Study of the magnetic properties of the permanent magnets by Mössbauer spectroscopy

This paper presents methods that can be used in order to determine the relative remanent magnetization and uniaxial magnetic anisotropy constant of particles in powder-based permanent magnets using Mössbauer spectroscopy. The methods were verified on the permanent magnet barium ferrite.     

Eu and Fe Mössbauer study of mechanically alloyed EuFeO3

EuFeO₃ was prepared by mechanical alloying starting from europium and iron oxides. After 20 h of milling the resulting compound is pure EuFeO₃. Samples were studied as a function of milling period using XRD, Mössbauer, SEM, and magnetic measurements. Mössbauer spectroscopy was used to probe both the transition metal and the rare-earth sites. Results are compared with previous works on EuFeO₃ prepared by different methods.     

Inversion degree and saturation magnetization of different nanocrystalline cobalt ferrites

The inversion degree of a series of nanocrystalline samples of CoFe₂O₄ ferrites has been evaluated by a combined study, which exploits the saturation magnetization at 4.2 K and ⁵⁷Fe Mössbauer spectroscopy. The samples, prepared by sol-gel autocombustion, have different thermal history and particle size. The differences observed in the saturation magnetization of these samples are explained in terms of different inversion degrees, as confirmed by the analysis of the components in the Mössbauer spectra. It is notable that the inversion degrees of the samples investigated are set among the highest values reported in the literature.     

Magnetic and structural features of amorphous FeMo-based alloys

NANOPERM-type FeMoCuB alloys are studied using magnetic and Mössbauer measurements in the as-prepared amorphous state. It is shown that the Fe₇₆Mo₈Cu₁B₁₅ (A) and Fe₇₄Mo₈Cu₁B₁₇ (B) alloys exhibit the magnetic dipole and electrical quadrupole interactions well detected in the room-temperature Mössbauer spectra. The thermomagnetic measurements above the room temperature indicate a vanishing of the magnetic interactions at approximately 310 K (A) and at 340 K (B), respectively. The low-temperature DC magnetic measurements show an anomaly around 200 K which is also a boundary at which zero-field Mössbauer measurements of both samples reflect the gradual “vanishing” of the electrical quadrupole interactions and appearance of another magnetically ordered component. The Mössbauer measurements in the field of 4 MA/m yield a survival of quadrupole and an enhancement of magnetic dipole interactions.     

Spin glass ordering of Zn0.75Co0.25Fe0.5Cr1.5O4 cubic spinel

The linear and nonlinear low field AC susceptibilities of Zn_0.75Co_0.25Fe_0.5Cr_1.5O₄ show peaks due to non-critical contributions, which mask the peak due to spin glass ordering. They extend into the region of temperatures in which Mössbauer spectra do not show any magnetic component. When a DC field of 200 Oe suppresses the non-critical contributions, peak due to spin glass ordering is clearly visible. The spin glass ordering is thus shown to be a thermodynamic transition. The critical exponent is found to fall within the range found using other spin glasses. Mössbauer spectra in zero fields provide T_SG, which agrees with the peak temperature of AC susceptibilities in the absence of non-critical contributions. 〈S_Z〉 determined using Mössbauer spectra does not show any anomaly. In the presence of a field of 5 T, the spectra show SG ordering at 4.2 K, which converts into ferrimagnetic ordering at higher temperatures.     

Morphology and magnetic properties of ultrafine ZnFe2O4 particles

Well-crystallized ultrafine ZnFe₂O₄ particles of several nanometers in size have been prepared by the coprecipitation method, and their particle morphology and magnetic properties, especially at low temperatures, examined. Room-temperature X-ray diffraction, transmission electron microscopy, magnetization measurements at various temperatures from 300 K to 4.2 K, and Mössbauer spectroscopy at various temperatures from 300 K to 4.2 K, and at 4.2 K with a longitudinal magnetic field of 16.4 kOe applied have been employed. The formation of short-range and long-range magnetic order in small ZnFe₂O₄ particles above and below approximately 30 K is discussed. Below 30 K, the appearance of spontaneous magnetization and its hysteretic property is confirmed for small ZnFe₂O₄ particles.     

