A Mössbauer and ESR study of LiNbO3-Fe2O3 for low Fe2O3 concentrations

Samples of the system LiNbO₃-Fe₂O₃ prepared by water quenching and by the double-roller quenching method in the range up to 24 mol% Fe₂O₃ were investigated by Mössbauer and ESR spectroscopy. In the water quenched samples up to 11 mol% Fe₂O₃ only the Fe³⁺ and the Fe²⁺ valence states could be detected. The Fe²⁺ concentration decreased with increasing Fe₂O₃ content. Above 11 mol% Fe₂O₃ magnetically split Mössbauer spectra indicated the presence of Fe₂O₃ clusters. The isomer shift values of Fe³⁺ as a function of Fe₂O₃ concentration showed jumps at 6 and 11 mol% Fe₂O₃, whereas no significant changes could be detected in the quadrupole splitting values. The ESR data already exhibited the existence of isolated Fe³⁺ ions and of clusters with Fe-Fe distances less than 8 Å for the lowest Fe₂O₃ concentration. The cluster signal intensity increased with increasing Fe₂O₃ content. The roller quenched samples showed increased Fe²⁺ concentration as compared to the water quenched samples, which suggests that slow quenching results in iron oxidation and cluster formation. For low Fe₂O₃ concentrations a valence state change Fe³⁺Fe²⁺ can easily be obtained by heat treatments in various atmospheres, whereas for higher Fe₂O₃ contents (9.8 mol%) precipitations of-Fe (in reducing atmosphere) and Fe₂O₃ (in air) could be observed in addition to the valence state changes of a remaining part of dissolved Fe ions. On the basis of the obtained results a model was suggested for the unusual behaviour of the lattice parameters observed in LiNbO₃-Fe₂O₃.     

57Fe and119Sn Mössbauer investigations on some substituted barium hexaferrites

⁵⁷Fe and¹¹⁹Sn Mössbauer measurements have been carried out on powder samples of three differently substituted M-type barium hexaferrites. By⁵⁷Fe Mössbauer measurements in an external magnetic field applied parallel to the -ray direction, we found a canted spin structure for all samples. Furthermore, we detected a strong preference of the Sn⁴⁺ ions for the 4f₂ sites. From⁵⁷Fe Mössbauer measurements aboveT _N, we conclude that the substitution does not influence the 2b sites. The analysis of the magnetically split¹¹⁹Sn Mössbauer spectra at room temperature in the case of the Co-Sn and Zn-Sn substituted samples shows a strong difference between the two. The spectra were interpreted due to the different surroundings of the Sn⁴⁺ ions.     

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.     

High pressure Mössbauer spectroscopy using a diamond anvil cell

Recent applications of high pressure Mössbauer spectroscopy using a diamond anvil cell are presented. High pressure Mössbauer studies of two perovskite-related iron oxides SrFeO_2.97 and CaFeO₃, magnetite Fe₃O₄, and wüstite Fe_1– O have been carried out at 300 K at pressures of up to 74 GPa. A preliminary result by the resonant forward scattering of synchrotron radiation for high pressure Mössbauer spectroscopy using a diamond anvil cell is also presented.     

Iron-57 Mössbauer spectroscopic studies of materials of composition Fe x NbTiP3O12: materials with low concentrations of iron and the effects of treatment in air

The⁵⁷Fe Mössbauer spectrum recorded from the material of composition Fe_0.25NbTiP₃O₁₂ shows the presence of Fe²⁺ in a distribution of approximately octahedral type I sites within the channels of the NbTiP₃O₁₂ structure. A comparison of the results with those recorded from the material Fe_0.33NbTiP₃O₁₂ demonstrates the existence of an upper limit to the occupation by the Fe²⁺ species of the type I sites. Lattice parameter measurements and⁵⁷Fe Mössbauer spectroscopy show that treatment of Fe_0.25NbTiP₃O₁₂ in air induces the migration of the incorporated iron from the channels to form macroscopic -Fe₂O₃.     

Detection of an α-Muonium-substituted methyl radical

Mössbauer spectroscopic and magnetic measurements have been made on a novel magnetic protein produced by the controlled reconstitution of ferritin. The data indicate that the predominant mineral form in the iron-containing cores is maghemite (-Fe₂O₃) rather than magnetite (Fe₃O₄).     

