Local states of iron in iron implanted hematite Fe2O3

Powder samples of⁵⁷Fe₂O₃ and⁵⁶Fe₂O₃ were implanted with⁵⁶Fe and⁵⁷Fe ions, respectively. By the use of Conversion Electron Mössbauer Spectroscopy it was possible to observe the local states of implanted ions (⁵⁷Fe in⁵⁶Fe₂O₃) or the states of iron atoms from the target which were displaced during implantation due to the ballistic processes (⁵⁶Fe in⁵⁷Fe₂O₃). The implanted and displaced iron atoms appear in three different states: (i) in regular substitutional positions of Fe₂O₃, (ii) as magnetite Fe₃O₄-type structures and (iii) paramagnetic FeO_1?x state. The observed fractions of each state agree rather well with the calculated values obtained from the local iron atom enrichment at the surface as well as from the analysis of the equilibrium phase diagram for the binary Fe?O system. However, in⁵⁷Fe implanted samples some enhancement of the FeO_1?x fraction was found in comparison with the⁵⁶Fe implanted hematite.     

Investigation of Glasses and Glaze Coats of Composition R2O–RO–Fe2O3(FeO)–Al2O3–B2O3–SiO2 by the EPR Method

The valence state and the coordination environment of the paramagnetic centers of iron ions in glasses and vitreous coats of composition R₂O–RO–Fe₂O₃(FeO)–Al₂O₃–B₂O₃–SiO₂ have been investigated by the EPR method. The tetrahedral and octahedral coordinations of Fe³⁺ ions have been revealed. The character of change in the EPR spectra of the materials studied in the vitreous and vitrocrystalline state has been determined. It is shown that the coordination number of iron ions is dependent on the crystallization processes.     

Electronic structures of Fe in La1−x Ba x FeO3−y (0≤x≤0.70)

Mössbauer spectra of La_1–x Ba _x FeO_3–y recorded at room temperature for various values of x show a six-line and/or a single-line subspectrum. The six-line subspectrum with IS=0.41 mm/s and H=52 T results from an orthorhombic perovskite containing only Fe³⁺ ions. The single-line subspectrum at 0.17 mm/s from a cubic perovskite can be assigned to neither Fe³⁺ nor Fe⁴⁺ but to an intermediate valence state, which may be due to electron hopping between the Fe³⁺ and Fe⁴⁺ ions on the identical octahedral sites. The temperature dependence of electron hopping in the compound La_0.40Ba_0.60FeO_3–y is presented.     

Relationship between structural and magnetic properties in (Ti,Fe)O2 powders obtained by mechanical milling

Fe-doped TiO₂ samples with different Fe content were prepared by mechanical alloying starting from TiO₂ rutile and FeO. The samples were structurally and magnetically characterized by XRD, Mössbauer spectroscopy, X-ray absorption spectroscopy (XAS), AC-susceptibility and magnetization measurements. XAS results showed that Fe ions were incorporated into the rutile phase with oxygen coordination that was lower than that expected in this phase. The oxygen coordination number decreased with the increase of Fe²⁺ ions such as it was previously found in the milled samples of TiO₂ doped with hematite. The RT Mössbauer spectra were reproduced using two paramagnetic interactions, one corresponding to Fe²⁺ (δ∼0.87 mm/s) and the other to Fe³⁺ (δ∼0.31 mm/s). Magnetometry measurements showed the presence of paramagnetic and ferromagnetic-like interactions at room temperature. Although saturation and coercivity of the ferromagnetic phase increased with iron, the effective magnetic moment per iron atom decreased, probably due to the precipitation of Fe rich antiferromagnetic structures.     

Magnetic properties of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> surface

The magnetic properties of the magnetite Fe₃O₄(110) surface have been studied by spin resolved Auger electron spectroscopy (SRAES). Experimental spin resolved Auger spectra are presented. The results of calculation of Auger lines polarization carried out on the basis of electronic state density are presented. Problems related to magnetic moments of bivalent (Fe²⁺) and trivalent (Fe³⁺) ions on the Fe₃O₄(110) surface are discussed. It is established that the deposition of a thin bismuth film on the surface results in significant growth of polarization of iron Auger peaks, which is due to additional spin-orbit scattering of electrons by bismuth atoms.     

