Raman scattering studies of spin‐waves in hexagonal BaFe12O19

We present the results of polarized Raman spectroscopy of hexagonal BaFe₁₂O₁₉ single crystal. The spectra, recorded from 200 to 800 cm^–1 and 1100 to 1700 cm^–1 in the 20–250 K temperature range, are analyzed on the basis of both crystal vibrations and spin‐waves. In the low wavenumber range, the Γ‐point phonons are observed. In the high wavenumber range, phonon mixings are observed; more interestingly, four modes of spin‐waves are identified in hexagonal BaFe₁₂O₁₉. Both have not been studied previously. Our analyses of the spin‐waves provide an optical method for quantitatively estimating the spin exchange interactions in hexagonal BaFe₁₂O₁₉. The four strong exchange integrals are found to have the values of J_ce = 1.31 meV, J_ae = 1.36 meV, J_cd = 1.46 meV, and J_bd = 1.71 meV. Our results also indicate that at ~200 and ~80 K, there would be additional spin‐ordering transitions in hexagonal BaFe₁₂O₁₉. Copyright © 2012 John Wiley & Sons, Ltd.     

Depth-selective conversion-electron Mössbauer spectroscopy of the surface of Ba-M hexaferrite single crystals

The magnetic properties of a 50-to 2-nm-thick surface layer in hexagonal ferrite BaFe₁₂O₁₉ single crystals are investigated for the first time. Measurements are made on a conversion-electron Mössbauer spectrometer constructed on the basis of a unique ultrahigh-vacuum magnetostatic electron analyzer of the “orange” type. An analysis of the experimental Mössbauer spectra obtained from the surface layer of BaFe₁₂O₁₉ 50-to 2-nm-thick single crystals reveals that (1) the spectral line widths are close to the natural widths of Mössbauer lines and neither changes nor a set of the values of effective magnetic fields, as well as a paramagnetic state of iron ions, could appear due to a defect such as the “surface,” and (2) the experimental spectra are best described only under the assumption that the surface of a hexaferrite BaFe₁₂O₁₉ single crystal contains a 2-nm-thick layer, in which the magnetic moments of iron ions are deflected through ～20° from the crystallographic C axis along which the magnetic moments of ions located in the bulk of the crystal are oriented.     

The dynamics of bipyramidal ions in magnetoplumbite-like hexagonal ferrite systems revisited

The dynamics of the bipyramidal 4e–Fe ions in the M-type hexagonal ferrite La_0.7Na_0.3Fe₁₂O₁₉ single crystal, is investigated by using Mössbauer spectroscopy. We show that a photon self-interference phenomenon can be used to explain the available experimental data. From this model we have deduced the jumping distance of the Fe(4e) ions. This model can also be succesfully used to investigate the existing data on the isomorphous CaAl₁₁FeO₁₉ and BaFe₁₂O₁₉ oxides. In all cases, the calculated jumping distances are in a excellent agreement with X-ray diffraction results. For CaAl₁₁FeO₁₉ and BaFe₁₂O₁₉ we have deduced the thermal dependence of the jumping distance. Any evidence of an atomic freezing is not found in the temperature range 80–300 K.     

Mössbauer studies of the surface and bulk magnetic structure of scandium-substituted Ba-M-type hexaferrites

A direct comparison of the magnetic structures of a surface layer and of the bulk of Ba-M-type hexagonal ferrites with iron ions partially replaced by Sc diamagnetic ions (BaFe_12?x Sc_xO₁₉) has been made by simultaneous Mössbauer spectroscopy with detection of gamma rays, characteristic x-ray emission, and electrons. It has been found that, if the magnetic lattice of a Ba-M-type hexagonal ferrite is weakly diluted by Sc diamagnetic ions, a ～300-nm thick macroscopic layer forms on the surface of a BaFe_11.4Sc_0.6O₁₉ crystal, in which the iron-ion magnetic moments are noncollinear with the moments in the bulk. The noncollinear magnetic structure forms in the near-surface layer of BaFe_12?x Sc_xO₁₉ crystals because the exchange interaction energy is additionally reduced by the presence of such a “defect” as the surface. This is the first observation in ferromagnetic crystals of an anisotropic surface layer whose magnetic properties, as predicted by Néel, differ from those of the bulk.     

