with PM phase. At lower temperature, these FM clusters compete with antiferromagnetic (AFM) ones between Fe³⁺ ions, which are associated with a distinct field-cooled (FC) effect in characteristic of cluster-glass state.     

Magnetic properties of the novel nanocomposite (Zn0.15Ni0.85Fe2O4)0.15/(SiO2)0.85 at room temperature

The value of the effective magnetic anisotropy constant of the ferrimagnetic nanoparticles Zn_0.15Ni_0.85Fe₂O₄ embedded in a SiO₂ silica matrix, determined through ferromagnetic resonance (FMR), is much higher than the magnetocrystalline anisotropy constant. The higher value of the anisotropy constant is due to the existence of surface anisotropy. However, even if the magnetic anisotropy is high, the ferrimagnetic nanoparticles with a 15% concentration, which are isolated in a SiO₂ matrix, display a superparamagnetic (SPM) behavior at room temperature and at a frequency of the magnetization field equal to 50 Hz. The FMR spectrum of the novel nanocomposite (Zn_0.15Ni_0.85Fe₂O₄)_0.15/(SiO₂)_0.85, recorded at room temperature and a frequency of 9.060 GHz, is observed at a resonance field (B_0r) of 0.2285 T, which is substantially lower than the field corresponding to free electron resonance (ESR) (0.3236 T). Apart from the line corresponding to the resonance of the nanoparticle system, the spectrum also contains an additional weaker line, identified for a resonance field of ∼0.12 T, which is appreciably lower than B_0r. This line was attributed to magnetic ions complex that is in a disordered structure in the layer that has an average thickness of 1.4 nm, this layer being situated on the surface of the Zn_0.15Ni_0.85Fe₂O₄ nanoparticles that have a mean magnetic diameter of 8.9 nm.     

Exchange coupling behavior in bimagnetic CoFe2O4/CoFe2 nanocomposite

In this work we report a study of the magnetic behavior of ferrimagnetic oxide CoFe₂O₄ and ferrimagnetic oxide/ferromagnetic metal CoFe₂O₄/CoFe₂ nanocomposite. The latter compound is a good system to study hard ferrimagnet/soft ferromagnet exchange coupled. Two steps were followed to synthesize the bimagnetic CoFe₂O₄/CoFe₂ nanocomposite: (i) first, preparation of CoFe₂O₄ nanoparticles using a simple hydrothermal method, and (ii) second, reduction reaction of cobalt ferrite nanoparticles using activated charcoal in inert atmosphere and high temperature. The phase structures, particle sizes, morphology, and magnetic properties of CoFe₂O₄ nanoparticles were investigated by X-Ray diffraction (XRD), Mossbauer spectroscopy (MS), transmission electron microscopy (TEM), and vibrating sample magnetometer (VSM) with applied field up to 3.0 kOe at room temperature and 50 K. The mean diameter of CoFe₂O₄ particles is about 16 nm. Mossbauer spectra revealed two sites for Fe³⁺. One site is related to Fe in an octahedral coordination and the other one to the Fe³⁺ in a tetrahedral coordination, as expected for a spinel crystal structure of CoFe₂O₄. TEM measurements of nanocomposite showed the formation of a thin shell of CoFe₂ on the cobalt ferrite and indicate that the nanoparticles increase to about 100 nm. The magnetization of the nanocomposite showed a hysteresis loop that is characteristic of exchange coupled systems. A maximum energy product (BH)_max of 1.22 MGOe was achieved at room temperature for CoFe₂O₄/CoFe₂ nanocomposites, which is about 115% higher than the value obtained for CoFe₂O₄ precursor. The exchange coupling interaction and the enhancement of product (BH)_max in nanocomposite CoFe₂O₄/CoFe₂ are discussed.     

Green synthesis of soya bean sprouts-mediated superparamagnetic Fe3O4 nanoparticles

Superparamagnetic Fe₃O₄ nanoparticles were first synthesized via soya bean sprouts (SBS) templates under ambient temperature and normal atmosphere. The reaction process was simple, eco-friendly, and convenient to handle. The morphology and crystalline phase of the nanoparticles were determined from scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and X-ray diffraction (XRD) spectra. The effect of SBS template on the formation of Fe₃O₄ nanoparticles was investigated using X-ray photoemission spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FT-IR). The results indicate that spherical Fe₃O₄ nanoparticles with an average diameter of 8 nm simultaneously formed on the epidermal surface and the interior stem wall of SBS. The SBS are responsible for size and morphology control during the whole formation of Fe₃O₄ nanoparticles. In addition, the superconducting quantum interference device (SQUID) results indicate the products are superparamagnetic at room temperature, with blocking temperature (T_B) of 150 K and saturation magnetization of 37.1 emu/g.     

