Synchrotron Mössbauer source of57Fe radiation

A nonradioactive source of Mössbauer radiation is described for use in Mössbauer absorption and scattering spectroscopy. The radiation is generated by synchrotron Xrays in an iron borate single crystal set in diffraction conditions at the Néel temperature (75.3°C). Like a conventional Mössbauer source the new Synchrotron Mössbauer (SM) source emits singleline radiation of about natural linewidth, but in addition the emitted radiation is fully recoilless, highly directed and of pure linear polarization. An extremely high suppression of the electronic scattering is achieved. The latter circumstance allows one to perform Mössbauer experiments using pulsed synchrotron radiation in a steady state mode as in a normal Mössbauer measurement.The theory of the SM source is developed. First Mössbauer spectra obtained with the SM source are shown. Applications of the SM source are discussed.     

57Fe Mössbauer investigations of manganese-containing spinels

Cation distributions and related order-disorder phenomena in the naturally occurring Mn-spinels: iwakiite, galaxite and franklinite, have been investigated by means of⁵⁷Fe Mössbauer spectroscopy. Previous measurements on an iwakiite sample indicated the existence of Mn-rich and Mn-poor regions. This interpretation has been confirmed in this investigation by further measurements on annealed iwakiite samples. The⁵⁷Fe Mössbauer spectrum of galaxite from Bald Knob, NC, is a well-resolved quadrupole doublet and indicates the presence of a single crystallographic Fe³⁺ species. A galaxite sample from Thailand exhibited a complex spectrum of Fe²⁺ and Fe³⁺ quadrupole doublets: This sample has been misidentified and should be regarded as a member of the (Mg, Fe)(Al, Fe)₂O₄ series. The⁵⁷Fe hyperfine parameters of a rare franklinite from Längban, Sweden, are very close to those for synthetic zinc ferrite, confirming electron microprobe results of an unusually high zinc content.     

Ferrous ammonium sulphate hexahydrate Mössbauer revisited: a combined 57Fe Mössbauer and X-ray single crystal study

This paper investigates the electric-field gradient (efg) tensor for the Fe^2?+? ion in ferrous ammonium sulphate hexahydrate single crystals at 295 K from two different, but apparently equivalent, standpoints. Firstly, we calculate the expected angular dependence of the thin-crystal-limit reduced intensity ratios and total intensities of the quadrupole doublet utilizing earlier determined macroscopic intensity tensor data and X-ray-determined atomic-displacement parameters (ADPs) for the iron nucleus. The computer program used (MOSREF) utilizes matrix diagonalization in an arbitrary coordinate frame to calculate Mössbauer intensities for sites of any specified symmetry in crystals of any specified symmetry. Secondly we attempt to measure, directly by Mössbauer spectroscopy, the Lamb–Mössbauer factors that may, via the mean-squared-displacement tensor, be related to the Fe^2?+? ADPs. From the experimental angular dependence of the reduced intensities (areas), corrected to the thin crystal limit, and experimental Mössbauer-determined mean-squared displacements, we determine the microscopic electric-field-gradient tensors for the two symmetry-related sites in the unit cell. This is achieved using the refinement options of program MOSREF where reduced intensities and total intensities are refined simultaneously. Successful determination of microscopic tensors depends on anisotropy in the absorber recoilless fractions that are in turn related to anisotropic Lamb–Mössbauer factors.     

57Fe Mössbauer spectroscopy and X-ray diffraction study of complex metamict minerals. Part II

The magnetic behaviour of the nanocrystalline Ni_0.5Cu_0.5Fe₂O₄, synthesized by the co-precipitation method has been studied. The X-ray diffraction patterns confirm the formation of cubic spinel structure. The dc magnetization measurements show that the samples are superparamagnetic above the blocking temperatures and the blocking temperature increases with particle size. The reduction in saturation magnetization in the case of nanoparticles as compared to their bulk counterpart has been explained on the basis that the magnetic moments in the surface layers of a nanoparticle are in a state of frozen disorder. The hump in ZFC curve progressively shift to a lower temperature with increasing field and broader curves at higher field, suggests the spin-glass nature of the system.     

Magnetization and Mössbauer studies of 57Fe doped SrCoO3

⁵⁷Fe (1%) doped SrCoO₃ obtained by high-pressure method, has been investigated by magnetization and Mössbauer spectroscopy studies (MS) in the temperature range 4.2 K to 300 K. The ferromagnetic ordering temperature T _C obtained is 272(2) K. Isothermal magnetization curves have been measured at various temperatures, from which the saturation moments (M _sat) have been deduced. The ⁵⁷Fe MS spectra display standard six-line patterns with an isomer shift typical of Fe^3?+? and a very small quadrupole splitting (QS = 0.14(1) mm/s above T _C). The magnetic hyperfine field at 4.2 K is 276(1) kOe. The temperature dependencies of the iron hyperfine field and M _sat (1.83 µ _B at 5 K) are almost identical. This shows that the Fe^3?+? is replacing Co^4?+?, both of the same electronic configuration. They also interact similarly, namely the Fe–Co exchange is almost identical to the Co–Co exchange.     

