Mossbauer study of the Cu-Cd ferrite system

The magnetic properties of the Cd_xCu_1?xFe₂O₄ ferrite system (x = 0 to 1) have been investigated by means of Mossbauer Spectroscopy. Mossbauer Spectra for x = 0.0 to 0.6 suggest the existence of two hyperfine fields, one due to the Fe³⁺ tetrahedral ions (A-sites) and the other due to Fe³⁺ octahedral ions (B-sites), while for x = 0.7 it shows relaxation behaviour and for x ? 0.8 it exhibits a paramagnetic quadrupole doublet. The systematic dependence of the isomer shift, quadrupole interactions and nuclear fields of ⁵⁷Fe³⁺ ions in both A- and B-sites has been determined as a function of cadmium content. The variation of nuclear magnetic fields at the A- and B-sites are explained on the basis of A-B and B-B supertransferred hyperfine interactions. Analysis of the relaxation spectrum observed at x = 0.7 (300 K) suggests that the relaxation mechanism is due to domain wall oscillations. It has been found here that the QS increases from CuFe₂O₄ as the cadmium concentration is increased.     

Enhanced atomic-scale contrast on Fe3O4 (100) observed with an Fe STM tip

Clean (100) surfaces of a synthetic single crystal of magnetite (Fe₃O₄) have been prepared in situ using current pulses in a scanning tunneling microscope without subsequent annealing. We have observed atomically resolved terraces with rows of Fe²⁺ and Fe³⁺ ions of the B-sublattice (octahedrally coordinated lattice sites). Along these rows a long-distance corrugation (∼12 ?) has been observed at 300 K using in situ prepared Fe tunneling tips. This corrugation is interpreted as a Wigner localization associated with a Verwey transition above 300 K in the top surface layer. Received: 26 September 2000 / Accepted: 27 October 2000 / Published online: 3 May 2001     

Mössbauer study of the spinel system GexCu1−xFe2O4

The magnetic properties of the spinel series Ge_xCu_1?xFe₂O₄ (X = 0 to 0.8) have been investigated by means of Mössbauer spectroscopy. Mössbauer spectra for X = 0.0 to 0.6 suggest the existence of two hyperfine fields, one due to the Fe³⁺ tetrahedral ions (A-sites) and the other due to Fe³⁺ octahedral ions (B-sites), while for X = 0.8 it shows the superposition of hyperfine field split spectra from A- and B-site ions and a broad central line spectrum. For 0.2 ? X ? 0.4, fast electron exchange among octahedral iron ions occurs as in Fe₃O₄. The variations of nuclear magnetic fields at the A- and B-sites are explained on the basis of AB and BB supertransferred hyperfine interactions.     

Low-temperature Mössbauer study of the MgCd ferrite system

Samples of the magnesium-cadmium ferrite series Cd_xMg_1?xFe₂O₄ (X = 0 to 0.8) have been studied by the Mössbauer-effect technique at 4.2 K. Mössbauer spectra for X = 0.0 to 0.8 suggest the existence of two hyperfine fields, one due to the Fe³⁺ tetrahedral ions (A-sites) and the other due to Fe³⁺ octahedral ions (B-sites). The systematic dependence of the isomer shifts, quadropole interactions and nuclear magnetic fields of ⁵⁷Fe³⁺ ions in both A- and B-sites has been determined as a function of cadmium content. The variations in the isomer shifts with Cd content are consistent with the variations in the Fe³⁺ -O^-₂ internuclear separations. It has been found here that supertransferred hyperfine interactions do not contribute to the systematics of the A- and B-site hyperfine fields.     

The magnetic properties of the MgZn ferrite system by Mössbauer spectroscopy

Samples of the magnetism-zinc ferrite series Zn_xMg_1?xFe₂O₄ (x = 0.0 to 1.0) have been studied by the Mössbauer effect technique at 77 K. Mössbauer spectra for x = 0.0 to 0.6 suggest the existence of two hyperfine fields, one due to the Fe³⁺ tetrahedral ions (A-sites) and the other due to the Fe³⁺ octachedral ions (B-sites), while for x=0.7 it shows relaxation behaviour and for x?0.8 it exhibits a paramagnetic quadrupole doublet. The variation of nuclear magnetic fields at the A and B sites is explained on the basis of the AB and BB supertransferred hyperfine interactions. Analysis of the average Mössbauer line width as a function of zinc concentration suggests that the relaxation spectrum observed at x=0.7 (77 K) is possibly due to domain wall oscillations.     