Magnetic properties of Ni-substituted BiFeO3

BiFe_1−xNi_xO₃ ceramic powders with x up to 0.10 have been prepared by the sol-gel technique. The band gap of BiFeO₃ is 2.23 eV, and decreases to 2.09 eV for BiFe_0.95Ni_0.05O₃ and BiFe_0.90Ni_0.10O₃. The Mössbauer spectra show sextet at room temperature, indicating the magnetic ordering and the presence of only Fe³⁺ ions. Superparamagnetism with blocking temperature of 31 K for BiFe_0.95Ni_0.05O₃ and 100 K for BiFe_0.90Ni_0.10O₃ was observed. Enhanced magnetization at room temperature have been observed (1.0 emu/g for BiFe_0.95Ni_0.05O₃ and 2.9 emu/g for BiFe_0.90Ni_0.10O₃ under magnetic field of 10,000 Oe), which is one order larger than that of BiFeO₃ (0.1 emu/g under magnetic field of 10,000 Oe). The enhanced magnetization was attributed to the suppression of the cycloidal spin structure by Ni³⁺ substitution and the ferrimagnetic interaction between Fe³⁺ and Ni³⁺ ions.     

Magnetic and rheological properties of monodisperse Fe3O4 nanoparticle/organic hybrid

Fe₃O₄ nanoparticle/organic hybrids were synthesized via hydrolysis using iron (III) acetylacetonate at ∼80 °C. The synthesis of Fe₃O₄ was confirmed by X-ray diffraction, selected-area diffraction, and X-ray photoelectron spectroscopy. Fe₃O₄ nanoparticles in the organic matrix had diameters ranging from 7 to 13 nm depending on the conditions of hydrolysis. The saturation magnetization of the hybrid increased with an increase in the particle size. When the hybrid contained Fe₃O₄ particles with a size of less than 10 nm, it exhibited superparamagnetic behavior. The blocking temperature of the hybrid containing Fe₃O₄ particles with a size of 7.3 nm was 200 K, and it increased to 310 K as the particle size increased to 9.1 nm. A hybrid containing Fe₃O₄ particles of size greater than 10 nm was ferrimagnetic, and underwent Verwey transition at 130 K. Under a magnetic field, a suspension of the hybrid in silicone oil revealed the magnetorheological effect. The yield stress of the fluid was dependent on the saturation magnetization of Fe₃O₄ nanoparticles in the hybrid, the strength of the magnetic field, and the amount of the hybrid.     

Magnetic properties of RE0.7Ca0.3Mn0.95Fe0.05O3 (RE=Sm and Gd) manganites at low temperature

The magnetic properties of RE_0.7Ca_0.3Mn_0.95Fe_0.05O₃ perovskite with rare-earth cations (RE=Sm and Gd) were investigated by means of X-ray diffraction, Mössbauer spectroscopy, and low temperature (4.2-266 K) magnetization measurements. Structural characterization of these compounds shows that they both have orthorhombic (Pbnm) structure. The Mössbauer spectra show clear evidence of local structural distortion of the Mn(Fe)O₆ octahedron, which is based on the non-zero nuclear quadrupole interactions for high-spin Fe³⁺ ions. It was found that the local structural distortion increases significantly when Sm³⁺ is replaced by Gd³⁺. This distortion is attributed to the Jahn-Teller coupling strength as estimated from the Mössbauer effect results. The magnetic results indicate that the Curie temperature decreases as a result of replacing Sm by Gd. This is due to the decrease of the average A-site cationic radius 〈r_A〉. The rapid increase of magnetization at low temperature indicates the magnetic ordering of rare earth ions at the A-site.     

