Processing of gadolinium–iron garnet under non-equilibrium conditions

We have investigated the mechanosynthesis of gadolinium iron garnet (GdIG) by high-energy ball-milling of 3.(Gd₂O₃)?+?10.(α-Fe) followed by thermal annealing conducted at moderate temperatures (1100 °C). The samples were characterized by X-ray diffraction and Mössbauer spectroscopy in order to determine the influence of the milling time on the final products. For as-milled samples the results revealed the enlargement of the magnetic component belonging to iron and a discrete paramagnetic component. The formation of a garnet phase was observed in all as-annealed samples treated at 1100 °C for 6 h in quantities proportional to the time of grinding the precursors. Evidently, high-energy ball milling of Gd₂O₃?+?α-Fe powders is an important step in GdIG synthesis by a ceramic method. Single-phase garnet is observed for the samples milled for 12 and 24 h treated at 1100 °C for 6 h.     

Size dependence of the magnetic and hyperfine properties of nanostructured hematite (α-Fe 2 O 3 ) powders prepared by the ball milling technique

In this work we present the study of hematite (α-Fe₂O₃) nanostructures synthesized by the ball milling technique. The structural characterization and the crystallite size estimation have been carried out using the X-ray diffraction (XRD) technique. Data analyses indicate that the hematite phase (space group, R-3C) is preserved after the milling process. As the milling time is increased, a second phase (α-Fe) appears. The mean crystallite size shows a decreasing tendency as the milling time is increased. High-resolution transmission electron microscopy (HRTEM) images show the formation of grains composed of crystallites with irregular shapes. Mössbauer spectra of milled powders carried out at 297 and 77 K are well modeled with a histogram distribution of hyperfine fields. The presence of one additional sextet which corresponds to the ∝-Fe phase is also determined in agreement with XRD data analysis. Magnetic measurements suggest the suppression of the Morin transition in the milled samples and the absence of thermal relaxation effects in agreement with the Mössbauer spectroscopy results.     

Laser deposition of iron on graphite substrates

Pulsed laser deposition of iron atoms on graphite substrates was performed to produce iron carbide films. Mössbauer spectra of the sample revealed that iron carbide was produced on the substrate surface and that an α-Fe layer was produced above the iron carbide layer. When the substrate temperature was maintained at 300 K, the iron carbide layer had a hyperfine magnetic distribution because it contained high density of defects. Laser deposition of Fe at 570 K produced cementite Fe₃C with fewer defects due to enhancement of thermal reactions or annealing of the films. The orientation of hyperfine field of the Fe₃C film was parallel to the substrate surface.     

Correlation between microstructure and first-order magnetization reversal in the SmCo5/α-Fe nanocomposite magnets

SmCo₅/α-Fe nanocomposite magnets with different morphology have been fabricated by ball milling of the micrometer sized SmCo₅ and α-Fe powders. The α-Fe grains vary from elongated nano-strips to spherical nanoparticles with increasing milling time. The inter-phase exchange coupling is enhanced with increasing milling time due to reduced grain size. The first-order reversal curves (FORCs) are taken to identify optimal conditions for exchange coupling. It has been found that the stripped morphology results in weak inter-phase exchange coupling, while enhanced exchange coupling is observed with further reduction of the soft-phase grain size. Compared with the measurement of demagnetization curves, FORC analysis provides more information on the magnetostatic as well as the exchange interactions.     

Mössbauer study of products from the arc synthesis of Fe-carbon nanoclusters

This paper presents the results of research into the phase and magnetic state of products of the arc synthesis of Fe-carbon nanoclusters by Mössbauer spectroscopy. These nanoclusters are prepared by the burning of iron-graphite electrodes and carbon-condensate extraction in organic solvents of varying polarity. The local inhomogeneity of the distribution of iron atoms is revealed in the studied samples. It is found that iron atoms are distributed between four iron-containing phases: α-Fe, γ-Fe, FeC _n and iron carbide FeC₂ at different ratios with an accuracy to the resonant absorption factor f. It is shown that the singlet line with a negative chemical shift observed in the Mössbauer spectra of the samples corresponds to the γ-Fe phase and not to iron metallofullerene.     

