Mössbauer spectroscopy of zirconium alloys

Mössbauer investigations of zirconium alloys were examined. Data about the chemical state of iron atoms in the zirconium alloys of different composition has been provided. Mössbauer spectroscopy revealed that small quantities of iron in binary zirconium alloy are in the solid solution α-Zr (up to 0.02 wt.%). Different iron atoms concentration and thermo-mechanical treatments may lead to formation the intermetallic compounds Zr₃Fe, Zr₂Fe, ZrFe₂. Adding tin atoms does not affect the formation and shape of Mössbauer spectra of these compounds. Adding Cr and Nb atoms makes significant changes in the shape of Mössbauer spectra and leads to the formation of complex intermetallic compounds. Adding Cu and W atoms, the shape of the binary alloys spectra (Zr-Fe) remains unchanged, but a change in the temperature dependence behavior of the spectral parameters occurs and also, changes to the properties of the alloys.     

169Tm Mössbauer effect in Tm2Fe14B

The compound Tm₂Fe₁₄B was investigated by means of ¹⁶⁹Tm Mössbauer spectroscopy in the temperature range from 4.2 to 300 K. The temperature dependencies of the hyperfine fields and quadrupole splittings for the two Tm sites were determined. The data were analysed on the basis of the spin structure determined by Yamada et al., which appears to be only partially compatible with the observed spectrum.     

The temperature dependence of the Mössbauer hyperfine parameters in Nd2Fe14B

We have determined the temperature dependence of the internal hyperfine field, isomer shift, and quadrupole shift at each of the six iron sites in Nd₂Fe₁₄B. The hyperfine parameters are consistent with the local iron site environments. The quadrupole and isomer shifts and their temperature dependences support our assignments of the relative ordering of the internal hyperfine fields as j₂>k₂>ck₁>j₁>c. We obtain a Mössbauer temperature of 390 K for Nd₂Fe₁₄B, which compares well with the Debye temperature of 420K for pure iron.     

Mössbauer spectroscopy in catalysis

Application of in situ Mössbauer spectroscopy for studying catalysts and catalytic processes is discussed. Examples are presented to illustrate the potentials of the method by describing studies on supported heterogeneous catalysts performed with ¹¹⁹Sn and ⁵⁷Fe spectroscopies in cases with certain metals and alloys, oxides and porous substances. The results are interpreted in comparison to the catalytic performance.     

Atomic short-range order in Fe1−xCrx alloys studied by 57Fe Mössbauer spectroscopy

The room temperature Mössbauer spectra of ⁵⁷Fe were measured for iron-based solid solutions Fe_1?xCr_x with x in the range of 0.01≤x≤0.10. Analysis of the obtained spectra gave clear evidence that the distribution of impurity atoms in the first coordination spheres of ⁵⁷Fe nuclei is not homogeneous and it cannot be described in terms of binomial distribution. Quantitatively, the effects were described in terms of the short-range order parameters.     

Tin Mössbauer spectroscopy of tin-rich iridium-tin alloys

Ir₅Sn₇, Ir₃Sn₇ and newly obtained IrSn₄ /4/ exhibit complex Mössbauer spectra. The positions of the individual lines range from 0.82 to 3.0 mm/s and the average isomer shift \(\overline {IS} \) derived for each compound of Sn atomic percentage x follows the relationship: \(\overline {IS} = 0.60 + 0.0194 x\) . Rather large quadrupole splittings are obtained. The f factors are about 0.20 at 295 K and 0.37 at 78 K, from which Debye temperatures of 200 to 300 K have been calculated.     

Mössbauer spectroscopy in molecular magnetism

The aim of this paper is to highlight some selected research activities on molecular magnetic materials using Mössbauer spectroscopy as a technique carried out in our laboratory in recent years. The first part of the present article is devoted to the studies of the various magnetic interactions, metal-to-metal electron-transfer phenomenon, glass transition occurring in molecular magnetic materials, whereas the second part deals with the iron(II) high spin (S = 2)–low spin (S = 0) transition phenomenon occurring in some isoxazole ligand based iron(II) compounds as examples with unusually complicated spin transition behaviour. Also, an example of a dinuclear a spin crossover compound of iron(II) is described, where Mössbauer spectroscopy has most convincingly unraveled the mechanism of the spin transition process. Finally, an example from our most recent studies of spin crossover materials exhibiting both thermal spin crossover and liquid crystalline properties in the same temperature interval near room temperature will be presented.     

