Octahedral cation partitioning in Mg,Fe2+-olivine. Mössbauer spectroscopic study of synthetic (Mg0.5 Fe2+ 0.5)2SiO4 (Fa50)

The high-temperature partitioning of Fe²⁺ and Mg between the two non-equivalent octahedral M1 and M2 sites in synthetic olivine (Fa₅₀) was studied by Mössbauer spectroscopy. Powder samples have been equilibrated in annealing experiments performed under reducing oxygen fugacity at temperatures between 500 and 800°C followed by rapid quenching in order to prevent redistribution of cations. M-site ordering with Fe²⁺ preferring M1, Mg preferring M2 sites increases continuously with rising equilibrium temperature. K _D values increase from 1.21 at 500°C to 1.48 at 750°C. The results are consistent with both room temperature as well as in situ high temperature single crystal X-ray diffraction experiments of Heinemann et al. [8, 9].     

Mössbauer studies of Fe2+ in paramagnetic fayalite (Fe2SiO4)

Mössbauer absorption spectra in Fe₂SiO₄ were taken over the temperature range 80 – 1000°K. The quadrupole splitting of the absorption line as a function of temperature was measured. The results show, that the electric field gradient tensor at the sites of the Fe²⁺ ions has different values, corresponding to the two sites of different point symmetry which are known from x-ray data.     

Mössbauer study of synthetic jarosites

The structure around the metal site of mavicyanin, a protein molecule with a copper site, was investigated in solution by using time-differential perturbed angular correlation of ¹¹⁷In. The electric field gradient (EFG) of the metal site was deduced from the measurement. It demonstrated that the site in a mutant-type mavicyanin, Thr15Ala-Mav, gives an EFG different from that in the wild-type mavicyanin does. The pH dependence of the EFG was also observed for both proteins.     

57Fe hyperfine interactions in M1 and M2 sites of olivine from Omolon meteorite: study using Mössbauer spectroscopy

Study of olivine (Fe, Mg)₂SiO₄ from Omolon meteorite was performed using Mössbauer spectroscopy with a high velocity resolution at 295 and 90 K. Components related to ⁵⁷Fe in crystallographically non-equivalent M1 and M2 sites in olivine were determined and its Mössbauer hyperfine parameters were evaluated at both temperatures. A Fe^2?+?–Mg^2?+? distribution coefficient and a temperature of cation equilibrium distribution for olivine from Omolon were evaluated on the basis of Mössbauer parameters.     

Mössbauer study of Fe2+ in some normal spinels

The present note describes the results of the Mössbauer study of FeAl₂O₄ and Mg_0.98Fe_0.02^80%57Al₂O₄ in order to clarify the electronic state of the Fe²⁺ ion from an atomic point of view.     

Low temperature Mössbauer spectra and magnetic ordering of lithiated ferric molybdate: Li2Fe2(MoO4)3

Powder x-ray diffraction, variable temperature magnetic susceptibility, and zero field Mössbauer spectroscopy measurements were used to characterize the new phase Li₂Fe₂ (MoO₄)₃. This material is obtained topochemically simply by the mixing of solutions of lithium iodide in acetonitrile with solid Fe₂(MoO₄)₃ at ambient temperature. Li₂Fe₂(MoO₄)₃ possesses the high temperature orthorhombic ferric molybdate $$\begin{gathered} Fe_2 (MoO_4 )_3 + 2LiI\xrightarrow{{CH_3 CN}}Li_2 Fe_2 (MoO_4 )_3 + I_2 \hfill \\ (solid)(solution)(solid)(solution) \hfill \\ \end{gathered}$$ structure. Guinier photographs were completely indexed in space group Pnca. Magnetic hyperfine splitting of the zero field Mössbauer spectrum below 12.5 K indicates a three-dimensional magnetically ordered state which susceptibility results show to be weakly ferromagnetic owing to probable canting of antiferromagnetically coupled sublattices.     

57Fe Mössbauer study of new multiferroic AgFeO2

The present work reports results of the ⁵⁷Fe Mössbauer measurements on AgFeO₂ powder sample recorded at various temperatures including the points of both magnetic phase transitions. The ⁵⁷Fe Mössbauer spectra of AgFeO₂ measured in the paramagnetic range (T > T _N1) consist of one quadrupole doublet with rather high quadrupole splitting of Δ_300K = 0.66 ± 0.01 mm/s for Fe³⁺ ions. In order to predict the sign of electric field gradient (EFG) at ⁵⁷Fe nuclei, we calculated the lattice contribution to the electric field gradient (EFG) at ⁵⁷Fe nuclei, which emphasized the importance of the dipolar contributions, with resultant oxygen polarizabilities in the range of α _O = 0.83 ų, in agreement with the results obtained previously for other delafossite-like oxides. In the temperature range of T _N2 < T < T _N1, Mössbauer spectra gave clear evidence for the existence of a distribution of the hyperfine magnetic fields H _hf at ⁵⁷Fe nuclei. We present the results of a model fitting of the spectra based on an assumption of the cycloid magnetic structure of AgFeO₂ at T < T _N2. The obtained data were analysed in comparison with published data on Mössbauer studies of oxide multiferroics.     