Magnetic properties of CuZn ferrite investigated by Mössbauer spectroscopy

The magnetic properties of the Zn_xCu_1?xFe₂O₄ ferrite system (x = 0 to 1) have been investigated by means of Mössbauer Spectroscopy. Mössbauer spectra of the CuZn ferrite system, taken at room temperature for x = 0.0 to 0.4 suggest the existence of two hyperfine fields, one due to the Fe³⁺ tetrahedral ions (A-sites) and the other due to the Fe³⁺ octahedral ions (B-sites), while for x = 0.5 it shows relaxation behaviour and for x ? 0.6 it exhibits a paramagnetic quadrupole doublet. The systematic dependence of the isomer shifts, quadrupole interactions and nuclear magnetic fields of ⁵⁷Fe³⁺ ions in both tetrahedral and octahedral sites has been determined as a function of zinc content. The variation of nuclear magnetic fields at the A and B sites are explained on the basis of A-B and B-B supertransferred hyperfine interactions. Analysis of the relaxation spectrum observed at x = 0.5 (300 K) suggests that the relaxation mechanism is due to domain wall oscillations.     

High field Mössbauer effect study of LaFe12O19

Mössbauer effect measurements on ⁵⁷Fe in LaFe₁₂O₁₉ at room temperature and at 4.2 K in an external magnetic field of 10 T confirm the suggestion of Lotgering[2] that the replacement of Ba²⁺ in BaFe₁₂O₁₉ by La³⁺ is accompanied by a valence change of Fe³⁺ to Fe²⁺ in the 2a-sublattice. The corresponding Fe²⁺-subspectrum has been detected. The increased hyperfine fields of the 12k- and 2b-sites in LaFe₁₂O₁₉ are discussed in terms of the different exchange paths between the iron sublattices.     

A study of the new compound YBa4Fe3O11−y

The compound YBa₄Fe₃O _y was synthesized where the Fe atoms completely substituted for the Cu atoms in YBa₄Fe₃O _y . The X-ray phase analysis of the synthesized material showed that the diffraction pattern corresponds to the data for the compound YBa₄Fe₃O _y .⁵⁷Fe Mössbauer measurements of the compound were performed at room temperature after different heat treatments: high-temperature synthesis in an oxygen atmosphere and in air, and low-temperature annealing in oxygen and in vacuum. No magnetic components are observed after any heat treatments. The Fe atoms in the compound have two valence states, Fe³⁺ and Fe⁴⁺. The idealized model of the 1-4-3 Fe structure is discussed.     

Etude De La Conductivite Electrique Des Ferrites Oxyfluores A Structure Spinelle

An investigation of the electrical conductivity of some oxyfluoride spinels of formula Zn_x²⁺Fe_1?x³⁺[M²⁺ Fe³⁺]O_4?xF_x (M = Fe, Co, Ni) and Fe³⁺[N_x²⁺Fe²⁺Fe_1?x³⁺]O_4?xF_x (N = Fe, Ni) shows that the conduction depends on the composition of the B sites: the activation energy increases, the conductivity and the Fe₃O₄ transition temperature decrease as the substitution rate of Fe³⁺ by N²⁺ in the B sites increases. The authors conclude to a hopping mechanism between the B cations; the anionic sublattice and the cationic A sublattice do not participate in the conduction.     