Characterization of Fe and Fe50Ni50 ultrafine nanoparticles synthesized by inert gas-condensation method

Nanoparticles of Fe and Fe₅₀Ni₅₀ were synthesized by inert gas-condensation method under pure helium atmosphere. The prepared nanoparticles samples were examined by high-resolution transmission electron microscopy, X-ray diffraction and Mössbauer spectroscopy. The synthesized nanoparticles consisted of core-shell type structure nearly spherical shape with a size comprised within the range 4-70 nm and they occur as clusters or chains. The Mössbauer measurements as well as X-ray diffraction showed, in both cases, the presence of iron-oxide phases.     

Microstructure and magnetic properties of bulk amorphous and nanocrystalline Fe61Co10Zr2.5Hf2.5Nb2W2B20 alloy

The microstructure and magnetic properties, i.e. the initial magnetic susceptibility, its disaccommodation, core losses and approach to ferromagnetic saturation of the bulk amorphous and partially crystallized Fe₆₁Co₁₀Zr_2.5Hf_2.5Nb₂W₂B₂₀ alloy are studied. From X-ray, Mössbauer spectroscopy and electron microscopy studies we have stated that all samples in the as-quenched state are fully amorphous. However, after annealing the samples at 850 K for 30 min the crystalline α-FeCo grains embedded in the amorphous matrix are found. Moreover, from Mössbauer spectra analysis we have stated that the crystalline phase in those samples exhibits the long-range order. The alloy in the as-quenched state shows good thermal stability of the initial magnetic susceptibility. Furthermore, the intensity of the magnetic susceptibility disaccommodation in the rod is lower than in the ribbon. It is due to low quenching rate during the rod preparation which involves the reduction of free volumes. From the analysis of the isochronal disaccommodation curves, assuming the Gaussian distribution of relaxation times, we have found that activation energies of the elementary processes responsible for this phenomenon range from 1.2 to 1.4 eV. After the annealing of the samples the initial susceptibility slightly enhances and disaccommodation drastically decreases. From high-field magnetization studies we have learned that the size of structural defects depends on the quenching rate (the shape of the samples) and changes after annealing.     

Effect of mechanical milling on the magnetic properties of garnets

Rare earth garnets after milling to nanosizes are found to decompose into rare earth orthoferrite and other rare earth and iron oxide phases. The magnetization for the yttrium iron garnet decreases in the nano state due to the formation of antiferromagnetic phases. But for the gadolinium iron garnet when milled up to 25 h, the room temperature magnetization increases despite the formation of antiferromagnetic and non-magnetic phases. This is attributed to the uncompensated moments of the sublattices because of the weakening of the superexchange interaction due to change in bond angles and the breaking of some superexchange bonds on account of the defects and oxygen vacancies introduced on milling. For the 10 h milled gadolinium iron garnet at 5 K, after correcting for the non-magnetic phases present, there is an increase in the magnetic moment of about 10% as compared to the value for the as-prepared garnet. The magnetic hyperfine fields corresponding to the various phases were measured using ⁵⁷Fe Mössbauer spectroscopy at 16 K. The isomer shift values indicate the loss of oxygen for the samples milled for larger duration.     

Effect of atomic environment on the Fe hyperfine structure and the thermal stability of magnetic order in L10 ordered Fe-Pt alloys

The ⁵⁷Fe Mössbauer effect measurements were made for the L1₀ ordered Fe-Pt alloys with 39-62 at% Pt and the effect of local atomic environment on the hyperfine structure was investigated. Furthermore, the thermal stability of magnetic order was investigated for the alloys with high Pt concentration. From the analyses of the observed Mössbauer spectra, we found that dipole-field-like anisotropic transferred hyperfine fields are mainly responsible for the large difference in hyperfine field between Fe-site and Pt-site in the Fe-rich alloys. In the Pt-rich region far from stoichiometry, the existence of many Fe-sites occupied by excess Pt atoms causes a distribution of exchange fields. Therefore, the iron atoms in different local environments may have their several hyperfine fields with different temperature dependence. The anomalous temperature dependence of the averaged hyperfine field and line broadening observed for the 61, 62 at% Pt alloys can be understood from the co-existence of various sub-spectra with different temperature dependence. As a result, the thermal stability of magnetic order is largely reduced as the Pt concentration exceeds 60 at%.     