Monitoring by Mössbauer spectroscopy the thermal reduction of hematite into magnetite: the surface effect and charge disproportionality in iron oxide nanoparticles

Nanoparticles of magnetite Fe₃O₄ were synthesized by thermal reduction of hematite α-Fe₂O₃ powder in the presence of high boiling point solvent. The structural transformations and magnetic properties of the obtained nanoparticles were investigated by the ⁵⁷Fe Mössbauer spectroscopy, X-ray diffraction, and magnetic measurements. The content of hematite and magnetite phases was evaluated at each step of the chemical and thermal treatment of the product. An increase of saturation magnetization with the reaction time correlates with an increase of concentration of magnetite in the samples. The electron hoping between Fe^2?+? and Fe^3?+? ions in the octahedral sites of the magnetite nanoparticles and Verwey phase transition were investigated. It was established that not all iron ions in the octahedral sites participated in electron hoping Fe^2?+????Fe^3?+? above the Verwey temperature T _V, and the charge distribution could be expressed as $\big( {{\rm Fe}^{3+}}\big)_{{\rm tet}} \big[ {{\rm Fe}_{1.85}^{2.5+} {\rm Fe}_{0.15}^{3+} }\big]_{{\rm oct}} {\rm O}_4$ .     

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.     

Magnetic ordering of monoclinic FeNaP2O7 studied by Mössbauer spectroscopy

Several perlites of different colours originating from east Rhodope (Bulgaria) have been studied by Mössbauer spectroscopy. Several types of iron are revealed (i) paramagnetic Fe²⁺ and Fe³⁺ down 4.2K which correspond to iron dispersed into the glass matrix (ii) small aggregates of Fe²⁺ and hematite in colloidal type phase with superparamagnetic properties (iii) large aggregates and microlites of hematite and magnetite. Alteration effects and colour problem are discussed.     

Relation between the fine structure of the vibrational spectrum of the crystal lattice and the cation distribution in Co1+2xFe2−3xSbxO4 ferrites

The infrared reflection spectra in the region of lattice vibrations (1500–200 cm^–1) of ferrite spinels Co_1+2xFe_2–3xSb_xO₄ with x=0.0–0.4 are investigated. The permittivity spectra are calculated using the Kramers-Kronig relations. A dispersion analysis of the ₁(v); ₂(v) spectra, carried out using the multiscintillator model, enabled the fine structure of the bands of the spectra to be determined. It was found that for CoFe₂O₄ ferrite the short-wave band (v=590 cm^–1) consists of two components, while the long-wave band (v=375 cm^–1) consists of fur components. Since cobalt ferrite is inverted spinel, in which there are only Fe³⁺ ions in the tetra positions, the doublet structure with v=590 cm^–1 must obviously belong to vibrations of the ion groups FeO₆ and CoO₆, while the second band may belong to vibrations of the ion complexes consisting of the tetra-cation (Fe³⁺), oxygen and the three closest octa-cations [3Fe], [2Fe1Co], [2Co1Fe] and [3Co]. The replacement of some of the iron ions with antimony leads to the appearance of additional lines from the short-wave edge of both bands. The intensity of these lines increases as the value of the diamagnetic substitution increases, which enables the highest-frequency component to be uniquely related to the vibrations of the complex formed by the tetra-cations Fe³⁺ or Co²⁺, the anion and the three octa-cations Sb⁵⁺.V. I. Ul'yanov-Lenin Kazan State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 105–109, July, 1995.     