Mössbauer studies of stoichiometry of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>: characterization of nanoparticles for biomedical applications

The iron oxide Fe₃O₄, the mineral magnetite sometimes called ferrosoferric oxide, is notoriousy non-stoichiometric even in bulk form so its formula may be written Fe_3?δO₄. In nanoparticle form, where it has applications in medicine and information technology, it is even more susceptible to oxidation. In this paper we report synthesis and studies of superparamagnetic Fe₃O₄ nanoparticles with controlled diameters of 5.3, 10.6 and 11.9 nm. In room temperature spectra, departures from stoichiometry δ of up to 0.02 were estimated from the relative amounts of Fe ³⁺/ Fe ²⁺ and from their isomer shifts. This cannot be used for very small particles of diameter 10.6 nm and less as they are superparamagnetic at room temperature and do not show hyperfine splitting owing to fast relaxation. Such particles have promise for use in enhancing MRI signals. The magnetic spectrum is restored by the application of a relatively small magnetic field (10 kG). As the temperature is lowered the relaxation slows down and 6-line magnetic hyperfine patterns appear below a blocking temperature T_B. The values of T_B obtained are lower than those of many other researchers reported in the literature, suggesting that our particles are less affected by magnetic interactions between them. At low temperatures all the spectra are similar and closely resemble that of bulk Fe₃O₄ confirming that departures from stoichiometry are small.     

Magnetic structure of molecular magnet Fe[Fe(CN)<Subscript>6</Subscript>]·4H<Subscript>2</Subscript>O

We have studied the magnetic structure of Fe[Fe(CN)₆]·4H₂O, prepared by precipitation method, using neutron diffraction technique. Temperature dependent DC magnetization study down to 4.2 K shows that the compound undergoes from a high temperature disordered (paramagnetic) to an ordered magnetic phase transition at 22.6 K. Rietveld analysis of neutron diffraction pattern at 60 K (in its paramagnetic phase) revealed a face centred cubic structure with space group Fm3m. The structure contains three-dimensional network of straight Fe³⁺-C≡N-Fe³⁺ chains along the edges of the unit cell cube. Fe³⁺ ions occupy 4a (0, 0, 0) and 4b (1/2, 1/2, 1/2) positions. Fe³⁺(0, 0, 0) is surrounded octahedrally by six nitrogen atoms and Fe³⁺ (1/2, 1/2, 1/2) is surrounded octahedrally by six carbon atoms. Magnetic Rietveld refinement of neutron diffraction data at 11 K shows a ferromagnetic coupling between the two inequivalent Fe³⁺ sites. Refinement yielded an ordered moment of 4.4(6) and 0.8(6) μ_B per Fe ion located at (0, 0, 0) and (1/2, 1/2, 1/2), respectively. Ordered moments are found to align along the face diagonal. The observed net moment from low temperature neutron diffraction study is consistent with DC magnetization results.     

Electron spin resonance investigation of the substitution of Fe3^＋ for Ti4^＋ ions in rutile TiO2 single crystal

A Fe doped rutile TiO 2 single crystal is grown in an O 2 atmosphere by the floating zone technique.Electron spin resonance (ESR) spectra clearly demonstrate that Fe 3+ ions are substituted for the Ti 4+ ions in the rutile TiO 2 matrix.Magnetization measurements reveal that the Fe:TiO 2 crystal shows paramagnetic behaviour in a temperature range from 5 K to 350 K.The Fe 3+ ions possess weak magnetic anisotropy with an easy axis along the c axis.The annealed Fe:TiO 2 crystal shows spin-glass-like behaviours due to the aggregation of the ferromagnetic clusters.     

ODMR and EPR investigations of Fe centers in KTaO3

The analysis of EPR spectra obtained from iron doped KTaO₃ crystals in the as-grown state revealed three dominant iron centers: Fe³⁺-O_I, axial Fe-centers with spinS = 3/2 and rhombic Fe³⁺. By comparison with data from literature possible assignments for the center withS = 3/2 are discussed. For the rhombic species the temperature dependence of the main parameters of the Spin- Hamiltonian was measured. The result makes it most plausible that only one rhombic iron center exists in KTaO₃, in contrast with literature. The understanding of the EPR spectra allows us to assign transitions, observed at very low magnetic fields by optically detected magnetic resonance (ODMR), to this rhombic Fe center. On this basis, the magnetic circular dichroism (MCD) of this defect could be identified using the method of tagged-MCD. This spectrum is compared to the tagged-MCD of Fe³⁺-O₁ and of axial Fe⁴⁺ centers, which may be generated metastably by optical charge transfer. Considerably different structures in the MCD spectra of both Fe³⁺ centers indicate different local surroundings and electronic states.Dedicated to O. F. Schirmer on the occasion of his 60th birthday     