Mössbauer spectroscopy in physical metallurgy

In this anniversary contribution the natural and intimate match making which occurs between the two star performers-⁵⁷Fe in Mössbauer spectroscopy and iron in physical metallurgy—is described by selecting typical examples reflecting the author's interest: phases, f.c.c. -Fe, defects, diffusion and amorphous metals.     

Mössbauer spectroscopy of the Zr-rich region in Zr–Nb–Fe alloys with low Nb content

Intermetallic phases and solid solutions in the Zr-rich region of the Zr–Nb–Fe system with low Nb content are studied by Mössbauer spectroscopy complemented with X-ray diffraction, optical and scanning electron microscopy and electron microprobe analysis. The phases found in each sample were those expected from the corresponding binary Zr–Fe system. Furthermore, one of the samples showed a ternary cubic Ti₂Ni type phase with a similar stoichiometry to the tetragonal Zr₂Fe compound. Mössbauer parameters were suggested to this phase (IS: - 0.12 mm/s, QS: 0.30 mm/s), to the bcc Zr(β) phase (IS: (-0.11 α 0.01) mm/s, QS: (0.23 α 0.02) mm/s), and to the hcp Zr(β^T) phase (IS: (-0.24 α 0.02) mm/s, QS: (0.45 α 0.02) mm/s).     

Mössbauer spectroscopy in determining the gas molecular state

A possibility of conversion electron Mössbauer spectroscopy for determining the gas molecular state is shown. For acceleration of gas interaction with active surface the thin iron layer enriched with ⁵⁷Fe was applied on aluminum foil and gas discharge is used.     

Mössbauer spectroscopy of H,L and LL ordinary chondrites

Fifteen fragments of H, L and LL ordinary chondrites were studied using Mössbauer spectroscopy with a high velocity resolution at 295 K. A new approach to fit troilite magnetic sextet using simulation of the full static Hamiltonian was applied that decreased spectra misfits. This approach permitted to obtain more correct and reliable parameters for the minor spectral components. Small variations in the ⁵⁷Fe hyperfine parameters were revealed for the M1 and M2 sites in both olivine and orthopyroxene as well as for α-Fe(Ni, Co), α ₂-Fe(Ni, Co) and γ-Fe(Ni, Co) phases in different ordinary chondrites. Some Mössbauer parameters showed the possibility to distinguish ordinary chondrites from H, L and LL groups that may be useful for their systematics.     

Magnetic and 57Fe Mössbauer studies of collinear spin rotation in Ho2Fe14B

Magnetic properties of Ho₂Fe₁₄B compounds have been studied by the ⁵⁷Fe Mössbauer effect and magnetization measurements. The axes of easy and hard magnetizations lie along the [001] and the [100] directions in the tetragonal structure, respectively, above T_sc = 58 K. From the comparison of the Mössbauer results with the magnetization measurements, it became clear that the Fe and the Ho moments tilt collinearly from the c-axis to the [110] direction throughout the temperature range of 4.2–58 K, and the canting angle reaches to 22° at 4.2 K. The Mössbauer spectra are consistently resolved with six subspectra above T_sc and with twelve below T_sc, together with reasonable site-assignments. We have estimated the mean Ho moment at 10.0μ_B, using the mean Fe moment of 2.3μ_B derived from the average hyperfine field or using the magnetization of Y₂Fe₁₄B as the Fe-sublattice magnetization of Ho₂Fe₁₄B.     

Mössbauer spectroscopy study of the disordering process of Fe-rich FeAlSi alloys

In this work we study systematically the influence of different Al/Si ratios on the magnetic and structural properties of mechanically disordered powder Fe₇₅Al_25?x Si _x , Fe₇₀Al_30?x Si _x and Fe₆₀Al_40?x Si _x alloys by means of Mössbauer spectroscopy and X-ray diffraction measurements. In order to obtain different stages of disorder the alloys were deformed by ball milling annealed (ordered) alloys during different number of hours. X-ray and Mössbauer data show that mechanical deformation induces the disordered A2 structure in these alloys. The results indicate that addition of Si to binary Fe–Al alloys makes the disordering more difficult. The study of the hyperfine fields indicates that depending on the Fe content the magnetic behaviour of these ternary alloys varies. For Fe₇₅Al_25?x Si _x series, the alloys have different magnetic behaviours with deformation depending on the Si content. The magnetization of the alloys with high Si content decreases with deformation, as it happens to binary Fe₇₅Si₂₅ and the magnetization of the alloys with low Si content increases with deformation, as it happens to binary Fe₇₅Al₂₅. For Fe₇₀Al_30?x Si _x series the mean hyperfine fields show that there are two different stages with the disordering, in a first stage the mean hyperfine fields decrease and in the second stage they increase. Finally, for Fe₆₀Al_40?x Si _x alloys there is a magnetic transition, from a paramagnetic ordered state to a magneticdisordered state.     