Improved quantification of alite and belite in anhydrous Portland cements by Si MAS NMR: Effects of paramagnetic ions

The applicability, reliability, and repeatability of ²⁹Si MAS NMR for determination of the quantities of alite (Ca₃SiO₅) and belite (Ca₂SiO₄) in anhydrous Portland cement was investigated in detail for 11 commercial Portland cements and the results compared with phase quantifications based on powder X-ray diffraction combined with Rietveld analysis and with Taylor–Bogue calculations. The effects from paramagnetic ions (Fe³⁺) on the spinning sideband intensities, originating from dipolar couplings between ²⁹Si and the spins of the paramagnetic electrons, were considered and analyzed in spectra recorded at four magnetic fields (4.7–14.1 T) and this has led to an improved quantification of alite and belite from ²⁹Si MAS NMR spectra recorded at “high” spinning speeds of ν_R=12.0–13.0 kHz using 4 or 5 mm rotors. Furthermore, the impact of Fe³⁺ ions on the spin-lattice relaxation was studied by inversion-recovery experiments and it was found that the relaxation is overwhelmingly dominated by the Fe³⁺ ions incorporated as guest-ions in alite and belite rather than the Fe³⁺ sites present in the intimately mixed ferrite phase (Ca₂Al_xFe_2−xO₅).     

Optical emissions of products sputtered from Fe, Fe2O3 and Fe3O4 powders

Powder iron has been bombarded by a 5 keV Kr⁺ ions in a vacuum better than 10^-7 torr and under few 10^-6 torr ultra pure oxygen partial pressure. The optical spectra of the sputtered particles were recorded between 340.0 nm and 410.0 nm. These spectra exhibit discrete lines, which are attributed to neutral excited atoms of iron. Two iron oxides, namely hematite (Fe₂O₃)_{3}) and magnetite (Fe₃O₄)_{4}), in powder form, were studied under the same experimental conditions and identical lines were observed in the obtained spectra. The absolute intensities of the spectral lines in all spectra were measured and the differences in the recorded yield photons were discussed in term of electron-transfer processes between the excited sputtered atom and the bombarded surface. In accordance with the proposed interpretation, we suggest values for the energy gaps and electronic affinities for the studied oxides and for the oxide layer that might be formed by the adsorption of oxygen atoms.     

Vibrations and chemical states of iron ions in soda‐lime glasses determined by element‐specific X‐ray analyses

We systematically study medium‐range structures including more than three neighboring atoms around iron ions (Fe²⁺ and Fe³⁺) in soda‐lime glass samples with low iron oxide concentrations (M_Fe2O3) and a wide number ratio of Fe²⁺ to all iron ions (Fe²⁺/Σ_nFe). The precise medium‐range structures around iron ions in glass have not yet been revealed because of a lack of the appropriate measurement methods. To avoid this problem, we used element‐specific nuclear resonant inelastic scattering (NRIS) with synchrotron X‐rays to observe the vibrations of iron ions (⁵⁷Fe). The vibrations are related to medium‐range structures with more than three neighboring atoms and to the potential asymmetry and the coordination environment, around iron ions. The NRIS method has high sensitivity and can measure over a wide concentration range. Linear combination fitting of the X‐ray absorption fine structure spectra, which measures only the first neighbors but is a faster than using the NRIS method, was also used additionally. A systematically produced set of glasses with 0.015–5 wt% M_Fe2O3 and 0–0.85 Fe²⁺/Σ_nFe was measured with these methods. It was found that the soda‐lime glass possessed two different medium‐range structures with different iron ion valences (~2+ or ~3+), which were determined by the Fe²⁺/Σ_nFe, and that these structures were generated during production of the glass. Moreover, these medium‐range structures were the same from 0.015 to 5 wt% M_Fe2O3.     

Mixed valence of iron in natural vonsenite

The exchange of electrons between adjacent ions in different oxidation states in vonsenite was observed using Mössbauer spectroscopy. The Mössbauer spectra of a series of naturally occurring vonsenite were recorded over a temperature range of 120–773 K. Four quadrupole doublets were resolved by computer fitting and assigned to Fe²⁺(Fel), Fe²⁺(Fe3), Fe³⁺(Fe2, Fe4) and Fe²⁺-Fe³⁺(Fe2–Fe4). The percentage of iron sites participating in an electron exchange process increases from 17% between 120 and 298 K to 27% between 573 and 773 K.     