Surface magnetism of Sc-substituted Ba-M hexaferrites

A technique of simultaneous gamma-ray, x-ray, and electron Mössbauer spectroscopy is used to study the magnetic structure of the surface layer with direct comparison to the magnetic structure inside single crystal samples of hexagonal Ba-M ferrites, in which part of the iron ions have been replaced by diamagnetic Sc ions (chemical formula BaFe_12?δ Sc_δO₉). It is found that when the diamagnetic Sc ions are introduced into the crystal lattice of BaFe_12?δ Sc_δO₁₉ at concentrations (x=0.4 and 0.6) far below the level at which the collinear magnetic structure inside the sample is destroyed, a macroscopic layer of thickness ～300 nm develops on the surface, in which the magnetic moments of the iron ions are oriented noncollinearly with respect to the moments inside the sample. The deviation 〈θ〉 of the magnetic moments in BaFe_11.6Sc_0.4O₁₉ was 10° ± 62° for x=0.4, and when the Sc concentration was raised to 0.6, the angle 〈θ〉 increased to 17° ± 62°. The noncollinear magnetic structure in the surface layer in these crystals develops because of further reduction in the energy of the exchange interactions owing to the presence of a “defect,” such as the surface. For the first time, therefore, an anisotropic surface layer whose magnetic properties differ from those in the interior of a sample has been observed experimentally in ferromagnetic crystals, as predicted by Néel [L. Néel, Phys. Radium. 15, 225 (1954)].     

Simultaneous gamma, x-ray, and electron Mössbauer spectroscopy of the volume and surface magnetic structure of hexagonal M-ferrites

Direct comparative studies are made between the magnetic structures of a surface layer of thickness ～40 nm and the bulk magnetic structure of ferromagnetic single crystals of hexagonal M ferrites (BaFe₁₂O₁₉, SrFe₁₂O₁₉, PbFe₁₂O₁₉) with a magneto-plumbite structure. Measurements are made by simultaneous gamma, x-ray, and electron Mössbauer spectroscopy in order to investigate the properties of the surface layer and the bulk crystal simultaneously. Experimental data obtained with a depth resolution of ～ 10 nm show that the orientation of the magnetic moments of the iron ions (along the crystallographic c axis) does not change on approaching the surface from the crystal volume. Thus, to within an experimental error of ～ 10 nm, single crystals of the hexagonal ferrites BaFe₁₂O₁₉, SrFe₁₂O₁₉, and PbFe₁₂O₁₉ with a ferromagnetic structure do not have a “ transition” surface layer whose magnetic structure differs from that of the bulk crystal such as that which exists, with a depth of several hundred nm, in antiferromagnetic materials with weak ferromagnetism.     

Simple recipe to synthesize single-domain BaFe12O19 with high saturation magnetization

We report a new synthesis route for preparation of single-domain barium hexaferrite (BaFe₁₂O₁₉) particles with high saturation magnetization. Nitric acid, known as a good oxidizer, is used as a mixing medium during the synthesis. It is shown that formation of BaFe₁₂O₁₉ phase starts at 800 °C, which is considerably lower than the typical ceramic process and develops with increasing temperature. Both magnetization measurements and scanning electron microscope micrographs reveal that the particles are single domain up to 1000 °C at which the highest coercive field of 3.6 kOe was obtained. The best saturation magnetization of ≈60 emu/g at 1.5 T was achieved by sintering for 2 h at 1200 °C. Annealing at temperatures higher than 1000 °C increased the saturation magnetization, on the other hand, decreased the coercive field which was due to the formation of multi-domain particles with larger grain sizes. It is shown that the best sintering to obtain fine particles of BaFe₁₂O₁₉ occurs at temperatures 900-1000 °C. Finally, magnetic interactions between the hard BaFe₁₂O₁₉ phase and impurity phases were investigated using the Stoner-Wohlfarth model.     

Synthesis,Characterization, and Optical Properties of Poly(o-methoxyaniline)/BaFe12O19 Composite via an In Situ Polymerization Pathway

Poly(o-methoxyaniline)(POMA)/BaFe₁₂O₁₉ composite was synthesized via a facile in situ polymerization approach for the first time. The structures of the products were characterized by X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectra, which indicated the existence of BaFe₁₂O₁₉ particles in the composite. The morphology of the as-prepared samples was observed by using field-emission scanning electron microscopy (FESEM), which revealed that the POMA/BaFe₁₂O₁₉ composite appeared in the form of a general pseudo-sphere-like shape and consisted of numerous highly aggregated globules with rough surfaces. The optical properties of the POMA/BaFe₁₂O₁₉ composite were further investigated by UV-vis spectra. The decrease of band gap for the POMA/BaFe₁₂O₁₉ composite revealed that electronic structure of POMA was affected by BaFe₁₂O₁₉ particles.     

