The influence of Cu and Nb on the crystallization products of annealed FeCuNbSiB

Depending on different Nb and Cu concentration, we studied the formation of nano- and microcrystalline phases in differently annealed samples of FeCuNbSiB. First, the kinetics of crystallization was explored by measuring the temperature-dependent electrical resistivity and magnetization. After this, we collected Mössbauer spectra and did an X-ray diffraction analysis of annealed samples at chosen temperatures to discover the different crystalline phases. It was found how the onset of crystallization had been shifted towards other temperatures. The analysis of Mössbauer spectra shows that building up the well-known DO₃ structure of Fe₃Si is disturbed in the alloy without Cu. At higher Nb content, we resolve two different crystallization steps in the formation of Fe₃Si and a new crystalline phase, probably being a structure like Fe₂₃B₆.     

Kinetics of ordering in Fe3Si

Alloys of Fe₃Si were prepared as disordered bcc solid solutions by mechanical alloying. Chemical disorder D0₃ order transformations were studied by Mössbauer spectrometry and X-ray diffractometry. The evolution of short- and long-range order parameters showed that ordering probably occurs heterogeneously by nucleation and growth.     

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.     

Mössbauer study of the structure of amorphous invar and a two-level model of the expansion anomaly

The methods of Mössbauer spectroscopy and dilatometry are used to study the local atomic structure and thermal expansion of amorphous invar alloy Fe₈₃B₁₇. It is assumed that the alloy contains regions in which the local order corresponds to metastable orthorhombic and tetragonal phases of the composition Fe₃B. The quantitative ratio of these regions is determined from Mössbauer spectra and is found to be 1:3. A quantitative two-level model of volumetric striction is presented. It is proposed in the model that heating is accompanied by reversible relaxation of orthorhombic configurations of the Fe₃B type to tetragonal configurations, which in turn shortens the distance between iron atoms.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp. 43–46, December, 1989.     

Diffusion in ordered Fe-Si alloys

The measurement of the diffusional Mössbauer line broadening in single crystalline samples at high temperatures provides microscopic information about atomic jumps. We can separate jumps of iron atoms between the various sublattices of Fe-Si intermetallic alloys (D0₃ structure) and measure their frequencies. The diffusion of iron in Fe-Si samples with Fe concentrations between 75 and 82 at% shows a drastic composition dependence: the jump frequency and the proportion between jumps on Fe sublattices and into antistructure (Si) sublattice positions change greatly. Close to Fe₃Si stoichiometry iron diffusion is extremely fast and jumps are performed exclusively between the three Fe sublattices. The change in the diffusion process when changing the alloy composition from stoichiometric Fe₃Si to the iron-rich side is discussed.     

Grain growth process of two-phase nanocrystalline soft magnetic materials

In order to clarify the origin of the high thermal stability of the microstructure in bcc-Fe/amorphous two-phase nanocrystalline soft magnetic materials, we have investigated the changes in the magnetic and microstructural properties upon isothermal annealing at 898 K for an Fe₈₉Zr₇B₃Cu₁ alloy by means of transmission electron microscopy, Mössbauer spectroscopy and DC magnetometry. The mean grain size was found to remain almost unchanged at the early stage of annealing. However, rapid grain coarsening was evident at an annealing time of 7.2 ks where the intergranular amorphous phase begins to crystallize into Fe₂₃Zr₆. The grain growth process with a kinetic exponent of 1.6 is observed for the growth process beyond this annealing time, reflecting the disappearance of the intergranular amorphous phase. Our results confirm that the thermal stability of the bcc-Fe/amorphous two-phase nanocrystalline soft magnetic alloys is governed by the residual amorphous phase.     

Changes in the hyperfine interactions in the Fe80Nb3Cu1B16 metallic glass under tensile loading

The influence of tensile stress on the changes in hyperfine parameters obtained by Mössbauer spectroscopy of the ferromagnetic amorphous NANOPERM-type Fe₈₀Nb₃Cu₁B₁₆ alloy has been investigated. The bulk changes are obtained by Mössbauer spectroscopy in a transmission geometry using γ-rays; the surface properties are studied in a scattering geometry using conversion electrons. The Mössbauer spectra are analyzed by two distributions of hyperfine inductions, which result in high-field and low-field components corresponding with a model of clusters formed by predominantly iron atoms and intermediate phase containing mainly the Nb, Cu and B atoms. The obtained results are completed by the bulk and surface magnetic measurements, with observations of surface morphology by AFM and microstructure by SEM. The investigations yield approximately linear increase of hyperfine parameters and slight deterioration of the bulk as well as surface magnetic characteristics with tensile loading.     

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.     