High temperature ferromagnetism of the vacuum-annealed (In1−xFex)2O3 powders

(In_1−xFe_x)₂O₃ (x = 0.02, 0.05, 0.2) powders were prepared by a solid state reaction method and a vacuum annealing process. A systematic study was done on the structural and magnetic properties of (In_1−xFe_x)₂O₃ powders as a function of Fe concentration and annealing temperature. The X-ray diffraction and high-resolution transmission electron microscopy results confirmed that there were not any Fe or Fe oxide secondary phases in vacuum-annealed (In_1−xFe_x)₂O₃ samples and the Fe element was incorporated into the indium oxide lattice by substituting the position of indium atoms. The X-ray photoelectron spectroscopy revealed that both Fe²⁺ and Fe³⁺ ions existed in the samples. Magnetic measurements indicated that all samples were ferromagnetic with the magnetic moment of 0.49-1.73 μ_B/Fe and the Curie temperature around 783 K. The appearance of ferromagnetism was attributed to the ferromagnetic coupling of Fe²⁺ and Fe³⁺ ions via an electron trapped in a bridging oxygen vacancy.     

Effect of annealing atmosphere on magnetism for Fe-doped BaTiO3 ceramic

Ba(Ti_0.3Fe_0.7)O₃ ceramic was prepared by solid-state reaction and post-annealed in vacuum and oxygen, respectively. The as-prepared and annealed samples are all single-phase, crystallizing in a 6H-BaTiO₃-type hexagonal perovskite structure. Room-temperature ferromagnetism is exhibited in all ceramics. For the as-prepared sample, the super-exchange interactions of Fe³⁺ in different occupational sites (pentahedral and octahedral sites) are expected to produce the ferromagnetism observed. After annealing in vacuum, the magnetization is reduced while the exchange mechanism remains unchanged. On the contrary, O₂ annealing can effectively enhance the magnetization due to the presence of Fe⁴⁺, an unusual valence for iron. The simultaneous presence of Fe³⁺ and Fe⁴⁺ allows new exchange mechanism responsible for the ferromagnetic interaction. The exchange couplings of Fe ions with mixed valences (Fe³⁺ and Fe⁴⁺) determine the magnetic behavior.     

An investigation of FeCoCrO4 by Mossbauer spectroscopy

The spinel FeCoCrO₄ has been studied between 4.2 and 538°K. Characteristic Mossbauer spectra of paramagnetic, magnetic and electronic relaxation types have been observed. The Mossbauer parameters for Fe³⁺ ions situated at tetrahedral (A) and octahedral (B) sites have been calculated. The cation distribution in magnetic and paramagnetic phases is found to be approximately Fe_0.5³⁺Co_0.5²⁺[Co_0.5²⁺Fe_0.5³⁺Cr³⁺]O₄. The Neel temperature been determined by the temperature scanning method to be 310±5°K.     

Effects of doping site and pre-sintering time on microstructure and magnetic properties of Fe-doped BaTiO3 ceramics