A Mössbauer study of the chemical stability of iron oxide nanoparticles in PMMA and PVB beads

We have prepared magnetic beads consisting of iron oxide nanoparticles in a polymethyl methacrylate (PMMA) and a polyvinyl butyral (PVB) matrix. High-field Mössbauer studies show that the particles have an almost perfect collinear spin structure and magnetization measurements show that they are superparamagnetic at room temperature at a time scale of seconds. We have followed the oxidation of the particles, which initially have a stoichiometry close to magnetite. The oxidation is fast during the first 2–3 weeks and then continues slowly such that even after 30 weeks the particles have not completely transformed to maghemite. The PVB beads are hydrophilic and biocompatible and are therefore well suited for applications in medicine and biology.     

Structural and magnetic studies on mechanosynthesized BaFe12−xMnxO19

Barium hexaferrite powders with manganese substitution were prepared by mechanosynthesis. The structural and magnetic properties were characterized by X-ray diffractometer and vibration sample magnetometer, respectively. XRD patterns were refined by Rietveld method. Preferential site occupation of manganese ion was investigated by room temperature (RT) Mössbauer measurements. XRD results showed a single-phase barium hexaferrite with some residual hematite. Crystallite size was observed to decrease with substitution amount. Lower saturation magnetization and increased coercivity is observed in substituted samples. RT Mössbauer measurements showed that manganese ions preferentially occupy 12k, 4f₂, and 2a sites.     

Hyperfine interactions in some Aurivillius Bim+1Ti3Fem−3O3m+3 compounds

X-ray diffraction and Mössbauer spectroscopy were applied as complementary methods to investigate the structure and hyperfine interactions in the series of Bi_m+1Ti₃Fe_m−3O_3m+3 Aurivillius compounds with m=4, 6, 7 and 8. Samples were synthesized by the solid-state sintering method at various temperatures. As X-ray diffraction analysis proved, the compounds formed single phases at temperature above 993 K. Mössbauer studies have confirmed diffraction measurements. Compounds synthesized at 993 K contained residual hematite, however these sintered at elevated temperatures were single-phased materials. Room-temperature Mössbauer spectra of Bi_m+1Ti₃Fe_m−3O_3m+3 compounds revealed their paramagnetic properties, what is consistent with the literature data concerning the Néel temperature of these ceramics (T_N is smaller than room temperature). Detailed analysis of MS spectra allowed to state that iron ions may occupy both tetrahedral and octahedral sites in the crystallographic lattice of Aurivillius compounds.     

Grain growth process of two-phase nanocrystalline soft magnetic materials

In order to clarify the origin of the high thermal stability of the microstructure in bcc-Fe/amorphous two-phase nanocrystalline soft magnetic materials, we have investigated the changes in the magnetic and microstructural properties upon isothermal annealing at 898 K for an Fe₈₉Zr₇B₃Cu₁ alloy by means of transmission electron microscopy, Mössbauer spectroscopy and DC magnetometry. The mean grain size was found to remain almost unchanged at the early stage of annealing. However, rapid grain coarsening was evident at an annealing time of 7.2 ks where the intergranular amorphous phase begins to crystallize into Fe₂₃Zr₆. The grain growth process with a kinetic exponent of 1.6 is observed for the growth process beyond this annealing time, reflecting the disappearance of the intergranular amorphous phase. Our results confirm that the thermal stability of the bcc-Fe/amorphous two-phase nanocrystalline soft magnetic alloys is governed by the residual amorphous phase.     

Surface and bulk magnetic properties of as-quenched FeNbB ribbons

The surface and bulk magnetic properties of amorphous FeNbB ribbons in as-quenched state are investigated using various non-destructive methods. The conversion electron Mössbauer spectroscopy has detected the presence of crystalline phase at both surfaces of ribbon sample while the bulk was amorphous. The coexistence of crystalline and amorphous phase was shown also in the X-ray diffraction pattern. Magnetic properties measured by bulk sensitive vibrating sample magnetometer (VSM) strongly differs from the surface characteristics investigated by magneto-optical Kerr effect (MOKE).     

