Chemical reduction of hematite by sodium borohydride

Well-crystallized hematite was suspended in water and treated at room-temperature (RT) with sodium borohydride. The product of the reaction is a highly magnetic black powder, which is stable at RT. The NaBH₄ treatment converts about half of the hematite to an amorphous Fe–B alloy and to a small fraction of sub-micron sized, amorphous metallic-Fe nodules. Heating at 400°C of this composite has resulted in the crystallization and/or oxidation of more than half of the amorphous Fe–B phase to α-Fe and Fe₃O₄ and B₂O₃, respectively. After treatment at 800°C, the metallic Fe and the amorphous Fe–B have completely vanished, and the resulting product consists of hematite and FeBO₃ embedded in the matrix of α-Fe₂O₃.     

NMR study of rapidly quenched crystalline and amorphous Fe-B alloys

Amorphous and microcrystalline Fe-B alloys (4–25 at % B) obtained by rapid quenching of the melt were studied using the pulsed nuclear magnetic resonance (NMR) of ¹¹B nuclei at 4.2 K. Alloy samples were prepared from both a natural isotope mixture and a mixture of the ⁵⁶Fe and ¹¹B isotopes. The NMR spectra were measured as a function of the boron content. The maximum hyperfine fields at the ¹¹B nuclei sites are 25–29 kOe and overlap the values of the hyperfine fields at the ¹¹B nuclei sites in the tetragonal and orthorhombic Fe₃B phases and also in the α-Fe phase containing boron as a substitutional impurity. The short-range order and local atomic structure of the amorphous Fe-B alloys were determined. The amorphous alloys are found to consist of microregions (clusters) with a short-range order similar to that in the tetragonal or orthorhombic Fe₃B phase or the α-Fe phase.     

Mössbauer study of ultrafine amorphous Fe−B alloys

The chemical composition of ultrafine amorphous Fe−B powders prepared by a chemical reduction depends on the mixed molar ratio of KBH₄ to Fe ions. We propose the following reaction processes for the formation of ultrafine Fe−B powders: (1) 4Fe²⁺+2BH₄₋+6OH⁻→2Fe₂B+6H₂O+H₂ and (2) 4Fe²⁺+2BH₄₋+7OH⁻→2Fe₃B+Fe+BO₂+5H₂O+5/2H₂.     

<Superscript>57</Superscript>Fe NMR study of amorphous and rapidly quenched crystalline Fe-B alloys

Amorphous and crystalline Fe-B alloys (5–25 at % B) were studied using pulsed ⁵⁷Fe nuclear magneticr esonance at 4.2 K. The alloy samples were prepared from a mixture of the ⁵⁷Fe and ¹⁰B isotopes by rapid quenching from the melt. In the microcrystalline Fe-(5–12 at %) B alloys, the resonance frequencies were measured for local states of ⁵⁷Fe nuclei in the tetragonal and orthorhombic Fe₃B phases and also in α-Fe. The resonance frequencies characteristic of ⁵⁷Fe nuclei in α-Fe crystallites with substitutional impurity boron atoms in the nearest neighborhood were also revealed. In the resonance frequency distribution P(f) in the amorphous Fe-(18–25) at % B alloys, there are frequencies corresponding to local Fe atom states with short-range order of the tetragonal and orthorhombic Fe₃B phases. As the boron content decreases below 18 at %, the P(f) distributions are shifted to higher frequencies corresponding to ⁵⁷Fe NMR for atoms exhibiting a short-range order of the α-Fe type. The local magnetic structure of the amorphous Fe-B alloys is also considered.     

Silicon and transition metal-silicides implanted with57Fe

Si(111) single crystals were implanted with⁵⁷Fe in a broad dose range in order to overlap the concentration range of bulk amorphous Fe _x Si_1−x samples. At high (≥10¹⁶ atoms/cm²) doses the measured hyperfine interaction values were found to be the same as in the bulk amorphous samples, suggesting the same Fe−Si bonding and a very similar structure for the two amorphous phases produced by different methods. A comparison of the isomer shift (δ) and quadrupole splitting (ΔE) values with the values of the stoichiometric crystalliine phases showed the same δ but different δE values indicating similar Fe−Si bonding but different atomic arrangement around the iron atom.     

