Dynamical properties of semiconducting Fe: YBaCuO

The vibrational behavior of iron in oxygen deficient YBaCuO has been studied by Mössbauer spectroscopy up to 770 K. Iron coordinated by four oxygen atoms reveals a significantly softer and anharmonic temperature dependence (temperature dependent θ_D) than iron with higher coordination (θ_D=600 K). Above about 650K oxygen diffusion leads to relaxation effects for two of the observed iron species.     

An iron-57 Mössbauer spectroscopic study of titania-supported iron- and iron-iridium catalysts

⁵⁷Fe Mössbauer spectroscopy shows that titania-supported iron is reduced by treatment in hydrogen at significantly lower temperatures than corresponding silica- and alumina-supported catalysts. The metallic iron formed under hydrogen at 600°C is partially converted to carbide by treatment in carbon monoxide and hydrogen. In contrast to its alumina- and silica-supported counterparts, the remainder of the titania-supported iron is unchanged by this gaseous mixture. The⁵⁷Fe Mössbauer spectra and EXAFS show that iron and iridium in the titania-supported iron-iridium catalysts are reduced in hydrogen at even lower temperatures and, after treatment at 600°C, are predominantly present as the iron-iridium alloy. The treatment of these reduced catalysts in carbon monoxide and hydrogen is shown by Mössbauer spectroscopy and EXAFS to induce the segregation of iron from the iron-iridium alloy and its conversion to iron oxide.     

The magnetic hyperfine interaction of iron atoms isolated in a xenon matrix in the presence of an external magnetic field

The Mössbauer effect has been used to measure the magnetic hyperfine interaction of isolated ⁵⁷Fe atoms in solid xenon with an applied external magnetic field. A field dependent Mössbauer absorption spectrum is observed. The ground state of these iron atoms is a triplet, which is split in the external field. The Mössbauer spectrum was analyzed taking into consideration relaxation effects. For an applied external field of 28 kOe an internal magnetic field at the ⁵⁷Fe nucleus of 700± 15 kOe was observed (external field included).     

A Mössbauer study on TiBaCa3(Cu1−xFex)3O8.5 superconductors

Two main superconducting phases, 1223 and 2223 in TiBaCa₃Cu₃O_8.5 superconductor, are identified by powder x-ray analysis and⁵⁷Fe Mössbauer spectroscopy analysis. The Mössbauer fitting results shown that iron atoms in the lattice substitute two inequivalent sites of copper atoms for each main phase. The temperature dependence of Mössbauer parameters are obtained, and several problems are discussed which relate to the electric charge transfer which takes place around the superconducting transition temperature, the lattice dynamics and the effect on oxygen deficiency at different temperatures.     

Pure and impure clays and their firing products

Mössbauer spectroscopy is highly suited for the study of clays whose industrial uses depend on the iron content. Reactions that take place during clay firing can be readily monitored by Mössbauer spectroscopy. Following dehydroxylation of clay minerals, the quadrupole splitting of octahedrally coordinated iron (III) increases abruptly, but reverts to lower values upon the formation of new, better ordered phases at higher temperatures. It is also shown that iron oxides may account for a considerably higher proportion of the total iron content of many clays than is commonly recognized, and their existence must be taken into consideration for a correct interpretation of the Mössbauer spectra of clays.     

Investigations of crystal and magnetic properties of the Mn5−xFexGe3 intermetallic compounds

The Mn_5?xFe_xGe₃ intermetallic compounds are investigated with X-ray, neutron diffraction, magnetometric and Mössbauer effect methods. It is found that crystal structure of x = 1 compound is of D8₈ type while the structure of x = 3, 4 and 5 compounds is of B8₂ type. All are ferromagnets with collinearly ordered atomic spins. The lattice constants are derived from X-ray diffraction patterns, while magnetometric measurements yield the Curie temperatures and Weiss constants as well as the values of magnetic moments per molecule in ferromagnetic and paramagnetics states. The distributions of Fe and Mn atoms among two non-equivalent crystal sites are determined with the neutron diffraction method and are confirmed by the Mössbauer effect measurements. The parameters of hyperfine interactions are derived from Mössbauer absorption spectra and are attributed to iron atoms in two non-equivalent crystal sites.     

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.     