Effect of Magnetic Pulse Processing on the Structure and Magnetic Properties of Ferrites

The effect a pulsed magnetic field has on the crystal structure and macroscopic magnetic parameters of hexagonal ferrites BaFe₁₂O₁₉ and SrFe₁₂O₁₉ are studied. It is shown that changes in the physical properties of ferrites are due to the ordering of cation vacancies on the boundaries of hexagonal and spinel blocks that minimize local distortion of the oxygen polyhedrons. Violation of the collinear ordering of the magnetic moments of iron ions in the nonequivalent positions of SrFe₁₂O₁₉ ferrite is observed, due to the selective localization of such vacancies (and thus violations of the magnetic relationships in Fe–O–Fe).     

Mn离子取代M型钡铁氧体的研究

本文对Mn离子取代M型钡铁氧体BaFe_12-xMn_xO₁₉作了较系统的研究。主要结论如下:(1)在我们的实验条件下,Mn的取代量x可达4,其中约有0.1—0.3的Mn²⁺存在,其余Mn为三价。(2)Mn离子主要进入12k和2a晶位。(3)BaFe_12-xMn_xO₁₉的各向异性常数K₁₉,居里温度T_c和饱和磁化强度σ_s均随x的增加而下降。(4)Mn引起BaFe_12-xMn_xO₁₉的非共线自旋结构。(5)Mn³⁺在12k和2a晶位中的平均零场劈裂因子D^h比尖晶石中八面体B位上的Mn³⁺之D^c值小近一个数量级。 关键词：     

Effect of diamagnetic substitutions in BaFe12O19 on the magnetic properties

The exchange parameters of BaFe₁₂O₁₉ have been calculated from the temperature dependence of the saturation magnetization using the molecular field theory. Under the assumption that the exchange parameters do not change for diamagnetic substitutions of the Fe³⁺ ions, it is shown that the temperature coefficient of the magnetization at room temperature cannot be decreased without decreasing the magnetization. Diamagnetic substitution in the octahedralf ₂ site would solely increase the saturation magnetization.     

Fabrication and magnetic properties of hexagonal BaFe12O19 ferrite obtained by magnetic-field-assisted hydrothermal process

High magnetic field effects on the microstructure and magnetic properties of BaFe₁₂O₁₉ hexaferrites synthesized hydrothermal method have been investigated. The obtained results indicate that the lattice constant decreases gradually as the magnetic field strength increases, which may be attributed to the lattice distortion resulted from the high magnetic field. Polycrystalline BaFe₁₂O₁₉ samples prepared under magnetic field strength at zero and 5 T are single phase. It is found that application of external magnetic field during synthesis can induce orientated growth of the hexaferrite crystals along the easy magnetic axis. The magnetic properties can be effectively regulated by an application of high magnetic fields. It is observed that the BaFe₁₂O₁₉ prepared under a 5 T magnetic field exhibits a higher room-temperature saturation magnetization (66.3 emu/g) than that of the sample (43.6 emu/g) obtained without magnetic field. The results can be explained as the enhanced crystalline, improvement of Fe³⁺ ions occupancy and the oriented growth induced by the external magnetic field. The growing orientation of particles gives rise to increased coercivity due to the enhancement in shape anisotropy. It is expected that an application of magnetic field during the formation of magnetic nanoparticles could be a promising technique to modify magnetic properties with excellent performance.     

Observation of the exchange spring behavior in hard-soft-ferrite nanocomposite

Nanocomposite of hard (BaFe₁₂O₁₉) and soft ferrite (Ni_0.8Zn_0.2Fe₂O₄) are prepared by the mixing of the individual ferrite components at appropriate ratio and subsequent heat treatment. Initially the microstructure of the individual phases is controlled by suitable processing. We have observed the exchange spring behavior in the soft-hard ferrite composite for the first time by tailoring the particle size of the individual phases and by suitable thermal treatment of the composite. It is found that the exchange interaction dominates over the dipolar interaction for smaller particle sizes of the soft ferrite. The magnetization of the composite showed hysteresis loop that is characteristic of the exchange spring system. This gives experimental proof for some theoretical modeling as well as paves way for developing magnet with higher (BH)_max product based on ferrites.     