Local structure of amorphous and microcrystalline Fe-B alloys

Amorphous and microcrystalline Fe-B alloys in the composition range (4–25) at % B, fabricated by melt spinning, were investigated by pulse nuclear magnetic resonance (NMR) on ¹¹B nuclei at 4.2 K. Alloy samples were prepared both from a natural mixture of isotopes and an isotope mixture ⁵⁶Fe-¹¹B. The NMR spectra were measured at different boron contents. The local atomic structure of amorphous Fe-B alloys has been determined. The amorphous alloys consist of microregions (clusters) with short-range order of the tetragonal and orthorhombic Fe₃B-phase types, as well as of the α-Fe type.     

Relevance of Fe atomic volumes for the magnetic properties of Fe-rich metallic glasses

The atomic volume V_a-Fe that can be assigned to Fe atoms in Fe–metalloid (Fe–MD) and Fe–early transition metal (Fe–TE) glasses was deduced in a previous paper (I. Bakonyi, Acta Materialia 53 (2005) 2509) from an analysis of available density data for such amorphous alloys. In the present paper, based on a similarity of the amorphous and face-centered cubic (fcc) structures, the distinctly different magnetic behaviors of these two families of amorphous alloys are discussed in terms of the relative position of V_a-Fe and the critical volume V_fcc?-Fe≈11.7 Å³/atom separating the so-called low-spin (LS) and high-spin (HS) state of fcc-Fe. For Fe–MD systems, V_a-Fe is found to be definitely larger than V_fcc*-Fe whereas for Fe-TE systems V_a-Fe is fairly close to V_fcc*-Fe. Since in topologically disordered alloys a distribution of atomic volumes is inherently present, in Fe–MD glasses the Fe atoms can be assumed to exhibit exclusively the HS state whereas in Fe–TE amorphous alloys a comparable fraction of Fe atoms can be either in the LS or the HS state. According to previous theoretical band structure calculations, an antiferromagnetic state can also be stable just around V_fcc*-Fe. The simultaneous presence of Fe atoms with such a rich variety of magnetic states due to the specific position of the average of the atomic volume distribution can well explain the complex magnetic behavior observed in Fe-rich Fe–TE metallic glasses such as, e.g., in amorphous Fe–Zr alloys around 90 at% Fe.     

Short-range order in amorphous ferromagnetic Fe-B alloys

Amorphous and quenched crystalline Fe-B alloys in the composition range of 4–25 at % B were prepared by melt spinning and investigated by ⁵⁷Fe Mössbauer spectroscopy at T = 87 K. The states of iron atoms in the α-Fe phases, including iron atoms having boron atoms in the nearest coordination sphere, and in the orthorhombic (o) and tetragonal (T) Fe₂B phases are detected in the microcrystalline alloys. The short-range order and the local atomic structure of the amorphous Fe-B alloys are determined. The amorphous alloys consist of microregions (clusters) with short-range order of the t- and o-Fe₂B and α-Fe types. The dependence of the content of various types of clusters on the alloy composition is quantitatively estimated.     

Hyperfine field relaxations in the Fe−Co−B amorphous alloys

A systematic increase of the average hyperfine magnetic induction at⁵⁷Fe measured at room temperature during interrupted isothermal annealing was found to be inherent to the irreversible relaxation processes in the Fe−B based soft magnetic alloys at moderately elevated temperatures. Assuming superimposed asymptotic exponential field vs. time dependences. several processes can be distinguished, their relaxation times determined and from the Arrhenius-like log τ vs. 1/T plots average activation enthalpies estimated. Results on the Fe₇₀Co₁₀B₂₀ and Fe_85−x Co _x B₁₅ (x=17, 19 and 21 at. % Co) amorphous ribbons between 100 and 200°C are compared and discussed in terms of possible stress relief, free volume annihilation and short range ordering mechanisms.     

