Valence and magnetic states of impurity iron ions in the La<Subscript>0.75</Subscript>Sr<Subscript>0.25</Subscript>Co<Subscript>0.98</Subscript>Fe<Subscript>0.02</Subscript>O<Subscript>3</Subscript> perovskite

The local magnetic and valence states of impurity iron ions in the rhombohedral La_0.75Sr_0.25Co_0.98 ⁵⁷Fe_0.02O₃ perovskite were studied using Mössbauer spectroscopy in the temperature range 87–293 K. The Mössbauer spectra are described by a single doublet at 215–293 K. The spectra contained a paramagnetic and a ferromagnetic component at 180–212 K and only a broad ferromagnetic sextet at T < 180 K. The results of the studies showed that, over the temperature range 87–295 K, the iron ions are in a single (tetrahedral) state with a valence of +3. In the temperature range 180–212 K, two magnetic states of Fe³⁺ ions were observed, one of which is in magnetically ordered microregions and the other, in paramagnetic microregions; these states are due to atomic heterogeneity. In the magnetically ordered microregions in the temperature range 87–212 K, the magnetic state of the iron ions is described well by a single state with an average spin S = 1.4 ± 0.2 and a magnetic moment μ(Fe) = 2.6 ± 0.4μ _B .     

X-ray photoelectron and mössbauer spectroscopy studies of the valence state of transition metal ions in Co1–x Fe x Cr2O4 (x = 0.1, 0.2, 0.5) ceramics

The valence state of transition metal ions in the Co_1–x Fe _x Cr₂O₄ (x = 0.1, 0.2, 0.5) system has been investigated using X-ray photoelectron and Mössbauer spectroscopy. It has been shown that, in this system, there are Fe²⁺ and Fe³⁺ ions. The relative Fe³⁺/Fe²⁺ contents have been determined by fitting the experimental Fe 2p photoelectron spectra by a superposition of theoretical spectra of the Fe²⁺ and Fe³⁺ ions, as well as using Mössbauer spectroscopy.     

Electronic and magnetic properties of the iron borate Fe2BO4

Polycrystalline Fe₂BO₄ was prepared by solid state reactions and its electronic and magnetic properties were investigated by Mössbauer spectroscopy and magnetization measurements. The Mössbauer spectra of Fe₂BO₄ below 270 K indicate the presence of Fe²⁺ and Fe³⁺ sites in the structure, in a ratio 1 : 1. Above this temperature electron delocalization sets in between the divalent and trivalent iron ions and Fe^2.5+ states are observed. The temperature dependence of the Mössbauer spectra and magnetization measurements clearly show the onset of magnetic order below 155 K.     

Mössbauer effect of iron-57 intercalated in layered compound 2H−Fe0.5TaSe2

⁵⁷Fe Mössbauer effect study has been performed on intercalated compound 2H?Fe_0.5TaSe₂ over a temperature range between 14K and 500K. The highly concentrated intercalation samples 2H?Fe_xTaSe₂ with Fe atoms (x up to 2) are prepared by the electrochemical method for the first time. The Mössbauer measurement shows that iron is in Fe³⁺ high spin state and with the same probability occupies both octahedral and tetrahedral interstices of the Van der Waals gap. The fact that effective masses of iron ions in both sites are close to 57 amu and characteristic temperatures (Θ_M =130K, 107K respectively) are found to be relatively small is attributed to the weak forces on Fe³⁺.     

Characterisation of the reduction properties of La0.5Sr0.5Fe0.5Co0.5O3

We report here on the characterisation by temperature programmed reduction, ⁵⁷Fe Mössbauer spectroscopy and X-ray absorption spectroscopy of the phases resulting from treatment of the perovskite-related material La_0.5Sr_0.5Fe_0.5Co_0.5O₃ in a flowing 90% hydrogen/10% nitrogen atmosphere. The results show that treatment of La_0.5Sr_0.5Fe_0.5Co_0.5O₃ (which contains approximately 50% Fe⁴⁺ and 50% Fe³⁺) in the flowing 90% hydrogen/10% nitrogen atmosphere at 600°C does not result in the reduction of any of the constituent elements of the material and that the perovskite structure is still retained. The Mössbauer spectrum recorded following heating in the gaseous reducing environment at 1,000°C shows the presence of metallic iron, an Fe³⁺-containing phase with parameters compatible with the presence of SrLaFeO₄ which has a K₂NiF₄-type structure, and a paramagnetic Fe³⁺ phase. The X-ray absorption spectroscopy results show the presence of metallic cobalt. The Mössbauer spectrum recorded following heating at 1,200°C continues to show the Fe³⁺-containing components plus a larger contribution from metallic iron. The X-ray absorption spectroscopy results show the presence of metallic cobalt, SrLaFeO₄, La₂O₃ and SrO.     