Single-Crystal Fe Q-Band ENDOR Study of the 4 Iron–4 Sulfur Cluster in its Reduced [4Fe–4S] State

⁵⁷Fe Q-band ENDOR has been used to study the [4Fe–4S]¹⁺ state created by γ irradiation of single crystals of the synthetic model compound [N(C₂H₅)₄]₂[Fe₄S₄(SCH₂C₆H₅)₄] enriched in ⁵⁷Fe. This compound is an excellent biomimetic model of the active sites of many 4 iron–4 sulfur proteins, enabling detailed and systematic studies of its oxidized [4Fe–4S]³⁺ and reduced [4Fe–4S]¹⁺ paramagnetic states. Taking advantage of the fact that Q-band ENDOR, in contrast with X-Band ENDOR, allows for a very good separation of the ⁵⁷Fe transitions from those of the protons, the complete hyperfine tensors of the four iron atoms for the [4Fe–4S]¹⁺ species has been measured with precision. For each iron atom, the electron orbital and electron spin isotropic contributions have been determined separately. Moreover, it is remarkable that two ⁵⁷Fe hyperfine tensors attributed to the ferrous pair of iron atoms are very different. In effect, one tensor presents a much larger anisotropic part and a much smaller isotropic part than those of the other. This difference has been interpreted in terms of a differential electron orbital hyperfine interaction among the two ferrous ions.     

Studying local structural, valence, and magnetic states of iron ions in Bi0.9Ca0.1FeO3 perovskite

Mössbauer method was used to study a perovskite compound Bi_0.9Ca_0.1FeO₃ at T = 295 K and at temperature above T _N . It has been established that Bi_0.9Ca_0.1FeO₃ has a rhombohedral crystal structure similar to that of BiFeO₃. The substitution of Ca²⁺ for Bi³⁺ ions leads to the formation of three states of Fe³⁺ ions with an octahedral surroundings and one state with a tetrahedral oxygen surroundings with substantially different hyperfine magnetic fields. All Fe ions are in a trivalent state; the compensation of the charge deficit occurs via the formation of oxygen vacancies. Above T _N , two structurally nonequivalent states of Fe³⁺ ions exist in the Bi_0.9Ca_0.1FeO₃ sample, which correspond to the Fe³⁺ ions with an octahedral and tetrahedral oxygen coordination.     

Preparation and study of magnetic properties of silico phosphate glass and glass-ceramics having iron and zinc oxide

The magnetic properties of 25SiO₂–50CaO–15P₂O₅–(10−x)Fe₂O₃−xZnO (where x=0, 2, 5 mol%) glass and glass-ceramics have been studied. These glasses are prepared by melt quench technique and heat treated at 800 °C for 6 h. Electron Spectroscopy for Chemical Analysis (ESCA) revealed that the fraction of non-bridging oxygen decreases with the increase in zinc oxide content. Evolution of crystalline phases in glass-ceramics has been studied by X-ray diffraction (XRD). The microstructure as seen by scanning electron microscopy (SEM) exhibits formation of nanosize particles. Effect of controlled heat treatment on magnetic properties was studied by means of a Superconducting Quantum Interference Device (SQUID) magnetometer. Mössbauer spectroscopy at room temperature was also carried out to determine the state of iron ions in glasses and glass-ceramics. Isomer shift values of the glasses suggest that Fe³⁺ and Fe²⁺ are in tetrahedral coordination. The analysis of the glass without ZnO shows about 58 wt% of total iron ions is in the Fe³⁺ state. The samples on heat treatment show improved magnetic properties due to the formation of magnetic nanoparticles. Magnetic studies revealed the relaxation of magnetic particles and the increase in saturation magnetization with addition of 2 mol% ZnO. Increase in ZnO content results in decrease in the strength of dipolar interactions.     