Measurement of the spindependent relative conversion coefficients in α-Fe and α-Fe2O3

The relative differences δ _ns (n=1, 2, 3) of the spindependent conversion coefficients were measured for α-Fe and α=Fe₂O₃. In contrast to theoretical predictions of δ_1s≃−10⁻⁵ we found δ_1s≃−1.0(4)x10⁻² for both α-Fe and α-Fe₂O₃. As a possible source for this difference we consider a dynamic coupling with the atomic spin during the conversion process.     

On the determination of the volume fraction of the crystalline phase in amorphous-crystalline alloys

The possibility of determining volume fractions of crystalline and amorphous phases of partially crystalline alloys from X-ray diffraction data has been discussed. The crystallization of an amorphous microwire of the Fe_73.9B_13.2Si_10.9C₂ composition has been investigated. The crystallization leads to the formation of α-Fe and Fe(Si). An analysis has been made of the X-ray diffraction patterns recorded for a series of samples with different contents of the crystalline and amorphous phases. The angular range has been determined and the calibration graph has been constructed, which can be used to determine the volume fractions of the amorphous and crystalline components in amorphous-crystalline samples.     

Mössbauer emission and absorption studies on the reduction behaviour of supported Co,Co−Mo,Fe and Fe−Mo hydrotreating catalysts

In carbon-supported Fe−Mo catalysts an Fe−Mo alloy can be formed during reduction in H₂ at 673 K. In carbon-supported Co−Mo catalysts, instead of the formation of a Co−Mo alloy segregation of metallic Co is observed. In alumina-supported Fe and Fe−Mo catalysts, the interaction between the alumina support and the catalyst particles hinders reduction of the ions to an Fe⁰ phase. Most probably a surface “Fe(II)-aluminate” is formed.     

Local structure of Fe70Cr15B15 X-ray amorphous alloy

The local atomic and magnetic structure of Fe₇₀Cr₁₅B₁₅ X-ray amorphous alloy is studied by means of ¹¹B nuclear magnetic resonance (NMR) and ⁵⁷Fe Mössbauer spectroscopy. It is determined that Fe₈₅B₁₅ and Fe₇₀Cr₁₅B₁₅ X-ray amorphous alloys consist of microregions (nanocrystals) with short-range orders of t-Fe₃B and α-Fe phases. It was found out that chromium atoms in the Fe₇₀Cr₁₅B₁₅ X-ray amorphous alloy are evenly distributed in these two nanocrystals, forming t-(Fe,Cr)₃B and α-Fe(Cr) phases.     

Hyperfine interactions in ultrafine amorphous Fe−M−B (M=Ni,Co) alloys

Ultrafine amorphous (Fe, Co, Ni) B powders have been prepared by a chemical reduction method. The influence of the Co and Ni atoms on the distribution of internal magnetic fields P(B_hf) has been investigated. The quadrupole splitting distribution P(QS) of ultrafine amorphous Fe−Ni−B powders has a form similar to that derived for the dense random packing of atoms.     

Low temperature thermal annealing-induced α-FeSi2 derived phase in an amorphous Si matrix

Thermal annealing-induced recrystallisation in Fe ion-implanted Si was investigated by transmission electron microscopy. Single crystals of Si(111) were implanted with 120 keV Fe ions to a fluence of 1.0×10¹⁷ cm^-2 at cryogenic temperature. A buried amorphous Fe-Si layer in an amorphous Si matrix was formed in the as-implanted sample. Nanobeam electron diffraction revealed that metastable α-FeSi₂ precipitates embedded in the amorphous Si matrix were formed after annealing at 350 °C for 8 h. The formation of this α-FeSi₂-derived phase was unusual, because it has been observed only in epitaxially grown thin films. Based on the Fe_1-xSi (0<x<0.5) phase with the CsCl structure, which is another metastable phase in the Fe-Si binary system, we discuss the formation process of the metastable α-FeSi₂ in the amorphous matrix. PACS 61.43.Dq; 61.14.Lj; 61.80.Jh     