193Ir and 57Fe Mössbauer characterisation of iridium/iron bimetallic catalysts for methanol synthesis

Fe-Ir/MgO catalysts derived from the [Et₄N]₂[Fe₂Ir₂(CO)₁₂] cluster precursor, which exhibit a high activity in the synthesis of methanol from CO and H₂, were studied by ¹⁹³Ir and ⁵⁷Fe Mössbauer spectroscopy. The study extends from the precursors via the fresh to the aged catalysts. The presence of iridium in the metallic state as well as the presence of trivalent, divalent and alloyed iron is detected. The different structural features of catalysts prepared from mixed-metal cluster compounds and from inorganic salt precursors are discussed.     

238U and 57Fe Mössbauer Spectroscopic Study of UFe2

We have performed ⁵⁷Fe and ²³⁸U Mössbauer measurements of UFe₂ in order to investigate its magnetic properties. From the results of ⁵⁷Fe Mössbauer spectroscopy, the ferrromagnetic ordering at 167 K is caused by the iron 3d-electrons, which hybridize strongly with the uranium 5f-conduction electrons. It is also clarified from the results of ²³⁸U Mössbauer spectroscopy that there are no magnetic moments on the uranium atoms.     

Mössbauer effect and X-ray diffraction investigation of Si–Fe thin films

An X-ray diffraction and ⁵⁷Fe Mössbauer spectroscopy investigation of Si_{100– x} Fe _x (0?<?x?<?80) thin films prepared by combinatorial sputtering methods is reported. Resulting Mössbauer spectra were fit to Voigt-based distributions of quadrupole doublets for paramagnetic spectral components and Zeeman split sextets for ferromagnetic spectral components. In conjunction with the X-ray measurements, these results show that the Si-rich films are a mixture of dilute Fe in amorphous Si and an approximately equiatomic amorphous SiFe phase. Fe-rich films show the presence of a ferromagnetically ordered phase. For x?<?73, this ferromagnetic phase is amorphous or nanostructured and for x?≥?73, the phase is shown to be a crystalline bcc phase. Results are discussed in terms of short-range structural ordering in these alloys.     

Mössbauer and X-ray phase analysis of carburized steel

⁵⁷Fe backscattering Mössbauer phase analysis of the ASTM A295-70 type chromium bearing steel gas was performed for samples with varying phase composition achieved by gas carburization up to 3 wt% C followed by standard hardening, i.e. austenitizing and quenching procedures. Variations of contents of principal metallographic phases (alloyed martensite, austenite, magnetic and non-magnetic carbides) were determined and compared with reported X-ray data. Results are discussed in connection with the composition and heat treatment. Good mutual agreement of results was found, the Mössbauer phase analysis being superior for distinguishing magnetic and non-magnetic carbides, for finding the dependence on composition and also for detecting alloying element segregation. On the other hand, the Mössbauer method of determination of a small content of alloyed retained austenite suffers from the small difference between its satellites and non-magnetic carbides.     

57Fe Mössbauer spectroscopic study of nanostructured zinc ferrite

Nanosize zinc ferrite particles, prepared by nitrate method, were investigated by XRD, TEM, ⁵⁷Fe Mössbauer spectroscopy and VSM. The average particle size in this system varies from 10 to 62 nm as the sintering temperature increases from 300°C to 1,000°C. The lattice parameters in this system are almost constant at a value of ～8.41 Å. The Mössbauer spectra of all the sintered samples show a single doublet. The Mössbauer hyperfine parameters show little change with the change of sintering temperature. The doublets are ascribed to the presence of superparamagnetism in this system, which is also corroborated by the VSM measurements.     

57Fe Mössbauer study of new multiferroic AgFeO2

The present work reports results of the ⁵⁷Fe Mössbauer measurements on AgFeO₂ powder sample recorded at various temperatures including the points of both magnetic phase transitions. The ⁵⁷Fe Mössbauer spectra of AgFeO₂ measured in the paramagnetic range (T > T _N1) consist of one quadrupole doublet with rather high quadrupole splitting of Δ_300K = 0.66 ± 0.01 mm/s for Fe³⁺ ions. In order to predict the sign of electric field gradient (EFG) at ⁵⁷Fe nuclei, we calculated the lattice contribution to the electric field gradient (EFG) at ⁵⁷Fe nuclei, which emphasized the importance of the dipolar contributions, with resultant oxygen polarizabilities in the range of α _O = 0.83 ų, in agreement with the results obtained previously for other delafossite-like oxides. In the temperature range of T _N2 < T < T _N1, Mössbauer spectra gave clear evidence for the existence of a distribution of the hyperfine magnetic fields H _hf at ⁵⁷Fe nuclei. We present the results of a model fitting of the spectra based on an assumption of the cycloid magnetic structure of AgFeO₂ at T < T _N2. The obtained data were analysed in comparison with published data on Mössbauer studies of oxide multiferroics.     