Modifying the properties of ferrite materials with a hexagonal structure via treatment in corona discharge plasma

The influence of treatment in corona discharge plasma on the magnetic properties of BaFe₁₂O₁₉ single- and polycrystalline ferrites, as well as structural-chemical transformations in their crystal lattices, are studied. The revealed dependence between structural-sensitive microscopic parameters and the duration of corona-discharge-plasma treatment indicates the manifestation of the corona-electret effect in BaFe₁₂O₁₉ single crystals.     

Synthesis and magnetic properties of single-crystalline BaFe12O19 nanoparticles

Rod-like and platelet-like nanoparticles of simple-crystalline barium hexaferrite (BaFe₁₂O₁₉) have been synthesized by the molten salt method. Both particle size and morphology change with the reaction temperature and time. The easy magnetization direction (0 0 l) of the BaFe₁₂O₁₉ nanoparticles has been observed directly by performing X-ray diffraction on powders aligned at 0.5 T magnetic field. The magnetic properties of the BaFe₁₂O₁₉ magnet were investigated with various sintering temperatures. The maximum values of saturation magnetization (σ_s=65.8 emu/g), remanent magnetization (σ_r=56 emu/g) and coercivity field (H_ic=5251 Oe) of the aligned samples occurred at the sintering temperatures of 1100 °C. These results indicate that BaFe₁₂O₁₉ nanoparticles synthesized by the molten salt method should enable detailed investigation of the size-dependent evolution of magnetism, microwave absorption, and realization of a nanodevice of magnetic media.     

Magnetic contrast from domain walls in BaFe12O19 by tunneling stabilized magnetic force microscopy

The magnetic structure of BaFe₁₂O₁₉ is imaged with a scanning tunneling microscope having a flexible, magnetic tip. We find that Fe thin films evaporated on a silicon tip, integrated with a cantilever, behave as magnetically soft tips. Therefore, we are able to image domain walls with high lateral resolution. A different contrast along the domain wall due to surface magnetic charges is observed. We explain the data using previously established models for wavy domain walls. The obtained images are the first experimental evidence of magnetic charges induced on the wavy domain walls in BaFe₁₂O₁₉.     

Mössbauer investigation of In and Sc substituted barium hexaferrite

A detail Mössbauer analysis has been performed on polycrystalline samples of hexagonal ferrites with composition BaFe_12-x In _x O₁₉ (0x4) and BaFe_12-x ScxO₁₉ (0x3). The dependence on composition of the distribution of metallic cations among the five sublattices of the structure has been determined: these data confirm the strong preference of Sc and In ions for the sites belonging to the R block.As a consequence iron ions located in the main spin up sublattice (12k) with different number of neighbouring Fe³⁺ ions display different temperature dependences of the magnetization. The occurrence of non-collinear spin configurations, even for very low degrees of substitution of iron, has also been evidenced.     

Influence of diamagnetic cations Sc3+ on the magnetoelastic energy of M-type hexaferrites

The field and temperature dependences of the magnetostriction constants of a single-crystal BaFe_10.9Sc_1.1O₁₉ hexaferrite sample are investigated. It is demonstrated that the substitution of scandium ions for iron ions leads to a significant increase in magnetostriction constants and to their abnormal dependences on temperature below 250 K. The magnetoelastic interaction constants are estimated.     

Barium Ferrite Ball Milled in Vacuum

The structural and magnetic behaviour of BaFe₁₂O₁₉ subjected to milling in vacuum for 1000 h has been investigated by x-ray powder diffraction and Mössbauer effect spectroscopy techniques. Pronounced structural disorder is obtained along with partial decomposition of BaFe₁₂O₁₉ to α-Fe₂O₃ and evidence for superparamagnetic relaxation effects due to the fine particles produced on milling. Restoration of the fully crystallised BaFe₁₂O₁₉ structure on annealing at 1000 °C is accompanied by a six fold enhancement in the magnetic coercivity. This behaviour is linked with the fine crystallites.     

Superposition model analysis of the magnetocrystalline anisotropy of Ba-ferrite

Theoretical analysis of the first magnetocrystalline anisotropy constantK ₁ of BaFe₁₂O₁₉ is performed. Two contributions toK ₁ are considered — single ion anisotropy and dipolar anisotropy. ParameterD which determines the magnitude of the single ion contribution is calculated on the basis of the superposition model. It is argued that the disagreement between calculated and observed values ofK ₁ is most likely connected with the contribution of Fe³⁺ ions on bipyramidal sites, for which the value ofD is uncertain.