High-Energy Ball Milling of NiAl(Fe) System

High-energy ball milling was used to promote the solubilization of iron into NiAl powder for an iron concentration range of 10–30 wt.%. The microstructural evolution induced by the intense mechanical deformations, under different milling conditions, was followed by X-ray diffraction and Mössbauer spectroscopy. The Mössbauer spectra are dominated by a magnetic sextet of about 33 T. Increasing the time and the speed of milling gives rise to a non-resolved doublet, having parameters typical of a NiAl compound with Fe atoms in solution. At the same time a reduction of lattice parameter occurs, which can be correlated to composition variations and partial disordering of the NiAl structure. Subsequent annealing modifies the Mössbauer spectra noticeably. In particular, the non-magnetic component becomes a broad singlet. Both diffraction analysis and Mössbauer spectroscopy indicate that a fcc Ni(Al,Fe) solid solution is forming in samples milled in agate. It is observed that the grain size of the milled products remains in the nanometric range even after thermal treatment, which adds interest to possible applications.     

Heat-induced charge transfer in cobalt iron cyanide

The heating of Co(2+) ferricyanide above 80 °C induces an inner charge transfer from Co(2+) towards Fe(III) to form the mixed valence system Co(2+)Co(III) ferri- ferro-cyanide. This charge transfer takes place preserving the material framework and forming a solid solution of the initial and final species. The cell edge of the cubic cell (Fm-3m) of this solid solution follows a regular variation with the material composition. This mixed valence system was characterized using X-ray diffraction, infrared, thermo-gravimetric, Mössbauer and magnetic measurements. Its formation is easily detected by the appearance of an intermediate ν(CN) absorption band in the infrared spectra at around 2120 cm⁻¹, 40 cm⁻¹ below and above the observed frequency for this vibration in Co(2+) ferri- and ferro-cyanide, respectively.     

On the Role of Aluminum in Finemet

The role of aluminum with respect of its influence on some intrinsic magnetic properties of the nanocrystalline Finemet, such as saturation magnetization, Curie temperature, spin-wave stiffness constant and hyperfine magnetic fields was investigated. The strengthening effect of Al on the exchange interaction was observed for the alloys with small Al content (up to 3 at.%). Higher concentration of Al (5-7 at.%) led to considerably suppressed exchange interaction.     

Structural, microstructural and hyperfine properties of nanocrystalline iron particles

Nanocrystalline Fe particles were successfully prepared by the mechanical milling process using a high-energy planetary ball mill. The physical properties of the samples were investigated as a function of the milling time, t (in the 0-54 h range) by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and Mössbauer spectroscopy. After 54 h of milling, the lattice parameter increases from 0.28620 (3) nm for the starting Fe powder to 0.28667 (3) nm, the grain size decreases from 110 to 13 nm, while the strain increases from 0.09% to 0.7%. The powder particle morphology was observed by SEM at different stages of milling. For t less than 24 h, the Mössbauer spectra are characterized by one sextet corresponding to the crystalline bcc Fe phase, while for t greater than 24 h, the iron particles exhibit a two-component Mössbauer spectrum due to the presence of two phases: the crystallites bcc Fe phase and the grain-boundary region. The appearance and the increase in intensity of the second sextet with t may indicate that the interfacial region effect increases with milling time due to the grain size reduction and a probable disordered state of the grain boundaries.     

Recoilless fraction, structural, magnetic and thermal properties of Fe73.5Cu1Nb3Si13.5B9 alloy

Differential scanning calorimetry, X-ray diffraction and room temperature Mössbauer spectrum measurements of Fe_73.5Cu₁Nb₃Si_13.5B₉ (Finemet) alloy have been carried out in order to study its structural and magnetic properties as a function of annealing temperature. The DSC profile of as-quenched Finemet showed two exothermic peaks at 530 and 702 °C, corresponding to two crystallization processes. The Finemet alloy remains amorphous at 450 °C with one broad peak in XRD pattern and one broad sextet in Mössbauer spectrum. When the Finemet alloy was annealed at 550 °C, only well indexed body-center-cubic phase was detected. After being annealed at 650 and 750 °C, the XRD patterns showed the coexistence of α-Fe(Si) and Fe-B intermetallic phases with the increase in XRD peak intensities, indicating the growth of crystallites and the decomposition of Fe_73.5Cu₁Nb₃Si_13.5B₉ alloy at elevated temperatures. The Mössbauer spectra of annealed Finemet alloy could be fitted with 4 or 5 sextets and one doublet at higher annealing temperatures, revealing the appearance of different crystalline phases corresponding to the different Fe sites above the crystallization temperature. The appearance of the nanocrystalline phases at different annealing temperatures was further confirmed by the recoilless fraction measurements.     