Interface study of Ag/57Fe/Ag trilayer using Mössbauer and X-ray standing wave analysis

Interface of Ag/⁵⁷Fe/Ag trilayer has been studied with a depth resolution of a fraction of a nanometer using x-ray standing waves generated by a W/Si multilayer mirror used as a substrate. Two interfaces of 38 Å thick Fe layer in Ag/⁵⁷Fe/Ag trilayer are clearly resolved. It is found that the rms roughness of the two interfaces Fe-on-Ag and Ag-on-Fe are 10 ± 1.0 and 6 ± 1.0 Å, respectively. Conversion electron Mössbauer spectroscopy (CEMS) has been used to get information about the volume fraction of the intermixed region and the estimated roughness from the relative area of the two sextets of CEMS spectra is found to be 7.0 Å which is consistent with the average roughness obtained by X-ray fluorescence measurements. However, the asymmetry of the interfaces can not be inferred from CEMS measurements.     

Mössbauer and PAC studies of nanocrystalline Fe

High-purity Fe powder was mechanically milled under argon at ambient temperature using an SPEX 8000 mill. The local atomic and magnetic structure was studied using⁵⁷Co/Fe Mössbauer and¹¹¹In/Cd perturbed angular correlations (PAC) spectroscopies. After 32 hours of milling, X-ray diffraction revealed effective grain diameters of 18 nm and energy-dispersive X-ray analysis indicated a Cr impurity concentration of 5%, presumably introduced by mechanical attrition of steel ball bearings used for milling. In addition to a spectral component very similar to bulk iron metal, the Mössbauer spectra exhibited hyperfine field shifts attributed to the Cr impurities. PAC spectra on Fe milled for 5 h, with no contamination, exhibited two components: (1) A slightly broadened magnetic interaction attributed to interior, defect-free sites of In/Cd probes with a mean hyperfine field slightly greater than in macroscopic grains. The defect-free site fraction grew appreciably during milling, even though In is essentially insoluble in Fe. (2) An indistinct signal due to mixed magnetic and quadrupole interactions attributed to probes at surface or other defect sites.     

Mössbauer study of 57Fe in GaAs and GaP following 57Mn+ implantation

Ion implantation provides a precise method of incorporating dopant atoms in semiconductors, provided lattice damage due to the implantation process can be annealed and the dopant atoms located on regular lattice sites. We have undertaken ⁵⁷Fe emission Mössbauer spectroscopy measurements on GaAs and GaP single crystals following implantation of radioactive ⁵⁷Mn^?+? ions, to study the lattice sites of the implanted ions, the annealing of implantation induced damage and impurity–vacancy complexes formed. The Mössbauer spectra were analyzed with four spectral components: an asymmetric doublet (D1) attributed to Fe atoms in distorted environments due to implantation damage, two single lines, S1 assigned to Fe on substitutional Ga sites, and S2 to Fe on interstitial sites, and a low intensity symmetric doublet (D2) assigned to impurity–vacancy complexes. The variations in the extracted hyperfine parameters of D1 for both materials at high temperatures (T?> 400 K) suggests changes in the immediate environment of the Fe impurity atoms and different bonding mechanism to the Mössbauer probe atom. The results show that the annealing of the radiation induced damage is more prominent in GaAs compared to GaP.     

Mössbauer effect diffraction from polycrystalline57Fe

We built a Debye-Scherrer type powder diffractometer with a⁵⁷Co radiation source and a large-angle position-sensitive detector. We tuned the incident -ray beam on and off the Mössbauer effect resonance, and measured diffraction patterns from our textured samples of polycrystalline⁵⁷Fe. Mössbauer effect diffraction dominated over X-ray diffraction for the higher order Bragg peaks.     

Mössbauer and X-ray studies of an iron meteorite sample

Detailed analysis of the room temperature Mössbauer spectrum of an Fe-Ni ( 91.9% Fe, 7.5% Ni) meteorite from the Henbury crater region of northern Australia shows that it behaves identically to an Fe-Ni alloy. The enhanced resonance absorption is due to thickness effects, with the line broadening reflecting a range of atomic environments. The isotope ratio⁵⁶Fe/⁵⁷Fe for the meteorite agrees with the earth bound values.