Electrical and magnetic properties of ε-Fe3N nanoparticles synthesized by chemical vapor condensation process

ε-Fe₃N nanoparticles synthesized by chemical vapor condensation (CVC) are covered with shells of disordered Fe₃O₄ phase, as observed by a transmission electron microscopy. The zero-field cooling and field cooling temperature dependence of magnetization, ac susceptibility as a function of frequency, magnetic hysteresis loops, and the temperature dependence of resistivity of the ε-Fe₃N nanoparticles are systematically studied. The results indicate the existence of complex magnetic properties, such as superparamagnetic behavior, exchange bias, magnetic dipole interaction, and the possible coexistence of ferromagnetic and spin-glass-like states and/or disordered surface spins of the shells at low temperatures. The temperature dependence of resistivity ρ(T) for compacted ε-Fe₃N nanoparticles in a temperature range of 110 K< T< 300 K can be well described by the mechanism of fluctuation-induced tunneling conduction, while that below 110 K can be ascribed to conducting electrons scattered by localized magnetic moments and impurity as well as the influence of freezing of spin-glass-like moments and/or disordered surface spins of the shells.     

Dopant Spin States and Magnetic Interactions in Transition Metal (Fe3+)-Doped Semiconductor Nanoparticles: An EMR and Magnetometric Study

In this work, electron magnetic resonance (EMR) spectroscopy and magnetometry studies were employed to investigate the origin of the observed room-temperature ferromagnetism in chemically synthesized Sn_1?x Fe _x O₂ powders. EMR data clearly established the presence of two different types of signals due to the incorporated Fe ions: paramagnetic spectra due to isolated Fe³⁺ ions and broad ferromagnetic resonance (FMR) spectra due to magnetically coupled Fe³⁺ dopant ions. EMR data analysis and simulation suggested the presence of high-spin (S = 5/2) Fe³⁺ ions incorporated into the SnO₂ host lattice both at substitutional and at interstitial sites. The FMR signal intensity and the saturation magnetization M _s of the ferromagnetic component increased with increasing Fe concentration. For Sn_0.953Fe_0.047O₂ samples, well-defined EMR spectra revealing FMRs were observed only for samples prepared in the 350–600°C range, whereas for samples prepared at higher annealing temperatures up to 900°C, the FMRs and saturation magnetization were vanished due to diffusion and eventual expulsion of the Fe ions from the nanoparticles, in agreement with data obtained from Raman and X-ray photoelectron spectroscopy.     

Mössbauer spectroscopy studies of spin reorientations in amorphous and crystalline (Co0.2Fe0.8)72.5Si12.5B15 glass coated micro-wires

Thermo-gravimetric, differential scanning calorimetry and comprehensive ⁵⁷Fe Mössbauer spectroscopy studies of amorphous and crystalline ferromagnetic glass coated (Co_0.2Fe_0.8)_72.5Si_12.5B₁₅ micro-wires have been recorded. The Curie temperature of the amorphous phase is T_C(amorp) ∼730 K. The analysis of the Mössbauer spectra reveals that below 623 K the easy axis of the magnetization is axial-along the wires, and that a tangential or/and radial orientation occurs at higher temperatures. At 770 K, in the first 4 hours the Mössbauer spectrum exhibits a pure paramagnetic doublet. Crystallization and decomposition to predominantly α-Fe(Si) and Fe₂B occurs either by raising the temperature above 835 K or isothermally in time at lower temperatures. Annealing for a day at 770 K, leads to crystallization. In the crystalline material the magnetic moments have a complete random orientation. After cooling back to ambient temperature, both α-Fe(Si) and Fe₂B in the glass coated wire show pure axial magnetic orientation like in the original amorphous state. The observed spin reorientations are associated with changes in the stress induced by the glass coating.     

Structural and magnetic characteristics of Co1−xNix/2Srx/2Fe2O4 nanoparticles

Co_1−xNi_x/2Sr_x/2Fe₂O₄ (x=0–0.5 in steps of 0.1) ferrite nanoparticles have been synthesized at room temperature, without calcination, using a reverse micelle process. The site preference was determined by Mössbauer spectroscopy at 300 K. The hyperfine parameters were obtained, for the whole series of solid solutions. For the X≤0.20 samples, the spectra were fitted with two discrete sextets and for the X>0.20 samples, a magnetic hyperfine field distribution and a doublet were also imposed in the fit procedure. Hysteresis loops were measured using a superconducting quantum interference device magnetometer at 2 K and 300 K. The results indicate that the relative decrease in saturation magnetization of nanoparticles compared to the submicron particles could be attributed to a surface spin termination and disorder. Magnetic dynamics of the nanoparticles was studied by the measurement of ac magnetic susceptibility versus temperature at different frequencies and it is found that the results are well described by the Vogel–Fulcher model.     