Studies on Structural, Magnetic and Thermal Properties of xFe2TiO4-(1−x)Fe3O4 (0≤x≤1) Pseudo-binary System

The xFe₂TiO₄-(1−x)Fe₃O₄ pseudo-binary systems (0≤x≤1) of ulvöspinel component were synthesized by solid-state reaction between ulvöspinel Fe₂TiO₄ precursors and commercial Fe₃O₄ powders in stochiometric proportions. Crystalline structures were determined by X-ray powder diffraction (XRD) and it was found that the as-obtained titanomagnetites maintain an inverse spinel structure. The lattice parameter a of synthesized titanomagnetite increases linearly with the increase in the ulvöspinel component. ⁵⁷Fe room temperature Mössbauer spectra were employed to evaluate the magnetic properties and cation distribution. The hyperfine magnetic field is observed to decrease with increasing Fe₂TiO₄ component. The fraction of Fe²⁺ in both tetrahedral and octahedral sites increases with the increase in Ti⁴⁺ content, due to the substitution and reduction of Fe³⁺ by Ti⁴⁺ that maintains the charge balance in the spinel structure. For x in the range of 0 ≤x≤0.4, the solid solution is ferrimagnetic at room temperature. However, it shows weak ferrimagnetic and paramagnetic behavior for x in the range of 0.4<x≤0.7. When x>0.70, it only shows paramagnetic behavior, with the appearance of quadrupole doublets in the Mössbauer spectra. Simultaneous differential scanning calorimetry and thermogravimetric analysis (DSC-TGA) studies showed that magnetite is not stable, and thermal decomposition of magnetite occurs with weight losses accompanying with exothermic processes under heat treatment in inert atmosphere.     

Structural transformations and magnetic properties of Fe60Pt15B25 and Fe60Pt25B15 nanocomposite alloys

Structural and magnetic properties of two rapidly solidified and post-annealed Fe₆₀Pt₁₅B₂₅ and Fe₆₀Pt₂₅B₁₅ alloys are compared. The as-quenched Fe₆₀Pt₁₅B₂₅ ribbon was fully amorphous whereas in the Fe₆₀Pt₂₅B₁₅ alloy the amorphous phase coexists with an fcc FePt disordered solid solution. Differential scanning calorimetry curves of both alloys reveal a single exothermal peak with onset temperatures of 873 and 847 K for Fe₆₀Pt₁₅B₂₅ and Fe₆₀Pt₂₅B₁₅, respectively. Magnetically hard, tetragonal ordered L1₀ FePt and magnetically soft Fe₂B nanocrystalline phases were formed due to the annealing of the alloys, as indicated by X-ray diffraction and Mössbauer spectroscopy measurements. Two-phase behavior was detected in the temperature dependence of magnetization of the annealed samples. A magnetic hardening was observed for all annealed ribbons. Magnetic properties of the annealed alloys, studied by hysteresis loop measurements, were related to the differences in the relative fractions of the hard and soft magnetic phases calculated from Mössbauer spectra. The alloy with 25 at% Pt exhibits better hard magnetic properties (H_c=437 kA/m, M_r/M_s=0.74) than the alloy with smaller Pt content (H_c=270 kA/m, M_r/M_s=0.73) mainly due to the larger abundance of the ordered tetragonal FePt phase.     