57Fe and 151Eu Mössbauer studies of magnetoresistive Europium based cobalt perovskites

Eu_0.8Sr_0.2Fe _x Co_1?x O_3?z CMR perovskites with different iron concentrations (x?=?0, 0.025, 0.075, 0.15, 0.3) were investigated by X-ray diffraction, AC magnetic susceptibility, magnetotransport, as well as ⁵⁷Fe and ¹⁵¹Eu Mössbauer spectrometry. The valence state of europium ions was found to be trivalent, independently of the iron concentration. ⁵⁷Fe Mössbauer spectra and magnetic susceptibility of the investigated perovskites presented complementary results for the magnetic transitions.     

Temperature dependent Mössbauer and neutron diffraction studies of Cu x Fe1−x Cr2S4 compounds

The cation distribution and magnetic structure of Cu _x Fe_1?x Cr₂S₄ (x?=?0.1, 0.2, 0.3, 0.4, and 0.5) has been studied by X-ray and neutron diffraction, vibrating sample magnetometer (VSM), and Mössbauer spectroscopy. The charge state of Fe is found to be ferrous (Fe²⁺) for the x?=?0.1 sample; ferric (Fe³⁺) for the x?=?0.5 sample; mixed state (Fe²⁺, Fe³⁺) for the x?=?0.2, 0.3, and 0.4 samples. The Mössbauer spectra of the x?=?0.1 sample show asymmetric line broadening, which is considered to be due to the Jahn–Teller effect of Cu²⁺ ions, and a symmetrical six-line pattern is shown for the x?=?0.5 sample. The valence state of the Cu ions for the x?=?0.1 and 0.5 samples is found to be divalent and monovalent, respectively. The magnetic structure of the samples was determined to be a ferrimagnetic structure with antiparallel alignment of the Fe and Cr ion magnetic moments.     

Electron Paramagnetic Resonance and Mössbauer Studies of Fe3+ Ions in the Fe2O3 [dbnd] MoO3 System

The electron paramagnetic resonance (EPR) and Mössbauer spectra of ironmolybdenum mixed oxides system have been investigated. Both EPR and Mössbauer measurements revealed the formation of ferric molybdate, Fe₂ (MoO₄)₃ and the existence of two different Fe³⁺ species. The EPR spectra of Fe₂ (MoO₄)₃, show two resonance lines of Fe³⁺ ions indicating that a strong exchange interaction is dominates in pure iron molybdate. Mösbauer measurements revealed that the isomer shift (I. S) increases with increasing the iron content. A maximum of quadrupole splitting (Q. S) is observed at the stoichiometric concentration corresponding to the formation of Fe₂ (MoO₄)₃. The effect of a catalytaic dehydration process on the redox behaviour of Fe³⁺ located in iron molybdate frame work is investigated. Results indicate that the catalytaic dehydration of 2-proppanol over this catalyst reduces Fe³⁺ ions to Fe²⁺ leading to the formation of the inactive phase FeMoO₄. the essential role of oxygen, in the alcohol gas feed, in regeneration the activity of the catalysts was demonstrated.     

Magnetic properties of the mixed spinel Co1+xSnxFe2−2xO4

The structural and magnetic properties of the mixed spinel Co_1+xSn_xFe_2?2xO₄ system for 0.1≤x≤0.5 have been studied by means of X‐ray diffraction, magnetization, a.c. susceptibility and Mössbauer effect measurements. X‐ray intensity calculations indicate that Sn⁴⁺ ions occupy only octahedral (B) sites replacing Fe³⁺ ions and the added Co²⁺ ions substitute for A‐site Fe³⁺ ions. The lattice constants are determined and the applicability of Vegard's law has been tested. The Mössbauer spectra at 300 K have been fitted with two sextets in the ferrimagnetic state corresponding to Fe³⁺ at tetrahedral (A) and octahedral (B) sites for x≤0.4. The Mössbauer intensity data show that Sn possesses a preference for the B‐site of the spinel. As expected, the hyperfine field and Curie temperature determined from a.c. susceptibility decreases with increasing Sn content. The variation of the saturation magnetic moment per formula unit measured at 77 and 300 K with Sn content is satisfactorily explained on the basis of Néel's collinear spin ordering model for x=0.1–0.4.     