TDPAC andemission Mössbauer studies of Fe3O4(99Ru)

Hyperfine interactions of⁹⁹Ru(»⁹⁹Rh) nuclei in Fe₃O₄ were studied by means of TDPAC andemission Mössbauer spectroscopy. The isomer shift obtained from an emission Mössbauer spectrum andthe temperature dependence of the hyperfine magnetic field obtained from TDPAC measurements indicate that⁹⁹Ru ions arising from⁹⁹Rh nuclei dilutely doped in Fe₃O₄ exist as a mixed state of Ru²⁺ andRu³⁺, which is not common in ruthenium oxides. Fe₃O₄(⁹⁹Ru) is the first example where a Ru ion in a low valence state exhibits its own magnetization in oxides.     

Mössbauer Study of Iron-Containing Carbon Nanotubes

⁵⁷Fe transmission Mössbauer at temperatures between 18 and 298 K and magnetic measurements have been used to characterize Fe-filled carbon nanotubes which were prepared by pyrolisis of Ferrocene + C₆₀ at atmospheric pressure under an Ar atmosphere at 1050°C. The Mössbauer data have shown that the Fe phases encapsulated within the carbon nanotubes are -Fe, Fe₃C and -Fe. The magnetic results are compatible with the Mössbauer data. Taken together the results allow us to propose a simple picture of the distribution of iron phases within the carbon nanotubes which would consist of an -Fe core surrounded by an -Fe shell, finally covered by an Fe₃C layer.     

Superconductivity and magnetism in Y1−x Ca x Sr2GaCu2O7−δ

Samples of Y_1–x Ca _x Sr₂GaCu₂O_7– (x=0, 0.4) doped with⁵⁷Fe, prepared under various oxygen pressures, have been studied by magnetometry and Mössbauer spectroscopy. Most of the iron ions (Fe³⁺) enter the Ga(Cu(1)) site. For thex=0 sample, the Mössbauer spectra of the iron nuclei in the Cu(2) sublattice display magnetic order of Cu,T _N=370 K. The iron ions in the Ga site display magnetic order only at low temperatures. At temperatures above 90 K, these iron ions display a pure quadrupole doublet Mössbauer spectrum. The samplex=0.4 also displays magnetic order of the Cu(2) site,T _N370 K. A sharp drop in the hyperfine field is observed atT _N, probably associated with a first-order phase transition or two-dimensional ordering. The iron nuclei in the Ga site display paramagnetic long spin relaxation time phenomena at 4.2 K. Thex=0.4 sample prepared under 110 atm oxygen pressure, displays superconductivity,T _c50 K. The Mössbauer spectra give evidence of the presence of two phases. One displays magnetic order, the other is paramagnetic, the last is probably associated with the superconducting phase.     

Mössbauer analysis of the firing process of the sky-green glaze of the imitative ancient Chinese Ru porcelain

The variation of the Mössbauer parameters of the imitative ancient Ru porcelain skygreen glaze with the firing conditions is studied in detail in the present paper. The Mössbauer spectra show that the sky-green glaze contains three kinds of iron minerals, i.e. the structural iron (Fe²⁺ and Fe³⁺); Fe₂O₃ and Fe₃O₄. The relative intensity of the paramagnetic peak Fe²⁺ increases and the magnetic ratio of the magnetic peak decreases with increasing temperature. Based on the variation of the quadrupole splitting (QS) of the paramagnetic peak Fe²⁺, the phase transformation characteristics of the sky-green glaze in the firing process is discussed. The coloring mechanism of the sky-green glaze and the variation of its magnetism in the firing process are also investigated in the present paper.     

Study of hexagonal R-type BaFe4Sn2O11 by57Fe and119Sn Mössbauer spectroscopy

Mössbauer data have been obtained from both the⁵⁷Fe and¹¹⁹Sn isotopes for BaFe₄Sn₂O₁₁. Variable temperature studies show that magnetic ordering occurs at 77K and is probably complete at 4K. Average hyperfine fields of 504kG and 45kG were observed at the iron and tin nuclei respectively.     