Phase analysis of hard magnetic Nd4Fe77B19 ribbon

Amorphous Nd₄Fe₇₇B₁₉ ribbon was prepared by conventional single-roller technique. Room temperature transmission⁵⁷Fe Mössbauer spectra were taken in the as-prepared state and after annealing 650°C/30 min in N₂-atmosphere and compared with that of the crystalline master alloy. The broad hyperfine induction distribution in the amorphous state was fitted by two symmetric Gaussians reflecting its asymmetry. In the annealed state, the spectrum decomposes into a series of sharp sextets corresponding to -Fe (6%), Nd₂Fe₁₄B (38%) present also in the master alloy, tetragonal Fe₃B (39%) and probably an inter-grain remainder (17%). No traces of the Nd₂Fe₁₇ admixed in the master alloy were found in the crystalline state. The results of the Mössbauer spectroscopy are compared with those of the X-ray and magnetic methods.     

Microstructure of supersaturated fcc Al–Fe alloys: A comparison of rapidly quenched and mechanically alloyed Al98Fe2

Alloys of the composition Al₉₈Fe₂ have been prepared by rapid quenching from the melt and mechanical alloying methods and have been studied by Xray diffraction techniques and room temperature ⁵⁷Fe Mössbauer effect methods. Results may be summarized as follows: The rapidly quenched sample is a single phase supersaturated fcc Al–Fe alloy. Mössbauer effect spectra indicate the presence of a substantially greater degree of Fe clustering than is expected for a random distribution of atoms on the lattice sites. Mechanically alloyed samples have been studied as a function of milling time and show the initial formation of a supersaturated fcc phase with microstructural properties which are quite similar to those of the rapidly quenched sample. Further milling results in the reduction of the average grain size and the formation of an amorphous phase. Mössbauer studies and previously reported phase diagrams suggest that a substantial fraction of the Fe resides in this phase.     

X-ray and Mössbauer study of rapidly solidified Ce20Fe80 ribbons; effect of the quenching rate

Ce₂₀Fe₈₀ ribbons have been produced by planar flow casting under an He atmosphere at linear wheel velocities between 19 and 29 m s^–1. Analysis of ribbons by X-ray diffraction and⁵⁷Fe Mössbauer spectrometry in the temperature range 77–300 K shows that the ribbons are crystallized. For higher velocities, the ribbon is constituted of the two equilibrium phases CeFe₂ and Ce₂Fe₁₇, but, for lower velocities, there appears a third iron metallic phase, which can be explained by the quenching rate of the melt. A coherent hyperfine parameter set was deduced from fitting Mössbauer spectra in the whole temperature range.     

Characterization of phases in the Fe-Nb system

The Fe-Nb system was investigated by means of X-ray diffraction and Mössbauer spectroscopy (at 300 and 77 K), in the range from 1 to 66.7 at%. We have found that the limit of solubility of Fe in Nb at 1100°C is between 3 and 4 at% Fe, and observed the coexistence of the Nb solid solution (Nbss) phase and Fe₂₁Nb₁₉ in the range from 4 to 40 at% Fe. The Mössbauer parameters of all the single phases are reported. The lattice parameters of Nbss phase present no significant variation with the Nb content. The X-ray pattern for the Fe₂₁Nb₁₉ phase could not be solved. The Laves phase Fe₂Nb presents Mössbauer and X-ray parameters that agree with the literature.     

Short-range order of quasicrystals after ball milling

Thermodynamically stable icosahedral Al₆₅Cu₂₀Fe₁₅ alloy is studied using⁵⁷Fe Mössbauer experiments. Its quasicrystalline structure is subjected to a low energy process of mechanical grinding up to 800 hours. The influence of ball milling on the electric field gradient magnitudes is discussed using an analysis of the Mössbauer spectra to different fitting models. The presence of an amorphous phase which co-exists with the quasicrystalline one is revealed in the early stage of mechanical grinding.     

Grain boundaries of nanocrystalline materials – their widths, compositions, and internal structures

Nanocrystalline materials contain many atoms at and near grain boundaries. Sufficient numbers of Mössbauer probe atoms can be situated in grain boundary environments to make a clear contribution to the measured Mössbauer spectrum. Three types of measurements on nanocrystalline materials are reported here, all using Mössbauer spectrometry in conjunction with X-ray diffractometry, transmission electron microscopy, or small angle neutron scattering. By measuring the fraction of atoms contributing to the grain boundary component in a Mössbauer spectrum, and by knowing the grain size of the material, it is possible to deduce the average width of grain boundaries in metallic alloys. It is found that these widths are approximately 0.5 nm for fcc alloys and slightly larger than 1.0 nm for bcc alloys. Chemical segregation to grain boundaries can be measured by Mössbauer spectrometry, especially in conjunction with small angle neutron scattering. Such measurements on Fe-Cu and Fe₃Si-Nb were used to study how nanocrystalline materials could be stabilized against grain growth by the segregation of Cu and Nb to grain boundaries. The segregation of Cu to grain boundaries did not stabilize the Fe-Cu alloys against grain growth, since the grain boundaries were found to widen and accept more Cu atoms during annealing. The Nb additions to Fe₃Si did suppress grain growth, perhaps because of the low mobility of Nb atoms, but also perhaps because Nb atoms altered the chemical ordering in the alloy. The internal structure of grain boundaries in nanocrystalline materials prepared by high-energy ball milling is found to be unstable against internal relaxations at low temperatures. The Mössbauer spectra of the nanocrystalline samples showed changes in the hyperfine fields attributable to movements of grain boundary atoms. In conjunction with SANS measurements, the changes in grain boundary structure induced by cryogenic exposure and annealing at low temperature were found to be somewhat different. Both were consistent with a sharper density gradient between the crystalline region and the grain boundary region.     