Mössbauer study of localized diffusion in an interstitial cage

Mössbauer investigations at various temperatures and in different directions with respect to an electron irradiatedAl ⁵⁷Co/⁵⁷Fe single crystal are reported. It is shown that the drastic decrease of the measured Mössbauer intensity in a narrow temperature range above 15 K is due to localized diffusion of Fe in an interstitial cage. The existence of the diffusive motion is demonstrated by the observation of a broadened component in the Mössbauer spectra above 15K. From the temperature dependence of the broadening the activation energy of the cage jumps is determined as 18±1 meV. Mössbauer spectra measured at sufficiently high temperature show only an unbroadened component, its intensity depending on the crystal orientation relative to the spectrometer. Comparison of this anisotropy with model calculations of the preceding part I of this paper shows that the Fe atom jumps between the corners of a cube, these corners being 0.52±0.02 Å distant in 111 directions from the octahedral lattice position.     

A 57Fe Mössbauer spectroscopy study of iron nanoparticles obtained in situ in conversion ferrite electrodes

Transmission Mössbauer spectroscopy and CEMS are powerful tools to study the changes in which iron-containing active materials of conversion electrodes are involved during lithium cell charge and discharge. The usual spectrum of pristine CoFe₂O₄ spinel with two sextets ascribable to Fe^3?+? ions in both tetrahedral and octahedral environments, changes dramatically after cell discharge to 0 V vs. Li, and can be interpreted as the result of iron reduction to the metallic state in the form of superparamagnetic metal nanoparticles dispersed in a Li₂O matrix. After cell charge to 3 V, the MS of the pristine sample is not recovered. Instead, two new doublets are visible with IS ascribable to Fe^3?+? ions. ⁵⁷Fe CEMS evidences the different environment of iron atoms in the surface of the nanodispersed material found in the used electrodes.     

Mössbauer study of magnetic order in RBa2Fe3O8

Complete replacement of copper by iron in RBa₂Cu₃O₇ leads to RBa₂Fe₃O₈ (R=Y, rare earth). Mössbauer spectroscopy measurements of⁵⁷Fe and¹⁵¹Eu in RBa₂Fe₃O₈ (R=Y, Eu, Ho, Er) at temperatures 4.2–800 K have been performed. Some of the spectra reveal two inequivalent iron sites, probably corresponding to iron in the Fe(2) site (fivefold oxygen coordination) and in the Fe(1) site (octahedral oxygen coordination). In all compounds the iron moments order antiferromagnetically at the same Néel temperatureT _N720 K. The¹⁵¹Eu Mössbauer spectra of EuBa₂Fe₃O₈ show that the Eu ion is trivalent and exposed to a small exchange field from the iron sublattices.     

A57Fe Mössbauer study of Nd(Fe0.5Co0.5)9Si2

A⁵⁷Fe Mössbauer study of Nd(Fe_0.5Co_0.5)₉Si₂ has been carried out over the temperature range 4.2–295 K. The analysis of the Mössbauer spectra, combined with X-ray diffraction on a magnetically aligned powder sample, shows that the easy-magnetization direction lies in the basal plane of this tetragonal BaCd₁₁ structure at 295 K, but is canted at an angle of 29(5) above the basal plane at 4.2 K. AC susceptibility measurements performed in the temperature range 77–295 K reveal a peak spanning the range 87–106 K, with the maximum occurring at 96 K. From these data, we conclude that there is a spin-reorientation from basal c-plane to a canted magnetic structure in this compound, with an onset at 96 K as the temperature decreases.     

Intersite cation partitioning in natural and synthetic alpha-(Fe,Mn)2O3 (bixbyite) solid solutions determined from57Fe Mössbauer spectroscopy

The partitioning of Fe³⁺ and Mn³⁺ between the 8b and 24d crystallographic sites in samples of alpha-(Fe, Mn)₂O₃ solid solutions was determined from⁵⁷Fe Mössbauer spectroscopy measurements at 298 K. In the case of synthetically prepared samples, we find that with increasing iron content and temperature of equilibration, Fe³⁺ preferentially enters the more distorted 24d sites. However, the intersite cation distribution coefficient (K _D) is only a function of the temperature of equilibration, and can therefore be used to estimate the temperature of formation of naturally occurring bixbyite. Using this technique, the temperature of formation of bixbyite samples from the Postmasburg manganese field in South Africa was calculated to be between 315 and 370 C. This is in good agreement with values obtained from other techniques, suggesting that it may be possible to use the intersite cation distribution in bixbyite as a geothermometer.     