Mössbauer study of cobalt ferrite nanocrystals substituted with rare-earth Y ions

Mössbauer spectroscopy is used to characterize the crystallite size and structure of CoFe_2−xY_xO₄ (x=0, 0.1, 0.3, 0.5) ferrite nanocrystallites synthesized by the sol-gel auto-combustion method. The effect of the substitution of Fe³⁺ ions by Y³⁺ ions on the structure of cobalt ferrite nanocrystallites is investigated. The Mössbauer spectra showed two sets of six-line hyperfine patterns for all the samples, indicating the presence of Fe in both A and B-sites. On increasing the concentration of doped Y, the hyperfine field strength and the isomer shift first increase and then decrease, whereas the quadrupole splitting continuously increases. The superparamagnetism was observed for all the samples and the change of ratio of the superparamagnetism component reflects the size of crystal grain.     

External influence on magnetic properties of Fe-based nanocrystalline alloys

Amorphous and nanocrystalline ribbons of NANOPERM, FINEMET and HITPERM were studied by Mössbauer spectroscopy (MS) after the influence of external factors: different annealing atmospheres, tensile stress and several kinds of corrosion. MS is a suitable tool for such studies because the spectral parameters are very sensitive to changes in the vicinity of the probe — ⁵⁷Fe nuclei. The most sensitive parameters were hyperfine magnetic field in crystalline component, average hyperfine field in amorphous component and direction of net magnetic moments. Influence of external factors modified also the structure of the alloys, i.e. new or modified phases were identified by MS phase analysis.     

Structure and anisotropy of epitaxial fcc FePt films

Pulsed laser deposition (PLD) was used to deposit FePt films onto single crystalline MgO substrates. When deposited at room temperature, films grow epitaxial within the A1 phase. Structure and magnetic properties were examined by X-ray diffraction, Rutherford Backscattering Spectrometry (RBS), magneto-optic Kerr effect, Mössbauer spectroscopy, and Magnetic Orientation Mössbauer Spectroscopy (MOMS). These measurements allow to exclude local ordering and reveal the anisotropic intrinsic and extrinsic magnetic properties. These results are discussed with respect to the texture and microstructure of these films.     

Polarized radiation in Mössbauer spectroscopy

Mössbauer polarimetry is a spectroscopic technique sensitive to the orientations of hyperfine fields. The technique is particularly effective with monochromatic, polarized radiation: the measured spectra do not contain many additional transitions present when nonmonochromatic radiation is used. The paper reviews recent achievements in the construction of sources of polarized monochromatic radiation. Recently, filter techniques were adopted for achieving circularly and linearly polarized radiation from commercially available radioactive isotopes. A synchrotron source with nano-eV energy width, suitable for Mössbauer measurements was constructed. Applications are reviewed, in particular determination of the direction of the hyperfine magnetic field and the orientation of the electric field gradient. Special attention is paid to cases when the distributions of the hyperfine fields and mixed interactions result in poorly resolved spectra. Recent achievements in methodology are described. An explicit form of the intensity tensor is derived, which allows the transition probabilities to be calculated omitting the diagonalization of the Hamiltonian. The concept of the velocity moments is introduced. It is shown that some averages of the whole Mössbauer spectra relate to the averages of hyperfine fields and possess tensor properties.     

Enhancement of the recoilless fraction in R2Fe10Co4Si2 (R=Gd, Er, Y) offstoichiometric compounds after hydrogenation

Samples of R₂Fe₁₀Co₄Si₂ (R=Gd, Er and Y) solid solutions were prepared by arc melting and exposed to hydrogenation. Characterization of hydrogenation effects was done using Mössbauer spectroscopy. The values of the magnetic hyperfine fields corresponding to the four inequivalent lattice sites were found to increase after hydrogenation in all offstoichiometric compounds investigated. Slight changes in the relative site occupancies were observed. Transmission Mössbauer spectra were also recorded for absorbers consisting of the intermetallic and the stainless steel etalon. The recoilless fraction was derived from these spectra using the method developed by us. Our study is the first to evidence that the recoilless fraction is enhanced after hydrogenation.