Investigation of the processes of iron-ion recharging on surfaces of natural nanoclays (Based on Mössbauer spectroscopy data)

Experimental results on studying charge exchange in iron ions in systems of reduced dimensionality (nanoclays) of natural origin is presented. The conditions for the observation and the effect of different external factors on the reversible transition of the valence change for iron ions (Fe³⁺ ai Fe²⁺) in typical representatives of clays is established using Mössbauer spectroscopy. A technique of the determination of the location of iron complexes on the aluminosilicate surface of clays for Earth group planets is developed.     

Specific features of local structural,valence, and magnetic states of iron ions in the perovskite Bi0.5Ca0.5FeO3

The perovskite Bi_0.5Ca_0.5FeO₃ has been investigated using the Mössbauer effect at temperatures of 295 and 675 K. The measured temperature of the magnetic phase transition (Néel temperature) is T _N = 640 ± 10 K. Above the Néel temperature, there are two nonequivalent structural states of iron ions. In the perovskite Bi_0.5Ca_0.5FeO₃ at room temperature, there are seven most probable nonequivalent magnetic states of iron ions with significantly different values of the hyperfine interaction parameters. Four iron states correspond to Fe³⁺ ions in the octahedral oxygen environment, and three iron states correspond to Fe³⁺ ions in the tetrahedral oxygen environment.     

Mössbauer study of iron uptake in cucumber root

⁵⁷Fe Mössbauer spectroscopy was used to study the uptake and distribution of iron in the root of cucumber plants grown in iron-deficient modified Hoagland nutrient solution and put into iron-containing solution with 10 μM Fe citrate enriched with ⁵⁷Fe (90%) only before harvesting. The Mössbauer spectra of the frozen roots exhibited two Fe³⁺ components with typical average Mössbauer parameters of δ?=?0.5 mm s^?1, Δ?=?0.46 mm s^?1 and δ?=?0.5 mm s^?1, Δ?=?1.2 mm s^?1 at 78 K and the presence of an Fe²⁺ doublet, assigned to the ferrous hexaaqua complex. This finding gives a direct evidence for the existence of Fe²⁺ ions produced via root-associated reduction according to the mechanism proposed for iron uptake for dicotyledonous plants. Monotonous changes in the relative content of the components were found with the time period of iron supply. The Mössbauer results are interpreted in terms of iron uptake and transport through the cell wall and membranes.     

The coordination of Co2+ions in Co substituted magnetites,Fe3−xCoxO4, with x⩽0.04

⁵⁷Fe Mössbauer spectra at room temperature, both with and without external magnetic field, indicate that Co²⁺ ions in Co_xFe_3?xO₄spinels (x?0.04) are situated on the octahedral B sites. The Mössbauer parameters are listed and the existence of unpaired Fe³⁺ ions is evidenced.     

Influences of La3+ substitution on the structure and magnetic properties of M-type strontium ferrites

M-type strontium ferrites with substitution of Sr²⁺ by rare-earth La³⁺, according to the formula Sr_1−xLa_xFe₁₂O₁₉, are prepared by the ceramic process. Influences of the substituted amount of La³⁺ on structure and magnetic properties of Sr_1−xLa_xFe₁₂O₁₉ compounds have systematically been investigated by XRD, VSM and Mössbauer spectrum. When the substituted amount x is below 0.30, X-ray diffraction shows that the samples are single M-type hexagonal ferrites. It is found that the suitable amount of La³⁺ substitution may remarkably increase saturation magnetization σ_s and intrinsic coercivity H_cJ. With the La³⁺ addition for the same sintering temperature, σ_s and H_cJ increase at first, then decrease gradually. However, the substituted amount x at the maximum value of H_cJ is bigger than that of σ_s. Mössbauer spectroscopy of ⁵⁷Fe in Sr_1−xLa_xFe₁₂O₁₉ has shown that the substitution of Sr²⁺ by La³⁺ is associated with a valence change of Fe³⁺ to Fe²⁺ at 2a or 4f₂ site. The magnetic properties are reflected in the Mössbauer spectra which indicate that the magnetic hyperfine field (H_hf) is detected with the highest value at x=0.20. The different exchange paths between the iron sublattices are discussed according to the increased hyperfine fields of the 12k- and 2b-site. The Curie temperature of Sr_1−xLa_xFe₁₂O₁₉ decreases linearly with increasing La³⁺ substitution.     