Mössbauer study of the Jahn-Teller effect in Fe0.3Mn2.7O4

The Mössbauer spectra of Fe_0.3Mn_2.7O₄ were investigated in the 288–1473°K temperature range; a tetragonal distortion of the lattice by the Jahn-Teller effect was observed. The results have been compared with point-charge calculations.     

Fe57 Mössbauer study in cobalt substituted magnetite

The Mössbauer effect has been studied in the mixed ferrites Co _x Fe_3–x O₄ (forx=0.8, 0.9 and 1) with the spinel structure in the temperature range between 78 and 380 K. The composition withx=1, showed an expected Zeeman spectrum with two overlapping magnetic hyperfine patterns related to the Fe³⁺ ions in tetrahedral and octahedral sites. While for samples withx=0.8 and 0.9 the Mössbauer spectrum for each compound was successfully analysed into three different patterns corresponding to the ferric ions placed at the tetrahedral and octahedral sites and ferrous ions at the octahedral sites, indicating no electron transfer between Fe³⁺ and Fe²⁺, where the quantity of cobalt is sufficiently large to be located at the six nearest neighbours to ferrous ions. The Mössbauer effect parameters were calculated for these observed sites and their variation with temperature reported. The reduced hyperfine magnetic fields of the Fe³⁺ (B) ions were found to follow the Brillouin curve forS=5/2 and one third power law. The magnetic ordering temperature was determined to be 815 K and the possible magnetic interactions were discussed.     

Mössbauer spectroscopy study of the EuO:Fe spintronic material

The states of iron and europium in the EuO:Fe composite spintronic material have been studied by means of room-temperature Mössbauer spectroscopy. In both cases, two sets of lines indicating the ferromagnetism and superparamagnetism of metallic iron nanoparticles in the composite and the appearance of a fraction of europium ions in the Eu³⁺ oxidation state in the matrix in addition to the main Eu²⁺ state have been observed in the respective spectra. In the europium case, the observation implies the possibility of a partial spin polarization of paramagnetic europium ions in Eu-Fe-O clusters and an increased specific magnetization of the composite.     

Mössbauer study of magnetic Fe/FeSi multilayers

Many useful properties of magnetic multilayers depend on the coupling between the ferromagnetic layers. The coupling often oscillates with the thickness of non-magnetic spacer layers: it is ferro- or antiferromagnetic or even non-collinear near a critical thickness. We investigated the magnetron-sputtered Fe/FeSi multilayers with spacer thickness around 1.7 nm by means of Conversion Electron Mössbauer Spectroscopy with oblique incidence of the γ beam in order to gain information on the orientation of the local magnetic moments in the multilayer plane. The results show that the local moments make an angle of 45°–50° with the direction of the remanent magnetization. This is consistent with strong biquadratic coupling which in turn is expected at this spacer thickness from our magnetic measurements. An analysis of the distribution ofB _hf corresponding to different numbers of n.n. Si atoms in the bcc Fe structure points to weak diffusion of Si through the Fe/FeSi interface characterized by a diffusion length of about twice the substrate roughness.     

A Mössbauer effect study of MgFe2O4

A slowly cooled sample of the ferrimagnetic spinel MgFe₂O₄ has been studied with ⁵⁷Fe Mössbauer spectroscopy over a wide temperature range both with and without high magnetic fields. The observed temperature dependence of the A and B site hyperfine parameters is discussed. Conclusions about the spin structure, the magnetic exchange interactions and the supertransferred hyperfine fields are presented.     

Magnetic and Mössbauer study of Mg0.9Mn0.1Cr x Fe2−x O4 ferrites

The ferrites Mg_0.9Mn_0.1Cr _x Fe_2?x O₄ ( The ferrites Mg_0.9Mn_0.1Cr _x Fe_2−x O₄ () were prepared using the conventional double sintering method. The XRD showed that the samples maintain a single spinel cubic phase. The M?ssbauer measurements were carried out at room and liquid nitrogen temperatures. From the area ratios of the A and B sites, it was found that the Fe cation population of the A and B sites decreases in proportion to Cr concentration. The contact hyperfine fields at the A and B sites were found to decrease with increasing Cr contents. This was found to be in approximate agreement with the results of magnetization measurement. The distributions of Mg and Mn cations versus Cr concentration were also determined using the M?ssbauer and magnetization results. The Curie temperatures were determined and found to agree with the reported values. As the Cr contents increases the relative magnetization, was found to increase at low temperatures and decreases at higher temperatures.