High pressure Mössbauer spectroscopy using a diamond anvil cell

Recent applications of high pressure Mössbauer spectroscopy using a diamond anvil cell are presented. High pressure Mössbauer studies of two perovskite-related iron oxides SrFeO_2.97 and CaFeO₃, magnetite Fe₃O₄, and wüstite Fe_1– O have been carried out at 300 K at pressures of up to 74 GPa. A preliminary result by the resonant forward scattering of synchrotron radiation for high pressure Mössbauer spectroscopy using a diamond anvil cell is also presented.     

Mössbauer spectroscopy studies of spin reorientations in amorphous and crystalline (Co0.2Fe0.8)72.5Si12.5B15 glass coated micro-wires

Thermo-gravimetric, differential scanning calorimetry and comprehensive ⁵⁷Fe Mössbauer spectroscopy studies of amorphous and crystalline ferromagnetic glass coated (Co_0.2Fe_0.8)_72.5Si_12.5B₁₅ micro-wires have been recorded. The Curie temperature of the amorphous phase is T_C(amorp) ∼730 K. The analysis of the Mössbauer spectra reveals that below 623 K the easy axis of the magnetization is axial-along the wires, and that a tangential or/and radial orientation occurs at higher temperatures. At 770 K, in the first 4 hours the Mössbauer spectrum exhibits a pure paramagnetic doublet. Crystallization and decomposition to predominantly α-Fe(Si) and Fe₂B occurs either by raising the temperature above 835 K or isothermally in time at lower temperatures. Annealing for a day at 770 K, leads to crystallization. In the crystalline material the magnetic moments have a complete random orientation. After cooling back to ambient temperature, both α-Fe(Si) and Fe₂B in the glass coated wire show pure axial magnetic orientation like in the original amorphous state. The observed spin reorientations are associated with changes in the stress induced by the glass coating.     

Mössbauer and magnetic studies of orthorhombic FeSiO3

Magnetic properties of orthoferrosilite FeSiO₃ have been examined using susceptibility, magnetization measurements and Mössbauer spectroscopy. From magnetic and Mössbauer measurements, one obtains close values of the magnetic ordering temperature, T_N=39±1 K and T_N=41±1 K, respectively. The magnetic order is characterized by strong ferromagnetic coupling of Fe²⁺ moments within the ribbons and a weak antiferromagnetic coupling of the moments between adjacent ribbons. The 4.2 K Mössbauer spectra can be fitted with two different hyperfine magnetic fields H_hf=68 kOe and H_hf=314 kOe which can be assigned to Fe²⁺ in the octahedrally coordinated M1 and M2 sites, respectively, of the FeSiO₃ structure.     

Sol–gel synthesis of 8 nm magnetite (Fe3O4) nanoparticles and their magnetic properties

Magnetite (Fe₃O₄) nanoparticles were successfully synthesized by a sol–gel method. The obtained nanoparticles were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive analysis by X-ray (EDAX), transmission electron microscopy (TEM), superconducting quantum interference device (SQUID) and Mössbauer spectrometry. XRD and Mössbauer measurements indicate that the obtained nanoparticles are single phase. TEM analysis shows the presence of spherical nanoparticles with homogeneous size distribution of about 8 nm. Room temperature ferromagnetics behavior was confirmed by SQUID measurements. The mechanism of nanoparticles formation and the comparison with recent results are discussed. Finally, the synthesized nanoparticles present a potential candidate for hyperthermia application given their saturation magnetization.     

FINEMET type alloy without Si: Structural and magnetic properties

Magnetic and structural properties of a Finemet type alloy (Fe_73.5Ge_15.5Nb₃B₇Cu₁) without Si and high Ge content were studied. Amorphous material was obtained by the melt spinning technique and was heat treated at different temperatures for 1 h under high vacuum to induce the nanocrystallization of the sample. The softest magnetic properties were obtained between 673 and 873 K. The role of Ge on the ferromagnetic paramagnetic transition of the as-quenched alloys and its influence on the crystallization process were studied using a calorimetric technique. Mössbauer spectroscopy was employed in the nanocrystallized alloy annealed at 823 K to obtain the composition of the nanocrystals and the amorphous phase fraction. Using this data and magnetic measurements of the as-quenched alloy, the magnetic contribution of nanocrystals to the alloy annealed at 823 K was estimated via a linear model.