Mössbauer spectroscopy on57Fe in highT c superconductor Bi2Sr2Ca1Cu2O y

Mössbauer measurements were performed on polycrystalline⁵⁷Fe: Bi₂Sr₂Ca₁Cu₂O _y , super-conductor in the temperature range of 77–296 K. The samples were obtained in a solid phase synthesis using 0.01, 0.03, 0.1 and 0.5 mol fractions of α-Fe₂O₃ (96% enriched in⁵⁷Fe). A prevailing quadrupole doublet practically independent of temperature and iron concentration characterizes the obtained Mössbauer spectra. The corresponding hyperfine parameters suggest the presence of high spin Fe¹¹¹ ions in a strongly distorted octahedral symmetry which indicates a probable copper substitution by iron in the system.     

Hyperfine interactions in stabilized Fe1−δO:Al3+ system

Highly stable Fe_1?δO:Al³⁺ system has been synthesized by checking the spontaneous disproportionation of FeO. The novel preparation route of incorporating non-magnetic trivalent Al³⁺ ions in the wustite lattice is followed for the preparation of solid solutions. X-ray diffraction (XRD), chemical analysis and Fe⁵⁷ Mössbauer effect are used for the characterization. The hyperfine interaction parameters reported are characteristic of high spin Fe²⁺ state which confirmed the stabilization of FeO.     

On the iron valence states in B2O3-PbO-GeO2 glasses

The Mössbauer effect measurements performed on 20Fe₂O₃ 80 3B₂O₃ (1?x)PbO xGeO₂ glasses show that the ratio between the number of ferrous ions to the total number of iron ions decreases by increasing the GeO₂ content. The Curie constants calculated from the distribution of iron cations obtained by Mössbauer effect data are in agreement with the values determined from magnetic measurements. Finally, we discuss the influence of the glass composition and melting temperature on the iron valence states.     

X-Ray photoelectron and mössbauer spectroscopy studies on molybdenum-bearing ferrite

The X-ray photoelectron spectra of Mo 3d electrons (232.4–232.9 and 229.4–229.6 eV) for Mo-bearing ferrites have suggested that molybdenum ions are in the 4+ valence state on the lattice points in the spinel structure. The XPS data for Mo 3d and Fe 2p electrons combined with the Mössbauer data at room temperature suggest that Fe₂MoO₄ takes a valence state (Fe²⁺)_tet[Fe²⁺Mo⁴⁺]_octO₄.     

Magnetic properties of the mixed spinel Mg1+xMnxFe2-2xO4

The structural and magnetic properties of the mixed spinel Mg_1+xMn_xFe_2-2xO₄ system for 0.1<= x <= 0.9 have been studied by means of X-ray diffraction, magnetization, a.c. susceptibility and Mössbauer spectroscopy measurements. X-ray intensity calculations indicate that Mn⁴⁺ ions occupy only octahedral (B) sites replacing Fe³⁺ ions and the added Mg²⁺ ions substitute for A-site Fe³⁺ ions. All samples are magnetic at 12 K displaying Mössbauer spectra that have magnetic sextets coexisting with a central doublet that increases in population with increasing Mn concentration, indicating the presence of short range ordering (clustering). The Mössbauer intensity data show that Mn possesses a preference for the B-site of the spinel over the whole range of concentration. As expected, the hyperfine field and Curie temperature determined from a.c.susceptibility data decrease with increasing Mn content. Magnetization results indicate that on increasing dilution x, the collinear ferrimagnetic phase breaks down at x = 0.3 before reaching the ferrimagnetic percolation limit (x=0.6), as a result of the presence of competing exchange interactions, which is well supported by Mössbauer results. From all the above results, it is proposed that with increasing Mn content from x=0.6 to 0.9, the frustration and disorder increase in the system suppressing the ferrimagnetic ordering, and the system approaches to a cluster spin glass type of ordering at x=0.8 as reflected in the a.c.susceptibility and Mössbauer spectrum.