Study of solid-state reactions and order-disorder transitions in Pd/α-Fe(001) thin films

The formation of the hard-magnetic ordered L1₀-FePd phase in thin bilayer Pd/α-Fe(001) films has been experimentally studied. Solid-state reactions initiated by thermal heating in bilayer Pd/α-Fe(001) films with a thickness of 50–60 nm (the atomic ratio Pd: Fe ≈ 50: 50) separated from the substrate have been studied using the in situ electron diffraction methods. It has been shown that the solid-state reaction between the palladium and iron layers in Pd/α-Fe(001) starts at 400°C with the formation of the disordered Fe-Pd phase. At 480°C, the ordered L1₀-FePd phase is formed. The order-disorder phase transition has been studied. It has been established that the transition of the ordered L1₀-FePd phase to the disordered FePd phase starts at 725°C. At 740°C, only the disordered FePd phase is present over the whole volume of the film. The observed temperature of the order-disorder phase transition is shifted from the equilibrium value by 35°C to higher temperatures. This effect is assumingly associated with the higher concentration of palladium atoms at the boundaries of the Fe-Pd crystal grains owing to the grain-boundary adsorption.     

Density shift and broadening of dipole transitions in antiprotonic helium

The phase composition of carbon nanotubes (CNTs) with encapsulated iron atoms was examined by ⁵⁷Fe M?ssbauer spectroscopy. It was shown that iron atoms were stabilized in thermodynamically stable iron carbide and oxide phases and phases that are not usual under synthesis conditions (γ-Fe and γ-Fe₂O₃).     

Preparation,microstructure, and magnetic properties of a nanocrystalline Nd12Fe82B6 alloy by HDDR combined with mechanical milling

Nanocrystalline Nd₁₂Fe₈₂B₆ (atomic ratio) alloy powders with Nd₂Fe₁₄B/α-Fe two-phase structure were prepared by HDDR combined with mechanical milling. The as-cast Nd₁₂Fe₈₂B₆ alloy was disproportionated via ball milling in hydrogen, and desorption–recombination was then performed. The phase and structural change due to both the milling in hydrogen and the subsequent desorption–recombination treatment was characterized by X-ray diffraction (XRD). The desorption–recombination behavior of the as-disproportionated alloy was investigated by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The morphology and microstructure of the final alloy powders subject to desorption–recombination treatment were observed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), respectively. The results showed that, by milling in hydrogen for 20 h, the matrix Nd₂Fe₁₄B phase of the alloy was fully disproportionated into a nano-structured mixture of Nd₂H₅, Fe₂B, and α-Fe phases with average size of about 8 nm, and that a subsequent desorption–recombination treatment at 760 °C for 30 min led to the formation of Nd₂Fe₁₄B/α-Fe two-phase nanocomposite powders with average crystallite size of 30 nm. The remanence B_r, coercivity H_c, and maximum energy product (BH)_max of such nanocrystalline Nd₁₂Fe₈₂B₆ alloy powders achieved 0.73 T, 610 kA/m, and 110.8 kJ/m³, respectively.     

Magnetic and Structural Properties of the Mechanically Alloyed Nd2(Fe100 − x Nb x )14B System

In this work we report the magnetic and structural properties obtained by Mössbauer spectrometry, Vibrating Sample Magnetometer and X-ray diffraction of milled powders with initial composition Nd₂(Fe_{100 ? x} Nb _x )₁₄B with x = 0 and x = 4. The mixtures were ball milled for different times up to 240 h. Structural and microstructural parameters were derived from high statistics X-ray patterns and discussed as a function of milling time. The Mössbauer spectra of the samples were fitted by means of a sextet and an hyperfine field distribution, associated to a pure iron phase (α-Fe) and a disordered iron-based phase, respectively. The α-Fe grain size decreases from 50 nm for 6 h up to 5 nm for 240 h milling time. The Vibrating Sample Magnetometer results allow to conclude that these samples behave as soft ferromagnets.     

Iron oxide and iron carbide particles produced by the polyol method

Iron oxide (γ-Fe₂O₃) and iron carbide (Fe₃C) particles were produced by the polyol method. Ferrocene, which was employed as an iron source, was decomposed in a mixture of 1,2-hexadecandiol, oleylamine, and 1-octadecene. Particles were characterized using Mössbauer spectroscopy, X-ray diffraction, and transmission electron microscopy. It was found that oleylamine acted as a capping reagent, leading to uniform-sized (12-16 nm) particles consisting of γ-Fe ₂O₃. On the other hand, 1-octadecene acted as a non-coordinating solvent and a carbon source, which led to particles consisting of Fe₃C and α-Fe with various sizes.     