Structure and Mössbauer effect studies of Y2Sn2-xFexO7-δ pyrochlores

Y₂Sn_2-x Fe _x O_7- pyrochlores were studied by means of X-ray diffraction,¹¹⁹Sn and⁵⁷Fe Mössbauer spectroscopy. The single phase Y₂Sn_2-x Fe_xO_7- Y pyrochlores up tox=0.8 were produced by the chemical coprecipitation method. The quadrupole splittings of¹¹⁹Sn decrease linearly with increasing iron content. The⁵⁷Fe Mössbauer spectra forx=0.6 and 0.8 both are composed of a sextet and two doublets, indicating that some Fe³⁺ ion environments in the pyrochlores are magnetically ordered. The magnetic hyperfine splitting disappears in the sample withx= 1.0, which contains a second phase.This work was partially supported by the National Natural Science Foundation of PR China.     

Magnetic defect structure of iron-rich Fe x O

Mössbauer spectra were recorded at 80 and 4.2 K for Fe _x O (x> 0.95) samples that had been synthesized at 1000 C and pressures up to 10 GPa. The spectra, which consist predominantly of six broadened lines, were fit to three magnetic components: bulk Fe²⁺, defect cluster Fe²⁺ and defect cluster Fe³⁺. Mean hyperfine parameter values for bulk Fe²⁺ were calculated using second-order perturbation theory, and correlations between fluctuations were determined from the mean-square linewidths. Implications for the magnetic defect structure of Fe _x O are discussed.     

The magnetic hyperfine interaction of111Cd in the spinels Fe3O4 and Co3O4

The perturbed angular correlation (PAC) method was applied to study the temperature dependence of the magnetic hyperfine fields in¹¹¹In-doped polycrystalline Fe₃O₄ and Co₃O₄. The critical behaviour near the magnetic phase transitions has been investigated. The changes occuring near the Vervey transition in Fe₃O₄ and the path of the supertransferred magnetic fied in Co₃O₄ are discussed. The results are compared with results obtained from Mössbauer spectroscopy.     

The influence of the local surrounding on the hyperfine interactions in Zr(Fe1−x Ni x )2 compounds

Mössbauer spectroscopy and the TDPAC method have been used to study Zr(Fe_1–x Ni _x )₂ compounds forx0.30. The hyperfine magnetic field at the Fe sites and the quadrupole splitting as functions of nickel concentration were analysed by use of⁵⁷Fe Mössbauer spectroscopy. Values of the internal magnetic field on¹⁸¹Ta nuclei have been found by means of the TDPAC method.     

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.     

Effect of random magnetic fields on the hyperfine structure of Mössbauer spectra in paramagnetic single crystals

Under certain conditions, the⁵⁷Fe Mössbauer spectra of Al(NO₃)₃·9H₂OFe³⁺ single crystals exhibit new lines [1,2] (so-called z-lines) at an unusually high velocity of about 10.5 mm/s. The dependence of the positions and intensities of these z-lines on the magnitude and direction of an external magnetic field has been investigated. The appearance of the z-lines is explained by small random magnetic fields arising from magnetic nuclei in the crystal.     

High-field Mössbauer study of the randomly canted Li-Fe-Ti system

In-field Mössbauer studies have been performed on the Li_0.5(1+t)Fe_2.5–1.5t ,Ti _t ,O₄ system with 1.10 t 1.40. The disordered magnetic properties depend strongly on the chemical disorder and local order induced by thermal treatments. The results are in agreement with low- and high-field magnetization measurements. Locally canted states are observed, with the degree of magnetic disorder depending on the composition and (or) the local chemical disorder.     

Magnetic Study of Doped Ba Ferrites Prepared by Citrate Method

The M-type barium ferrite is doped with either Co²⁺-Ti⁴⁺ or Co²⁺-Zr⁴⁺ pairs to reduce its intrinsically high uniaxial magnetic anisotropy in order to make fine particles for magnetic recording. The magnetic parameters were investigated by magnetic measurements and the Mössbauer spectroscopy. Compounds (BaF) obtained from BaCo _x (Ti,Zr) _x Fe_12-2x O₁₉ with 0x1.0 have been prepared by the modified citrate method with the initial ratio of Ba:Fe equal to 1:10.8. The substitution of Co - Ti or Co - Zr for Fe³⁺ ions affects mainly the positions 2a and 4f ₂. Ba ferrite with the substitution x 0.8 is promising for perpendicular recording media applications.