Study of magnetic phases in mechanically alloyed Fe50Zn50 powder

The mechanosynthesis of Fe₅₀Zn₅₀ alloy resulted in the formation of the bcc Fe(Zn) solid solution after 20 h of milling. Structural transformations induced by mechanical alloying and heating, and magnetic properties of the powders were studied by Mössbauer spectroscopy, X-ray diffraction, Faraday balance and vibrating sample magnetometry techniques. All alloys studied exhibit strong magnetic ordering with Curie temperatures close to 900 K. Room temperature Mössbauer measurements revealed distinguished magnetic environments in the samples. The decrease of coercivity with prolonged milling time was attributed to the reduction or averaging of local magnetic anisotropies.     

Mössbauer effect study of fine atomic structure of Fe50Al40Ni10 powders

In the present paper, we discuss the local atomic environment of Fe atoms in the mechanically alloyed Fe₅₀Al₄₀Ni₁₀ powders on the basis of hyperfine data estimated from ⁵⁷Fe Mössbauer spectra. B_hf decreases with increasing milling time due to the diffusion of Al and/or Ni into Fe grains. Nickel atoms did not diffuse inside the first coordination sphere of Fe and if the diffusion takes place the number is not more than one atom. Analyses of P(B_hf), indicate that the high hyperfine field values ranging from 30 to 33 T have to be partially attributed to Fe crystalline nanograins and the presence of the defects in them, the hyperfine field values ranging from 15 to 30 T can be associated to the nanocrystalline bcc Fe(Al, Ni) solid solution while the low hyperfine field values (<15 T) result from Fe atoms located in the disordered grain boundaries.     

Low temperature study of micrometric powder of melted Fe50Mn10Al40 alloy

Melted Fe₅₀Mn₁₀Al₄₀ alloy powder with particle size less than 40 μm was characterized at room temperature by XRD, SEM and XPS; and at low temperatures by Mössbauer spectrometry, ac susceptibility, and magnetization analysis. The results show that the sample is BCC ferromagnetic but with a big contribution of paramagnetic sites, and presents super-paramagnetic and re-entrant spin-glass phases with critical temperatures of 265 and 35 K, respectively. The presence of the different phases detected is due to the disordered character of the sample and the competitive magnetic interactions. The obtained values of the saturation magnetization and the coercive field as a function of temperature present a behavior which indicates a ferromagnetic phase. However, the behavior of the FC curve and that of the coercive field as a function of temperature suggest that the dipolar magnetic interaction between particles contributes to the internal magnetic field in the same way as was reported for nanoparticulate powders.     

Evolution of structure, microstructure and hyperfine properties of nanocrystalline Fe50Co50 powders prepared by mechanical alloying

Nanostructured Fe₅₀Co₅₀ powders were prepared by mechanical alloying of Fe and Co elements in a vario-planetary high-energy ball mill. The structural properties, morphology changes and local iron environment variations were investigated as a function of milling time (in the 0-200 h range) by means of X-ray diffraction, scanning electron microscopy (SEM), energy dispersive X-ray analysis and ⁵⁷Fe Mössbauer spectroscopy. The complete formation of bcc Fe₅₀Co₅₀ solid solution is observed after 100 h milling. As the milling time increases from 0 to 200 h, the lattice parameter decreases from 0.28655 nm for pure Fe to 0.28523 nm, the grain size decreases from 150 to 14 nm, while the meal level of strain increases from 0.0069% to 1.36%. The powder particle morphology at different stages of formation was observed by SEM. The parameters derived from the Mössbauer spectra confirm the beginning of the formation of Fe₅₀Co₅₀ phase at 43 h of milling. After 200 h of milling the average hyperfine magnetic field of 35 T suggests that a disordered bcc Fe-Co solid solution is formed.     

Influence of milling time on the structural, microstructural and magnetic properties of mechanically alloyed Ni58Fe12Zr10Hf10B10 nanostructured/amorphous powders

This paper investigates structural, microstructural and magnetic properties of amorphous/nanocrystalline Ni₅₈Fe₁₂Zr₁₀Hf₁₀B₁₀ powders prepared by high energy milling. Ball milling of Ni, Fe, Zr, Hf and B leads to alloying of the element powders at 120 h. The results show that at 190 h the amorphous content is at the highest level and the grain size is about 2 nm. The magnetic measurements reveal that the coercivity and the saturation magnetization reach about 20 Oe and 30 emu/g at 190 h and become approximately 5 Oe and 40 emu/g after a suitable heat treatment, respectively.     