Crystal and magnetic structure of KFeO2

The crystal and magnetic structures of KFeO₂ have been determined by neutron and X-ray powder-diffraction and Mössbauer-effect techniques. The crystal structure at 4.2 K and 300 K is orthorhombic and the magnetic space group is Pbca'. The Fe³⁺-ions in this structure are tetrahedrally coordinated by oxygen ions, and each Fe³⁺-ion has a magnetic moment which is antiferromagnetically coupled to the moments of four Fe³⁺-neighbours. The direction of the moments is parallel to the a-axis. A crystal phase transition has been observed near the Néel temperature?960 K.     

Sol-gel derived nanoparticles of Zn substituted lithium ferrite (Li0.32Zn0.36Fe2.32O4): magnetic and Mössbauer effect measurements and their theoretical analysis

Nanoparticles of Zn substituted lithium ferrite (Li_0.32Zn_0.36Fe_2.32O₄) have been prepared by a sol-gel method where the ultra-sonication technique has been adopted to reduce the agglomeration effect among the nanoparticles. The samples were heat-treated at three different temperatures and the formation of the nanocrystalline phase was confirmed by X-ray diffractograms (XRD). The average particle size of each sample has been estimated from the (311) peak of the XRD pattern using the Debye-Scherrer formula and the average sizes are in the range of 10-21 nm. The average particle size, crystallographic phase, etc. of some selected samples obtained from the high-resolution transmission electron microscopy are in agreement with those estimated from the XRD patterns. Static magnetic measurements viz., hysteresis loops, field cooled and zero field cooled magnetization versus temperature curves of some samples carried out by SQUID in the temperature range of 300 to 5 K clearly indicate the presence of superparamagnetic (SPM) relaxation of the nanoparticles in the samples. The maximum magnetization of the SPM sample annealed at 500 °C is quite high (68 Am²/Kg) and the hysteresis loops are almost square shaped with very low value of coercive field at room temperature (827.8 A/m). The particle size, magneto-crystalline anisotropy, etc. have been estimated from the detailed theoretical analysis of the static magnetic data. The dynamic magnetic behavior of the samples was also investigated by observing the ac hysteresis loops and magnetization versus field curves with different time windows at room temperatures. The different soft magnetic quantities viz., coercive field, magnetization, remanance, hysteresis losses, etc. were extracted from dynamic measurements. Dynamic measurements confirmed that the samples are in their mixed state of SPM and ordered ferrimagnetic particles, which is in good agreement with the results of static magnetic measurements. Mössbauer spectra of the samples recorded at room temperature (300 K) and at different temperatures down to 20 K confirmed the presence of the SPM relaxation of the nanoparticles of the samples.     

Temperature-dependent Mössbauer and dielectric studies of Mg0.95Mn0.05Fe1.0Ti1.0O4

The effect of tetravalent Ti⁺⁴ substitution in Mg_0.95Mn_0.05Fe₂O₄ on its magnetic and electrical properties has been studied using X-ray diffraction, Mössbauer spectroscopy, isothermal dc magnetization and dielectric measurements. X-ray diffraction studies have shown the structural transformation from cubic to tetragonal with the Ti⁺⁴ substitution. The Mössbauer spectra of Mg_0.95Mn_0.05Fe_1.0Ti_1.0O₄ recorded in the temperature range 20-300 K shows the presence of the magnetic as well as quadrupole interactions. The isothermal hysteresis loop infers that the system exhibits a ferrimagnetic ordering at room temperature. The Zero-field-cooled (ZFC) and field-cooled (FC) magnetization studies support ferrimagnetic ordering of Mg_0.95Mn_0.05Fe_1.0Ti_1.0O₄ at room temperature. Signatures of ferroelectric transition have been observed in the temperature range 200-300 K from dielectric measurements. The observed magnetic and dielectric behaviour indicate that this material exhibits multiferroic behaviour.     

Magnetization studies of TbFeO3

The spontaneous magnetization and principal magnetic susceptibilities of TbFeO₃ were measured from 4.2 to 300 K. The weak ferromagnetic moment is along the c crystallographic axis in the entire temperature range. The field dependence of the magnetization at 4.2 K was also studied. The magnetic behavior is interpreted in terms of an interaction between the ordered Fe³⁺ spin system and the electrons occupying the lowest lying “accidental” doublet of the Tb³⁺ ions. The FeTb interaction and the Tb³⁺ Van Vl eck susceptibility along the c axis play significant roles in determining the magnetic configuration of the Fe³⁺ spin system. No indication was found that the TbTb interaction plays a significant role in the magnetic behavior of TbFeO₃ at temperature above 4.2 K.     