Mössbauer spectroscopy of Al substituted Fe in holmium iron garnet

A Mössbauer spectroscopy study was made on Ho₃Fe_5-xAl_xO₁₂ (x=0.0, 0.05, 0.7). X‐ray diffraction patterns indicate that the samples with x=0.0 and 0.05 have the garnet structure, while the sample with x=0.7 has an additional noncubic structural phase. The room temperature spectrum for samples with x=0.0 and 0.05 consists of two magnetic components corresponding to the octahedral and tetrahedral sites with hyperfine magnetic fields (B_hf) of 50 T and 40 T, respectively. For x=0.7 we observe a new magnetic component with B_hf= 45 T, a reduction in the intensity and broadening of the tetrahedral component, and the evolution of a nonmagnetic central component. These variations are evidently due to the addition of aluminium to the system. At liquid nitrogen temperature the samples with x=0.0 and 0.05 are nearly identical. It was also observed that the increase in B_hf for the octahedral site is smaller than that for the tetrahedral site as the temperature is lowered to 80 K.     

Mössbauer Study of the Fe3B/Nd2Fe14B Nanocomposite Magnet by the Addition of Co

The addition of Co to Nd₄Fe_77.5–x Co _x Hf_0.5Ga_0.5B_18.5 (0x5) was found to enhance the magnetic properties of Fe₃B/Nd₂Fe₁₄B nanocomposite magnets. The enhancement resulted from the fact that Co tends to retard the formation of Fe₃B from the amorphous matrix but to accelerate that of Nd₂Fe₁₄B. The decreased interval between the crystallization temperature of Fe₃B and Nd₂Fe₁₄B led to a uniform grain size distribution of both phases during the annealing treatment. The additive Co was confirmed to partition mainly to Nd₂Fe₁₄B crystals rather than to Fe₃B which was traced by XRD and Mössbauer spectroscopy as well. About 72 vol.% of Fe₃B, 27 vol.% of Nd₂Fe₁₄B, and a small amount of Fe around 1 vol.%, respectively, were found to form. However, the volume fraction of each phase did not vary by the addition of Co up to 5 at.%.     

Digital pulse processing in Mössbauer spectroscopy

In this work we present some advances towards full digitization of the detection subsystem of a Mössbauer transmission spectrometer. We show how, using adequate instrumentation, preamplifier output of a proportional counter can be digitized with no deterioration in spectrum quality, avoiding the need of a shaping amplifier. A pipelined architecture is proposed for a digital processor, which constitutes a versatile platform for the development of pulse processing techniques. Requirements for minimization of the analog processing are considered and experimental results are presented.     

Evaluation of the detection limit in electron-recording Mössbauer spectroscopy

A semiempirical formula is derived for evaluating the lowest concentration of Mössbauer atoms whose signal can be reliably recorded by electron Mössbauer spectroscopy. The concentration is calculated from the resonance effect magnitude in a sample of known chemical composition, on the basis of the cross sections of photoelectric absorption of source gamma photons by the sample atoms, the energy and probability of production of photoelectrons and their associated Auger electrons, and the probability of recoilless gamma-photon absorption in the sample. Experimental testing showed that the calculated and measured values of differ by not more than 20%.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 20–23, September, 1987.     

Mössbauer spectroscopy on57Fe: NaCl crystals

Mössbauer absorbtion spectra of⁵⁷Fe-doped NaCl crystal were measured and correlated with an adequate electric field gradient computation to describe the dipolar complexes occuring at the decay of Suzuki-phase under thermal treatment and X-ray irradiation. An electrostatic potential of the type was taken into account in the evaluation of EFG tensor.     

Mössbauer spectroscopy with the 93 keV-resonance in67Zn

The procedures and results of high resolution Mössbauer experiments performed with the 93.3 keV resonance in absorbers of⁶⁷ZnO,⁶⁷ZnS (both wurtzite and sphalerite structures),⁶⁷ZnSe,⁶⁷ZnTe and⁶⁷ZnF₂ are reported. An essentially linear dependence between the isomer shift and the Pauling electronegativity of the ligands was found. A value of r ²=+11×10^–3 fm² is estimated. The Mössbauer parameters for both ZnS structures are equal within present limits of error. In particular, no quadrupole interaction was observed in the wurtzite modification. This indicates a nearly identical local symmetry at the Zn site in the two ZnS structures.Work supported by the Bundesministerium für Forschung und Technologie, Federal Republic of Germany and the Kernfor-schungszentrum Karlsruhe