Crystallization kinetics of the Fe40Ni38Mo4B18 amorphous alloy

X-ray diffraction (XRD) and Mössbauer spectroscopy were used to study the annealing of the Fe₄₀Ni₃₈Mo₄B₁₈ amorphous alloy. The samples were isothermally annealed in the 858–878 K temperature range several times. Two crystalline phases were observed in the annealed samples: FeNi₃ and (Fe, Ni, Mo)₂₃B₆. Preliminary results indicate that assuming a linear relationship between the area under the main XRD peak associated with the FeNi₃ phase and its volume fraction, this can be fitted to a Johnson–Mehl–Avrami equation with an exponent n close to 1.0. Mössbauer results show a broad magnetic hyperfine field distribution in as-received samples and, consistent with XRD results, a sextet attributed to precipitates of FeNi₃ (B_hf=29.5 T) for long annealing times.     

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.     

Structural and magnetic properties of Co50Ni50 powder mixtures

In the present work, morphological, structural, thermal and magnetic properties of nanocrystalline Co₅₀Ni₅₀ alloy prepared by high energy planetary ball milling have been studied by means of scanning electron microscopy, X-ray diffraction, and differential scanning calorimetry. The coercivity and the saturation magnetization of alloyed powders were measured at room temperature by a vibration sample magnetization. Morphological observations indicated a narrow distribution in the particle and homogeneous shape form with mean average particle size around 130 μm². The results show that an allotropic Co transformation hcp→fcc occurs within the three first hours of milling and contrary to what expected, the Rietveld refinement method reveals the formation of two fcc solid solutions (SS): fcc Co(Ni) and Ni(Co) beside a small amount of the undissolved Co hcp. Thermal measurement, as a function of milling time was carried out to confirm the existence of the hcp phase and to estimate its amount. Magnetic measurement indicated that the 48 h milled powders with a steady state particles size have the highest saturation (105.3 emu/g) and the lowest coercivity (34.5 Oe).     

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.     

Characterization of nanocrystalline FeSiCr powders prepared by ball milling

FeSi₁₀Cr₁₀ powder was mechanically alloyed by high energy planetary ball milling, starting from elemental powders. The microstructural and magnetic properties of the milled powders were characterized by scanning electron microscopy, X-ray diffraction, ⁵⁷Fe Mössbauer spectrometry and a vibratory sample magnetometer.After 3 h of milling, the formation of two bcc solid solutions α-Fe₁ (Si, Cr) and α-Fe₂ (Si, Cr) is observed. Their grain sizes decrease with increase in milling time attaining, at 15 h of milling, 23 and 11 nm, respectively. Mössbauer spectra of the milled powder show the presence of two components. One is a ferromagnetic type with a broad sextuplet. Its distribution of hyperfine field is characterized by high and low hyperfine field’s peaks and a mean value of 26.5 T. The other is a single paramagnetic peak. Its low concentration increases to ∼4% at 15 h of milling. These results can be explained by different atomic environments affected by Si or/and Cr elements, as well as the increased disordered grain boundaries.Magnetic measurements of the milled FeSi₁₀Cr₁₀ alloy powder exhibit a soft ferromagnetic character with a decrease of both magnetization at saturation (Ms) and coercive force (Hc) with milling time attaining values of Ms=151 emu/g and Hc=2500 A/m at 30 h of milling time.     

Sn Mössbauer spectroscopy of Gd0.8L0.2Mn6Sn6 and Tb0.8L0.2Mn6Sn6 compounds (L=Sc,Y, Lu)

The HfFe₆Ge₆-type compounds Gd_0.8L_0.2Mn₆Sn₆ and Tb_0.8L_0.2Mn₆Sn₆ (L = Sc, Y, Lu) have been studied by ¹¹⁹Sn Mössbauer spectroscopy. The values of the apparent quadrupolar splitting clearly evidence the easy plane magnetization of the gadolinium compounds and the easy axis one in the terbium compounds. The three tin sites behave differently with the nature and size of the substituting L element. For a given series, the hyperfine field of the Sn_2d site is almost unchanged whatever the size of the L element. The hyperfine field of the Sn_2e site strongly varies with the L size in relation with atomic displacements. The hyperfine field of the Sn_2c site exhibits a more complicated behavior. The field difference in the easy plane and easy axis compounds confirms the angle-dependent anisotropic contribution of the Mn moment to the hyperfine field. The analysis of the results also suggests the play of angle-dependent contributions arising from the rare earth moment.     

α-Fe2O3-In2O3 mixed oxide nanoparticles synthesized under hydrothermal supercritical conditions

α-Fe₂O₃-In₂O₃ mixed oxide nanoparticles system has been synthesized by hydrothermal supercritical and postannealing route, starting with (1−x)Fe(NO₃)₃·9H₂O·xIn(NO₃)₃·5H₂O aqueous solution (x=0-1). X-ray diffraction and Mössbauer spectroscopy have been used to study the phase structure and substitutions in the nanosized samples. The concentration regions for the existence of the solid solutions in the α-Fe₂O₃-In₂O₃ nanoparticle system together with the solubility limits of In³⁺ ions in the hematite lattice and of Fe³⁺ ions in the cubic In₂O₃ structure have been evidenced. In general, the substitution level is considerably lower than the nominal concentration x. A justification of the processes leading to the formation of iron and indium phases in the investigated supercritical hydrothermal system has been given.     