BiFeO3 ceramic matrix with Bi2O3 or PbO added: Mössbauer, Raman and dielectric spectroscopy studies

In this paper Mössbauer, Raman and dielectric spectroscopy studies of BiFeO₃ (BFO) ceramic matrix with 3 or 10 wt% of Bi₂O₃ or PbO added, obtained through a new procedure based on the solid-state method, are presented. Mössbauer spectroscopy shows the presence of a single magnetically ordered phase with a hyperfine magnetic field of 50 T. Raman spectra of BFO over the frequency range of 100-900 cm⁻¹ have been investigated, at room temperature, under the excitation of 632.8 nm wavelength in order to evaluate the effect of additives on the structure of the ceramic matrix. Detailed studies of the dielectric properties of BiFeO₃ ceramic matrix like capacitance (C), dielectric permittivity (ε) and dielectric loss (tan δ), were investigated in a wide frequency range (1 Hz-1 MHz), and in a temperature range (303-373 K). The complex impedance spectroscopy (CIS) technique, showed that these properties are strongly dependent on frequency, temperature and on the added level of impurity. The temperature coefficient of capacitance (TCC) of the samples was also evaluated. The study of the imaginary impedance (−Z″) and imaginary electric modulus (M″) as functions of frequency and temperature leads to the measurement of the activation energy (E_ac), which is directly linked to the relaxation process associated with the interfacial polarization effect in these samples.     

Ultrathin Fe layers on Ag (1 0 0) surface

Iron layers (0.15-10 ML thick) deposited on Ag (1 0 0) substrates were investigated by conversion electron Mössbauer spectrometry over a broad temperature range. The layers were characterized by scanning tunneling microscopy. Different forms of the layers, depending on their thickness, were observed. Minimum roughness of the layers were found at 0.15 and 10 ML thickness values. The Mössbauer spectra showed systematic thickness dependence. At low thickness values, broad doublets were observed, while above 6 ML, magnetic split spectra appeared at room temperature. At low temperatures, magnetically split spectra appeared with parameter values characteristic of Fe-Ag and Fe-Fe atomic interactions. The hyperfine split spectra indicated magnetic anisotropy and an enhanced saturation hyperfine magnetic field of ?40 T. The latter value is the highest ever measured for iron in thin layers.     

Compositional and structural characterization of nanoporous films produced by iron anodizing in ethylene glycol solution

We report on the composition and morphology of as-grown anodic oxide films onto the iron surface in an ethylene glycol solution containing some NH₄F and H₂O by anodizing under direct current bias. Decrease in the content of NH₄F and the temperature of electrolyte allow us to form either nanochannel or nanotubular films over a larger potential window, ca. from 30 to 100 V. By this way, the films in thickness of up to10 μm have been formed. Mössbauer spectra recorded at room to cryogenic temperatures under conversion electron and transmission modes revealed the formation of lepidocrocite (γ-FeOOH) film containing some Fe(OH)₂ and/or FeF₂·4H₂O. An increase in anodizing voltage results in fabrication of more porous and less Fe(II) compounds containing films.     

Vibrational dynamics of biological molecules: Multi-quantum contributions

High-resolution X-ray measurements near a nuclear resonance reveal the complete vibrational spectrum of the probe nucleus. Because of this, nuclear resonance vibrational spectroscopy (NRVS) is a uniquely quantitative probe of the vibrational dynamics of reactive iron sites in proteins and other complex molecules. Our measurements of vibrational fundamentals have revealed both frequencies and amplitudes of ⁵⁷Fe vibrations in proteins and model compounds. Information on the direction of Fe motion has also been obtained from measurements on oriented single crystals, and provides an essential test of normal mode predictions. Here, we report the observation of weaker two-quantum vibrational excitations (overtones and combinations) for compounds that mimic the active site of heme proteins. The predicted intensities depend strongly on the direction of Fe motion. We compare the observed features with predictions based on the observed fundamentals, using information on the direction of Fe motion obtained either from DFT predictions or from single crystal measurements. Two-quantum excitations may become a useful tool to identify the directions of the Fe oscillations when single crystals are not available.     