Green synthesis and characterization of superparamagnetic Fe3O4 nanoparticles

In this paper, we have first demonstrated a facile and green synthetic approach for preparing superparamagnetic Fe₃O₄ nanoparticles using α-d-glucose as the reducing agent and gluconic acid (the oxidative product of glucose) as stabilizer and dispersant. The X-ray powder diffraction (XRD), X-ray photoelectron spectrometry (XPS), and selected area electron diffraction (SAED) results showed that the inverse spinel structure pure phase polycrystalline Fe₃O₄ was obtained. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results exhibited that Fe₃O₄ nanoparticles were roughly spherical shape and its average size was about 12.5 nm. The high-resolution TEM (HRTEM) result proved that the nanoparticles were structurally uniform with a lattice fringe spacing about 0.25 nm, which corresponded well with the values of 0.253 nm of the (3 1 1) lattice plane of the inverse spinel Fe₃O₄ obtained from the JCPDS database. The superconducting quantum interference device (SQUID) results revealed that the blocking temperature (T_b) was 190 K, and that the magnetic hysteresis loop at 300 K showed a saturation magnetization of 60.5 emu/g, and the absence of coercivity and remanence indicated that the as-synthesized Fe₃O₄ nanoparticles had superparamagnetic properties. Fourier transform infrared spectroscopy (FT-IR) spectrum displayed that the characteristic band of Fe-O at 569 cm⁻¹ was indicative of Fe₃O₄. This method might provide a new, mild, green, and economical concept for the synthesis of other nanomaterials.     

Spin-order and magnetic properties of BaZn2Fe16O27 (Zn2-W) hexagonal ferrite

M?ssbauer and magnetic measurements have been carried out both on single crystals and polycrystalline samples of BaZn₂Fe₁₆O₂₇ (Zn₂-W) hexagonal ferrite. The saturation magnetization at 0 K and at room temperature turns out to be very high, that is, 123 and 79 Gauss·cm³/g, respectively. The results have been interpreted by assuming a local reversal or a weakening of the Fe³⁺ magnetic moments due to the perturbing action of Zn²⁺ ions. The magnetic anisotropy is confirmed to be uniaxial with an anisotropy field at room temperature of 12.500 Oe.     

Microwave synthesis of magnetic Fe3O4 nanoparticles used as a precursor of nanocomposites and ferrofluids

Methods to synthesize magnetic Fe₃O₄ nanoparticles and to modify the surface of particles are presented in the present investigation. Fe₃O₄ magnetic nanoparticles were prepared by the co-precipitation of Fe³⁺ and Fe²⁺, NH₃·H₂O was used as the precipitating agent to adjust the pH value, and the aging of Fe₃O₄ magnetic nanoparticles was accelerated by microwave (MW) irradiation. The obtained Fe₃O₄ magnetic nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and vibrating sample magnetometer (VSM). The average size of Fe₃O₄ crystallites was found to be around 8–9 nm. Thereafter, the surface of Fe₃O₄ magnetic nanoparticles was modified by stearic acid. The resultant sample was characterized by FT-IR, scanning electron microscopy (SEM), XRD, lipophilic degree (LD) and sedimentation test. The FT-IR results indicated that a covalent bond was formed by chemical reaction between the hydroxyl groups on the surface of Fe₃O₄ nanoparticles and carboxyl groups of stearic acid, which changed the polarity of Fe₃O₄ nanoparticles. The dispersion of Fe₃O₄ in organic solvent was greatly improved. Effects of reaction time, reaction temperature and concentration of stearic acid on particle surface modification were investigated. In addition, Fe₃O₄/polystyrene (PS) nanocomposite was synthesized by adding surface modified Fe₃O₄ magnetic nanoparticles into styrene monomer, followed by the radical polymerization. The obtained nanocomposite was tested by thermogravimetry (TG), differential scanning calorimetry (DSC) and XRD. Results revealed that the thermal stability of PS was not significantly changed after adding Fe₃O₄ nanoparticles. The Fe₃O₄ magnetic fluid was characterized using UV–vis spectrophotometer, Gouy magnetic balance and laser particle-size analyzer. The testing results showed that the magnetic fluid had excellent stability, and had susceptibility of 4.46×10⁻⁸ and saturated magnetization of 6.56 emu/g. In addition, the mean size d (0.99) of magnetic Fe₃O₄ nanoparticles in the fluid was 36.19 nm.