Phase states and magnetic properties of iron nanoparticles in carbon nanotube channels

The structure, phase composition, and magnetic properties of carbon nanotubes filled with iron nanoparticles and obtained by thermolysis of a mixture of ferrocene and C₆₀ fullerene or ferrocene and orthoxylene at a temperature of 800°C are investigated. Electron microscopy, X-ray diffraction, and Mössbauer spectroscopy data lead to the conclusion that carbon nanotubes are multilayer systems partially filled with iron nanoparticles and/or nanorods. Metallic inclusions in nanotube channels form α-Fe, γ-Fe, and Fe₃C phases. The concentration of each phase in the samples is determined. It is shown that 10–20-nm iron clusters in nanotubes exhibit magnetic properties typical of bulk phases of iron. High elasticity of carbon nanotube walls facilitates stabilization of the high-temperature γ-Fe phase; the relative concentration of this phase in a sample can be increased by lowering the concentration of ferrocene in the initial reaction mixture.     

Re-examination of Dronino iron meteorite and its weathering products using Mössbauer spectroscopy with a high velocity resolution

Re-examination of Dronino iron meteorite and products of its weathering in the internal and external surface layers was carried out using Mössbauer spectroscopy with a high velocity resolution. New results showed the presence of α-Fe(Ni, Co), α ₂-Fe(Ni, Co) and γ-Fe(Ni, Co) phases with variations in Ni concentration in Dronino metallic iron alloy. The surface weathering products were supposed as magnetite and/or maghemite, goethite with different particles size and probably ferrihydrite in the internal layer and goethite with different particles size and probably ferrihydrite in the external layer.     

Comparative study of Aliskerovo,Anyujskij, Sikhote-Alin and Sterlitamak iron meteorites using Mössbauer spectroscopy

A comparative study of Sikhote-Alin IIAB, Anyujskij IIAB, Aliskerovo IIIE-an and Sterlitamak IIIAB iron meteorites was carried out using Mössbauer spectroscopy with a high velocity resolution as well as using metallography, scanning electron microscopy with energy dispersive spectroscopy and X-ray diffraction. Different numbers of spectral components were found in the Mössbauer spectra of Sikhote-Alin IIAB and Anyujskij IIAB and in the spectra of Aliskerovo IIIE-an and Sterlitamak IIIAB iron meteorites. The values of hyperfine field at the ⁵⁷Fe nuclei obtained for spectral components were related to α-Fe(Ni, Co), α ₂-Fe(Ni, Co) and γ-Fe(Ni, Co) phases with variations in Ni concentration.     

Local atomic and magnetic structures of nanocrystalline Fe75Cr10B15 alloy

The crystal, local atomic and magnetic structures of Fe₇₅Cr₁₀B₁₅ alloys annealed at 440?C473°C for 5 min have been studied using X-ray diffraction and ⁵⁷Fe M?ssbauer spectroscopy. At the annealing temperature T _a = 440°C, nanocrystals of the ??-Fe phase (??1%) precipitate in the amorphous matrix of the alloy. The complete crystallization of the amorphous alloy occurs at T _a = 473°C with the formation of ??-Fe nanocrystals 26 ± 2 nm in size and nanocrystals of tetragonal boride t-Fe₃B 47 ± 2 nm in size. It has been found that chromium atoms are located in nanocrystals of the ??-Fe and y-Fe₃B types. The distribution functions of hyperfine fields in the nanocrystalline Fe₇₅Cr₁₀B₁₅ alloy reconstructed from the M?ssbauer spectra (at T _a = 473°C) show that there are three allowed states of iron atoms in the ??-Fe phase and three equally probable crystallographic nonequivalent states of iron in the t-(Fe,Cr)₃B phase. The chromium concentration x in the ??-Fe(Cr) phase is found to be ??10 at %. The substitution of chromium atoms for iron atoms in t-Fe₃B substantially decreases local magnetic moments of the iron atoms.     

In situ Mössbauer spectroscopic study of iron III chloride intercalated in graphite under reaction conditions

In situ⁵⁷Mössbauer spectroscopy has been used to study the process of reduction and Fischer-Tropsch reactions on FeCl₃ intercalated in graphite layers. It is found that on flowing H₂ on graphite intercalated by FeCl₃ at 400° C, FeCl₃ converts to FeCl₂ and partly to small particles of α-Fe. The Mössbauer spectra of the reduced sample are superposition of a sextuplet and two quadrupole doublets indicative of metallic iron and two species of FeCl₂. However, at room temperature and at 400° C for a short period of reduction the magnetic hyperfine splittings (ca. 295 kOe and 262 kOe respectively) are smaller than the corresponding parameters for bulk metallic iron. The differences have been attributed to the interaction between the monolayers of iron atoms and the carbon nets of the graphite support. When the reduction was carried out for a longer period, α-Fe was formed. When a sample reduced for a short period of time is heated at 400°C in the presence of the synthesis gas, part of the iron particles sinter, and α-iron is observed. On heating the above sample once again at 400°C in the presence of the synthesis gas, the remaining small particles of iron are totally converted to the bulk phase (α-Fe). Experimental observations indicate that α-Fe and FeCl₂ are present on the surface as well as inbetween the intercalated graphite layers.     