Concerning the cation distribution in MnFe2O4 synthesized through the thermal decomposition of oxalates

A single phase manganese ferrite powder have been synthesized through the thermal decomposition reaction of MnC₂O₄·2H₂O-FeC₂O₄·2H₂O (1:2 mole ratio) mixture in air. DTA-TG, XRD, Mössbauer spectroscopy, FT-IR and SEM techniques were used to investigate the effect of calcination temperature on the mixture. Firing of the mixture in the range 300-500 °C produce ultra-fine particles of α-Fe₂O₃ having paramagnetic properties. XRD, Mössbauer spectroscopy as well as SEM experiments showed the progressive increase in the particle size of α-Fe₂O₃ up to 500 °C. DTA study reveals an exothermic phase transition at 550 °C attributed to the formation of a Fe₂O₃-Mn₂O₃ solid solution which persists to appear up to 1000 °C. At 1100 °C, the single phase MnFe₂O₄ with a cubic structure predominated. The Mössbauer effect spectrum of the produced ferrite exhibits normal Zeeman split sextets due to Fe³⁺ions at tetrahedral (A) and octahedral (B) sites. The obtained cation distribution from Mössbauer spectroscopy is (Fe_0.92Mn_0.08)[Fe_1.08Mn_0.92]O₄.     

NMR and Mössbauer Study of Al2O3–Eu2O3

Alumina–europia mixed oxides with 5 and 10 wt.% Eu₂O₃ were studied by Mössbauer spectroscopy, ²⁷Al MAS-NMR and X-ray diffraction (XRD). The samples were prepared by the sol–gel technique. The XRD patterns for the calcined samples show a broad peak around 2θ = 30° which is assigned to the Eu₂O₃; after treatment with hydrogen at 1073 K no reduction to Eu⁺² or Eu⁰ was observed. The NMR spectra show three peaks, which are assigned to the octahedral, pentahedral and tetrahedral aluminum sites; the intensity of each peak depends on the concentration of europium ions. The Mössbauer spectra of the calcined samples show a single peak near zero velocity which is attributed to the Eu⁺³; after H₂ treatment at 1073 K similar spectra were obtained, suggesting Eu⁺³ is not reducibly at this temperature.     

Structural study by X-ray diffraction and Mössbauer spectroscopy of a new synthetic iron phosphate: K4MgFe3(PO4)5

A new iron phosphate K₄MgFe₃(PO₄)₅ has been synthesized by the flux method and characterized by single-crystal X-ray diffraction and Mössbauer spectroscopy. It crystallizes in the tetragonal system with the space group and the unit cell parameters a=9.714(3) Å and c=9.494(5) Å. The crystal structure is of a new type. It exhibits a three-dimensional framework built up from corner-sharing MO₅ (M=0.75Fe+0.25Mg) trigonal bipyramids and PO₄ tetrahedra. The K⁺ ions are occupying large eight-sided tunnels running along c. A room temperature Mössbauer study confirmed the +3 valence state of iron and its five-coordination.     

Synthesis and cation distribution of copper-substituted spinel-related lithium ferrite

Single-phased Cu²⁺-substituted spinel-related Li_0.5Fe_2.5O₄ was synthesized by sintering a mixture of Cu²⁺-substituted corundum-related α-Fe₂O₃ and Li₂CO₃ at 700 °C which is ∼325-400 °C lower than the temperature at which the material is prepared by the conventional ceramic methods. X-ray powder diffraction, X-ray photoelectron spectroscopy, Mössbauer spectroscopy and magnetic measurements were used to characterize the material. In contrast to high-temperature synthetic routes, the present one leads to a Cu⁺-and Fe²⁺-cation free material, thereby optimizing its technological value. Rietveld refinement of the XRD data favors a structural model in which Cu²⁺ substitutes for both Fe³⁺ and Li⁺ at the octahedral sites. Mössbauer and magnetic data are consistent with this model if spin thermal reversal and/or spin canting are taken into account for the later.     