Near-ordering structural transitions in amorphous metal alloys

The temperature variations in the modulus of elasticity (Young’s modulus) E and internal friction Q ⁻¹ of the amorphous metal alloys Ti₅₀Cu_50−x Ni_x (5⩽x⩽20) are studied at temperatures of 300–800 K. There is an anomalous increase in E(T) at temperatures above T _x (which varies from 440 to 525 K, depending on the composition). When the amount of nickel in the alloy is high (x>12 at. %), a small peak shows up in Q ⁻¹(T). These effects are related to structural transitions in near-ordering regions (clusters). A model for structural relaxation of near ordering in amorphous alloys is proposed on the basis of these experiments. Fiz. Tverd. Tela (St. Petersburg) 40, 389–392 (March 1998)     

Crystallization kinetics of the Fe−Co−B amorphous alloys

A series of amorphous ribbons Fe_85−x Co _x B₁₅ was subjected to the isothermal crystallization annealing. The alloys forx=12, 15, 17, 19, 21, 23, and 25 at.% Co were measured at room temperature by standard transmission technique during interrupted annealing. The samples with 12 and 21 at.% Co were used for direct scanning at constant velocity of the outermost metallic peak. In both cases gradually increasing content of the metallic Fe−Co phase was observed in at least two stages. Several scanning temperatures applied with the 12 and 21 at.% Co samples made it possible to draw the Arrhenius plots and to estimate the activation enthalpies of the processes. By analysing the Avrami exponents and activation enthalpies, the first process is attributed to a comparatively fast primary Fe−Co crystallization followed by the transformations of the amorphous rest.     

Mössbauer study of Fe-B alloys containing Nd additives

The influence of a few percent neodynium additives to Fe-B alloy on the hyperfine parameters was investigated. It was found that Nd decreases the hyperfine field of amorphous Fe-B alloys. The samples annealed at temperatures between 600°C and 700°C contain α-Fe and Fe₃B phases. The average hyperfine field of Fe₃B phase increases with increasing Nd content and decreases with increasing annealing temperature. The average isomer shift of Fe₃B phase decreases with increasing Nd content. The experimental data show that the change of hyperfine parameters of the Fe₃B phase in the studied alloys is due to Nd atom.     

Stable and metastable phases in Nd−Fe binary alloys

Melt-spinning Nd _x Fe_100-x alloys over a wide composition range: 10≤x≤90, has lead to the identification of three metastable phases. Two of these correspond to phases which are stable in late rare earth-iron alloy systems, the third is related to the fcc grain boundary phase observed in sintered Nd−Fe−B permanent magnets. Structural and magnetic data are presented.     

Nuclear Spin-Lattice Relaxation of 82BrFe

The field dependence of the nuclear spin-lattice relaxation (SLR) of cold implanted ⁸²Br (T ≤ 25 mK) in α-Fe single crystals was investigated with nuclear magnetic resonance of oriented nuclei (NMR/ON) at low temperatures as experimental technique. The SLR at the lattice sites with the hyperfine fields found by earlier NMR/ON experiments was measured as a function of the applied external magnetic field B _ext parallel to the three principle axes [100], [110] and [111] of the iron single crystal. The data were evaluated with the full relaxation formalism in the single impurity limit and for comparison also with the often employed model of a single exponential function with an effective relaxation time T ₁′. With a phenomenological model the high field values of the relaxation rates r _{∞, [100]′} = 6.6(2) · 10⁻¹⁵ T²sK⁻¹, r _{∞, [110]} = 5.4(2) · 10⁻¹⁵ T²sK⁻¹ and r _{∞, [111]} = 5.2(1) · 10⁻¹⁵ T²sK⁻¹ were obtained.