Hyperfine interactions in metal extracted from ordinary chondrite Tsarev L5: A study using Mössbauer spectroscopy with high-velocity resolution

For the first time, a study of hyperfine interactions in metal grains extracted from ordinary chondrite Tsarev L5 was done using Mössbauer spectroscopy with high-velocity resolution. Three magnetic (sextets) and one paramagnetic (singlet) components were revealed in the Mössbauer spectrum of extracted metal. The evaluated values of the magnetic hyperfine field were 332.5, 335.4 and 347.2 kOe. On the basis of Mössbauer parameters and metallographic data, the magnetic components were related to the α-Fe(Ni, Co), α′-Fe(Ni, Co) and α₂-Fe(Ni, Co) phases of Fe(Ni, Co) alloy, while the paramagnetic singlet was related to the γ-Fe(Ni, Co) phase.     

Investigation of structure and magnetic properties of the as-deposited and post-annealed iron nitride films by reactive facing-target sputtering

Structure and magnetic properties of the as-deposited and post-annealed iron nitride films have been investigated systematically. A series of phases containing α-Fe, ?-Fe₃N, ξ-Fe₂N and γ″-FeN were obtained as nitrogen flow rate (FN₂) increases from 0.5 to 30 sccm. An increase of the nitrogen concentration in the as-deposited films could be concluded from the phase transition with the increasing FN₂. After being annealed, some of the iron nitride phases are decomposed and γ′-Fe₄N appears in the films. The magnetic characteristics are dependent on FN₂, which can be ascribed to the facts that the nitrogen in the films turns the valence states of Fe into Fe⁺ or Fe^dipole with high magnetic momentum or ever H-like bond Fe^+/dipole with low magnetic momentum based on the bond-band-barrier correlation mechanism.     

Multi-walled carbon nanotubes formed by condensed-phase conversions of Fe-C-based nanopowder in vacuum

We describe the formation of multi-walled carbon nanotubes (MWCNTs) which have grown during annealing at 800 °C of Fe-C-based nanopowder in vacuum. The Fe-C-based nanopowder was produced by a laser pyrolysis of gas-phase reactants. The as-synthesized and annealed samples were characterised by TEM, XRD, Mössbauer spectroscopy, Raman spectroscopy, and magnetic measurements. Under the TEM, MWCNTs were observed in the annealed sample. In addition, larger particles with the graphitic shells and various graphitic structures were found. XRD and Mössbauer analysis confirmed that only two iron phases were present in the annealed sample: α-Fe and Fe₃C. Phase transformations taking place during the thermal treatment of the sample are discussed.     

Structure and phases of low-neodymium NdFeB permanent magnets

Structures and phase compositions of two low-neodymium magnetically hard materials, differing by the way of preparation — centrifugal atomization and melt spinning — were compared using Mössbauer spectroscopy, X-ray diffraction and measurements of thermomagnetic curves. Better hard magnetic characteristics of the melt-spun material are explained on the basis of the differences in the content of surface and/or interface Fe(Nd,B) phases. Their remarkable presence in the centrifugally atomized material lowers the content of Fe₃B, Fe₂B, α-Fe, and Nd₂Fe₁₄B phases that are responsible for the magnetic quality of the material. There are only subtle differences in the phase compositions of both materials after thermomagnetic measurement, where the α-Fe phase prevails as a product of the thermal decomposition.     

Fe-doped TiO2 prepared by mechanical alloying

The effect of different milling conditions on the formation of Fe-doped TiO₂ powders by mechanical alloying was investigated by Mössbauer spectrometry. The milling conditions investigated were ball to powder weight ratio, milling time, rotation velocity of supporting disc, and the type of starting reactive iron and its concentration. X-ray diffraction shows that high energy mechanical milling of undoped anatase TiO₂ induce the anatase to rutile phase transformation via high pressure srilankite. Mössbauer spectra for the majority of the doped samples were decomposed into one sextet and one or two doublets. The sextets was attributed to the presence of α-Fe or hematite impurities. The doublets were assigned to Fe^3?+? incorporated in the TiO₂ structure, and to the Fe^2?+? located either at the surface or the interstitial sites of TiO₂. A greater incorporation of Fe in the TiO₂ structure was observed when samples were prepared from hematite instead of α-Fe.