Magnetic Relaxation in Nano-Phase Chromium Substituted Goethite

The magnetic and crystalline properties of chromium substituted goethite, -Fe_(1–x)Cr_(x)OOH (where x=0.00, 1.44, 3.00, 7.00, 10.14 wt.%) were studied using Mössbauer spectroscopy and X-ray diffraction. Transmission electron microscopy measurements showed that as the chromium concentration increased from 0 to 10.14 wt.%, the particle size decreased rapidly from 200 to 10 nm. X-ray diffraction analysis indicated that no lattice strain was present, even for chromium concentrations as high as 10.14 wt.%. Mössbauer spectra recorded at 300 K showed the presence of superparamagnetic relaxation in each sample. The relative area of the doublet component decreased, while that of the sextet component increased as the temperature decreased from 300 to 77 K. The mean hyperfine field measured at 77 K decreased from 49.6 T for the pure goethite to 44.9 T for the 10.14 wt.% chromium substitution. This decrease in the hyperfine field was attributed to both decreasing particle size and increasing chromium concentration.     

Electrical and magnetic characterization of a molecular material {[Ru(bpy)3][Fe(dca)3]2}n

Electrical and magnetic properties of {[Ru(bpy)₃][Fe(dca)₃]₂}_n (bpy=2,2′-bipyridine, dca=dicyanamide) have been studied. The compound is a non-extrinsic type of semiconductor and paramagnetic in nature. Mössbauer spectroscopy has established the presence of high spin Fe(II) as one major species in this compound, and no high spin-low spin transition of Fe(II) was detected down to 80 K under dark. The photo-response of electrical conductivity with time shows interesting behavior with repeated exposure.     

Magnetic properties of RE0.7Ca0.3Mn0.95Fe0.05O3 (RE=Sm and Gd) manganites at low temperature

The magnetic properties of RE_0.7Ca_0.3Mn_0.95Fe_0.05O₃ perovskite with rare-earth cations (RE=Sm and Gd) were investigated by means of X-ray diffraction, Mössbauer spectroscopy, and low temperature (4.2-266 K) magnetization measurements. Structural characterization of these compounds shows that they both have orthorhombic (Pbnm) structure. The Mössbauer spectra show clear evidence of local structural distortion of the Mn(Fe)O₆ octahedron, which is based on the non-zero nuclear quadrupole interactions for high-spin Fe³⁺ ions. It was found that the local structural distortion increases significantly when Sm³⁺ is replaced by Gd³⁺. This distortion is attributed to the Jahn-Teller coupling strength as estimated from the Mössbauer effect results. The magnetic results indicate that the Curie temperature decreases as a result of replacing Sm by Gd. This is due to the decrease of the average A-site cationic radius 〈r_A〉. The rapid increase of magnetization at low temperature indicates the magnetic ordering of rare earth ions at the A-site.     

On the role of lattice distortion in the catalytic properties of substituted orthovanadates La1−xFexVO4

A series of mixed orthovanadates with nominal compositions La_1−xFe_xVO₄ were synthesized and characterized using powder X-ray diffraction, Mössbauer spectroscopy and temperature-programmed reduction techniques. The substitution resulted in the co-presence of two distinct mixed metal compositions having either monoclinic LaVO₄ or a triclinic FeVO₄ structure. Both these constituent phases were however, found to be of distorted nature, with no measurable change in respective crystal symmetry. Furthermore, the extent of this distortion depended upon the value of x and is attributed to the partial substitutions at A-site, i.e. with a part of La by Fe in LaVO₄ lattice and a part of Fe by La in the FeVO₄ phase. The substitution-induced lattice distortion is found to result in the lowering of the reduction temperature in case of both the above mentioned phases, and also in the synergistic enhancement in catalytic activity for a model CO oxidation reaction.     

Mössbauer Spectroscopic Studies of an Oxidized Ordinary Chondrite Fallen at Itawa-Bhopji,India

Mössbauer studies of the Itawa-Bhopji meteorite fallen on May 30, 2000 in Rajasthan, India, show that the main iron minerals in it are Fe–Ni (kamacite/taenite), troilite, olivine and pyroxene. These provide characteristic signatures of an ordinary chondrite. Mössbauer absorption areas corresponding to different phases favour its classification as L/LL-type ordinary chondrite. The iron in the olivine is unusually high and the metallic iron is quite low, showing that it has faced oxidizing conditions prior to fall.