Step-shape angular spin distribution in layered systems by Fe Mössbauer spectroscopy: A general treatment

In the so-called ‘step-shape’ angular spin distribution model for layered systems, the non-collinear directions of the atomic magnetic moments are confined to the film plane and form a homogeneous fan spanning inside an (in-plane) angular interval Δφ centered at an angle φ₀. A general approach for deriving the two parameters φ₀ and Δφ via ⁵⁷Fe Mössbauer spectroscopy measurements is discussed. The analysis extends our previously reported treatment, which assumed that the angular aperture Δφ develops symmetrically versus a fixed direction φ₀ (e.g., the in-plane easy axis of magnetization) oriented either along or perpendicular to the in-plane projection of the Mössbauer γ-ray direction. The proposed approach is also applicable for those cases when not only the spin aperture Δφ is changing but also the aperture center φ₀ is rotating under the influence of different external parameters, such as applied field, temperature, stress, etc. The method is suitable for applications to nanoscale layered heterostructures with in-plane uniaxial or unidirectional magnetic anisotropy. The method is applied to experimental data obtained on a 2-nm thick defected Fe layer with in-plane magnetic texture.     

Hydrothermal synthesis and structural characterization of (1−x)α-Fe2O3-xSnO2 nanoparticles

Structural and morphological characteristics of (1−x)α-Fe₂O₃-xSnO₂ (x=0.0-1.0) nanoparticles obtained under hydrothermal conditions have been investigated by X-ray diffraction (XRD), transmission Mössbauer spectroscopy, scanning and transmission electron microscopy as well as energy dispersive X-ray analysis. On the basis of the Rietveld structure refinements of the XRD spectra at low tin concentrations, it was found that Sn⁴⁺ ions partially substitute for Fe³⁺ at the octahedral sites and also occupy the interstitial octahedral sites which are vacant in α-Fe₂O₃ corundum structure. A phase separation of α-Fe₂O₃ and SnO₂ was observed for x≥0.4: the α-Fe₂O₃ structure containing tin decreases simultaneously with the increase of the SnO₂ phase containing substitutional iron ions. The mean particle dimension decreases from 70 to 6 nm, as the molar fraction x increases up to x=1.0. The estimated solubility limits in the nanoparticle system (1−x)α-Fe₂O₃-xSnO₂ synthesized under hydrothermal conditions are: x≤0.2 for Sn⁴⁺ in α-Fe₂O₃ and x≥0.7 for Fe³⁺ in SnO₂.     

Mössbauer study of local environment effects in the ordered Fe70Al30 Invar alloy: Temperature dependence of isomer shift in the spin-glass phase

The systematic studies of the magnetic hyperfine field distribution for ⁵⁷Fe in the spin-glass (SG) phase of the ordered Fe₇₀Al₃₀ Invar alloy have been performed using Mössbauer spectroscopy technique in the temperature range from 5 to 80 K. Particular emphasis has been placed on the low-field component of the distribution, which is considered as corresponding to the Fe sites in the SG magnetic configurations. The main result is the observation of the pronounced temperature dependence of isomer shift for several atomic SG configurations. The temperature behavior of the local electron density is strongly correlated to the Invar properties of the Fe₇₀Al₃₀ alloy. We argue that the observed temperature dependence of the isomer shift due to a local volume effect. The temperature range, for which the pronounced decrease in atomic volume is observed, coincides with the range of the existence of the Invar effect. The influence of the competition between opposite in sign exchange interactions on the Invar properties is discussed.     

Effect of Fe substitution on multiferroic hexagonal YMnO3

Polycrystalline YMn_1−xFe_xO₃ (x=0.02-0.20) powders were synthesized by means of modified citrate method. Powder X-ray diffraction gives evidence that all the samples are single phase and exhibit hexagonal structure with P6₃cm space group as observed for YMnO₃. The solubility limit of Fe was determined as about 6 wt.%. Cell parameter values were found to increase with Fe content, since Fe³⁺ and Mn³⁺ have the same ionic radii. This can be attributed to the increase of the tilting of MnO₅ bipyramid and the buckling of Y atoms. In addition, ⁵⁷Fe Mössbauer spectrometry provides evidence of two Fe³⁺ sites attributed to two different nearest atomic neighbours. Magnetic properties reveal a paramagnetic-to-antiferromagnetic transition, a possible increase of the magnetic anisotropy, and a competition between ferromagnetic and antiferromagnetic interactions.     

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.