The A-site substituted BaTiO₃ ceramics were prepared by solid-state reaction via partial substitution of Fe for Ba²⁺. By comparison with the B-site substituted sample made under similar conditions, the effect of Fe doping site on microstructure and magnetism was investigated using X-ray diffraction, Mössbauer spectroscopy and vibrating sample magnetometer. It is found that A-site substitution can be realized to a certain extent at 7 at% Fe addition, whereas impurities are observed at higher Fe concentrations. In the nominal (Ba_0.93Fe_0.07)TiO₃ sample, the Fe ions are present as Fe²⁺ and Fe³⁺, respectively, replacing A-site Ba²⁺ and octahedral B-site Ti⁴⁺ in hexagonal perovskite lattice. The double-exchange Fe²⁺-O²⁻-Fe³⁺ interactions produce ferromagnetism well above room temperature, but the saturation magnetization and the Curie temperature are both obviously lower than those for B-site substitution due to different magnetic exchange mechanisms. In the B-site substituted sample Ba(Ti_0.93Fe_0.07)O₃, the super-exchange interactions between Fe³⁺ on pentahedral and octahedral Ti⁴⁺ sites are responsible for ferromagnetism. These results mean that B-site substitution is a better way for Fe-doped BaTiO₃ system to obtain high-Curie-temperature ferromagnetism. Moreover, increasing pre-sintering time can further improve the magnetism of B-site substituted samples, through which the saturation magnetization for Ba(Ti_0.93Fe_0.07)O₃ is enhanced ∼6 times.     

Mössbauer study of Fe1 + xV2−xO4 spinels for the determination of cation distributions and magnetic structure

Mössbauer experiments were carried out in the temperature range of 80–500 K on the spinel series of Fe_{1 + x}V_2?xO₄. The determined cation distribution has Fe²⁺ and Fe³⁺ at both A and B spinel sublattice sites for t whole series except for x = 0. Charge hopping was observed at the B lattice sites. The present cation distribution reasonably predicts several experimentally observed constants such as the lattice constant, the oxygen parameter, the saturation magnetic moment and the Curie constant. The magnetic structure in best agreement with the experimental values shows the AA spins to be antiparallel for Fe, the BB spins to be parallel for identical ions and antiparallel for different ions, and shows a strongly antiparallel AB interaction between trivalent iron ions. Crystal distortions due to the Jahn-Teller effect were observed at 80 K for compositions with 0 ? x ? 0.75.     

The relationship between magnetic behaviour and local structure around Fe ions in Fe-doped TiO2 rutile

The magnetic and structural characterization of Ti_1−xFe_xO₂ (x=0.025, 0.05, 0.07, 0.125, and 0.15) samples prepared by mechano-synthesis using TiO₂ and Fe₂O₃ as starting materials are reported. XANES measurements performed at the Fe K-edge show that Fe ions are in 3+ oxidation state in the 7 at% Fe-doped sample and in a mixture of 2+ and 3+ oxidation states in the other samples. EXAFS results show the incorporation of Fe ions substituting Ti ones in the rutile TiO₂ structure. They also reveal a strong correlation between the number of oxygen nearest neighbours and the Fe²⁺ fraction, i.e the number of oxygen near neighbours decreases when the Fe²⁺ fraction increases. All samples present ferromagnetic-like behaviour at room temperature. We found a clear dependence between saturation magnetization and coercivity with the fraction of Fe²⁺ and/or the number of Fe near neighbour oxygen vacancies.     

Synthesis and characterizations of water-based ferrofluids of substituted ferrites [Fe1−xBxFe2O4, B=Mn,Co (x=0–1)] for biomedical applications

Nanomagnetic particles have great potential in the biomedical applications like MRI contrast enhancement, magnetic separation, targeting delivery and hyperthermia. In this paper, we have explored the possibility of biomedical applications of [Fe_1−xB_xFe₂O₄, B=Mn, Co] ferrite. Superparamagnetic particles of substituted ferrites [Fe_1−xB_xFe₂O₄, B=Mn, Co (x=0–1)] and their fatty acid coated water base ferrofluids have been successfully prepared by co-precipitation technique using NH4OH/TMAH (Tetramethylammonium hydroxide) as base. In vitro cytocompatibility study of different magnetic fluids was done using HeLa (human cervical carcinoma) cell lines. Co²⁺-substituted ferrite systems (e.g. CoFe₂O₄) is more toxic than Mn²⁺-substituted ferrite systems (e.g. MnFe₂O₄, Fe_0.6Mn_0.4Fe₂O₄). The later is as cytocompatible as Fe₃O₄. Thus, Fe_1−xMn_xFe₂O₄ could be useful in biomedical applications like MRI contrast agent and hyperthermia treatment of cancer.