Hyperfine characterization of the crystallization of nanocrystalline NiFe2O4 from the amorphous silica gel

Nanocrystalline NiFe₂O₄ was in‐situ prepared in amorphous silica using tetramethylor‐thosilicate and nickel (iron) nitrate hydrate as the starting materials in a sol‐gel reaction. The magnetic nanocrystals in the amorphous silica glasses grew slowly with increasing temperature. Above 600^○C, nickel ferrite nanoparticles began to precipitate from the amorphous silica matrix. Mössbauer spectroscopy of the nanocomposites suggested that in the silica glasses, Fe ions were present exclusively as Fe³⁺ in octahedral coordination, and the chemical environment of the Fe³⁺ ions appeared to remain unchanged until the crystallization of nickel ferrite nanocrystals. The formation of NiFe₂O₄ nanocrystals was the result of partial transformation of the FeO₆ octahedra to FeO₄ tetrahedra. The nanocrystalline NiFe₂O₄ are characterized by super‐paramagnetic behaviour at room temperature.     

On the Valence State of Iron in Sr0.52+Ca0.52+Fe0.54+ Me0.54+O32−

Powder samples of Sr_0.5Ca_0.5Fe_0.5Me_0.5O₃ (Me = Co, Zr or Mn) and Sr_0.3La_0.7FeO₃ are investigated by X-ray diffraction and Mössbauer effect spectroscopy. Analysis of the completely ordered spectra suggested three kinds of iron ions coexist in general where the resolution into the different valence state is clearly seen. The Mössbauer effect parameters values are found to be close to those expected for Fe³⁺, Fe⁴⁺ and Fe⁵⁺ indicating that some of the tetravalent iron ions in its high spin state disproportionate into Fe³⁺ and Fe⁵⁺ ions passing through temperature dependent intermediate valence states.     

Phase transformation of strontium hexagonal ferrite

The phase transformation of strontium hexagonal ferrite (SrFe₁₂O₁₉) to magnetite (Fe₃O₄) as main phase and strontium carbonate (SrCO₃) as secondary phase is reported here. SrFe₁₂O₁₉ powder was obtained by a heat treatment at 250 °C under controlled oxygen flow. It was observed that the phase transformation occurred when the SrFe₁₂O₁₉ ferrite was heated up to 625 °C in confinement conditions. This transformation took place by a combination of three factors: the presence of stresses in the crystal lattice of SrFe₁₂O₁₉ due to a low synthesis temperature, the reduction of Fe³⁺ to Fe²⁺ during the heating up to 625 °C, and the similarity of the coordination spheres of the iron atoms present in the S-block of SrFe₁₂O₁₉ and Fe₃O₄. X-ray diffraction analysis confirmed the existence of strain and crystal deformation in SrFe₁₂O₁₉ and the absence of them in the material after the phase transformation. Dispersive X-ray absorption spectroscopy and Fe⁵⁷ Mössbauer spectroscopy provided evidences of the reduction of Fe³⁺ to Fe²⁺ in the SrFe₁₂O₁₉ crystal.     

On the transferred hyperfine interaction in substituted yig

NMR of⁵⁷Fe is studied in a number of (M_xY_3–x) Fe₅O₁₂ garnets for small concentrations of M (M is either trivalent RE ion –Ho 3+, Gd 3+, Nd3+, Pr 3+, La 3+ or Bi 3+ ion). Beside the main resonance lines, the satellites were observed, which correspond to those Fe, in vicinity of which the impurity M is located. After correcting for the dipolar field, the field corresponding to the change of the transferred hyperfine interaction in M³⁺–O^2–-Fe³⁺ vs. Y³⁺–O^2–-Fe³⁺ triad was deduced from the satellites splitting. The analysis of the results indicates that the observed change in the transferred hyperfine field is mainly connected with the transfer of electrons between M³⁺ and Fe³⁺ ions and not with the local deformation around the impurity.