Localisation of iron ions in NH4,Na-Y zeolite: A Mössbauer effect study

Localisation of Fe ions in deep-bed treated NH₄,Na-Y zeolite at 830K, 940K, and 1050K, as well as after reduction by hydrogen, and dealumination with subsequent calcination is studied by⁵⁷Fe Mössbauer spectroscopy. Most of the incorporated iron is present in the form of octahedrally coordinated ferric species with two distinct sets of hyperfine parameters assigned to atoms inside the zeolite structure and in extraframework positions. Fe²⁺ ions with high coordination are also detected and their amount increases with the temperature of deep-bed treatment. Low-temperature Mössbauer effect measurements at 77K and 4.2K were employed to facilitate the identification of iron sites.     

An iron-57 Mössbauer spectroscopy and EXAFS study of the hydrogen pretreatment of titania-supported iron-ruthenium catalysts

The changes in composition and structure which are induced in a titania-supported iron-ruthernium catalyst following treatment in hydrogen have been investigated in situ by⁵⁷Fe Mössbauer spectroscopy and by EXAFS. The results show that ruthenium dioxide is readily reduced at temperatures below ca. 500°C to ca. 20 Å clusters of metallic ruthenium whilst α-Fe₂O₃ is partially reduced at 130°C to Fe²⁺ and Fe⁰. The Fe³⁺ which is formed by the reoxidation of Fe²⁺ under the reducing conditions at 500°C segregates to the interface of the bimetallic phase and the titania support. It is suggested that continued treatment at 700°C produces a high dispersion of iron which is coordinated to oxygen atoms of the support. The ca. 20 Å clusters of metallic ruthenium may be envisaged as being anchored to the support via iron-ruthenium bonds     

Mössbauer study of cobalt and iron in the cyanobacterium (blue green alga)

Mössbauer emission and absorption studies have been performed on cobalt and iron in the cyanobacterium (blue-green alga). The Mössbauer spectrum of the cyanobacterium cultivated with⁵⁷Co is decomposed into two doublets. The parameters of the major doublet are in good agreement with those of cyanocobalamin (vitamin B₁₂) labeled with⁵⁷Co. The other minor doublet has parameters close to those of Fe(II) coordinated with six nitrogen atoms. These suggest that cobalt is used for the biosynthesis of vitamin B₁₂ or its analogs in the cyanobacterium. The spectra of the cyanobacterium grown with⁵⁷Fe show that iron is in the high-spin trivalent state and possibly in the form of ferritin, iron storage protein.     

Mössbauer spectra of Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cr<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>S solid solutions

Compounds in the CrS-FeS system over a wide range of compositions are investigated by Mössbauer spectroscopy. The analysis of the Mössbauer spectra demonstrates that the materials under investigation are substitutional solid solutions with a random distribution of chromium and iron atoms. The assumption is made that the observed broadened Zeeman sextets are superpositions of partial sextets corresponding to iron atoms with different nearest environments. The observed decrease in the hyperfine fields for the broadened sextets with an increase in the chromium content in the samples is in good agreement with a change in the concentration of the corresponding environments.     

A study of the sump beaver's dental enamel

The nature of the iron-containing phase in the dental enamel of sump beaver incisors has been studied by use of Mössbauer spectroscopy. All iron atoms are found to be trivalent and to be present in particles exhibiting superparamagnetic relaxation. The iron-containing phase has Mössbauer parameters similar to those of ferritin.     

Mössbauer,electron paramagnetic resonance and magnetic susceptibility studies of photosensitive nitrile hydratase fromRhodococcus sp. N—771

Mössbauer, magnetic susceptibility and electron paramagnetic resonance (EPR) studies of inactive and photoactivated NHase enzymes were performed to elucidate the electronic change of non-heme two-iron atom center of the enzyme by photoactivation. These spectroscopic investigations revealed that both the two iron atoms of the active NHase could be assigned to low-spin ferric state, and those of the inactive NHase could each be assigned to low-spin ferric and low-spin ferrous ones. From these results, it was concluded that one of the non-heme iron atoms is oxidized in the inactive NHase during photoactivation.     

197Au and125Te Mössbauer spectroscopic study on the low temperature phases of Ag3AuX2 (X=S,Se, and Te)

¹⁹⁷Au and¹²⁵Te Mössbauer spectroscopy has been applied for the low-temperature β-phases of Ag₃AuX₂ (X=S, Se, and Te). The values of I. S. and Q. S. for¹⁹⁷Au suggest that the gold atoms, linearly coordinated by two chalcogen atoms in these phases, exist as monovalent cations. The¹²⁵Te Mössbauer spectra suggest that the tellurium atoms are substantially ionic for both Ag₂Te and Ag₃AuTe₂. The nature of X-Au-X bonds is discussed on the basis of the Mössbauer data and the bond distances.     

Monte Carlo Simulations of Mössbauer Results in Fe–C Austenite

The Mössbauer signal of Fe–C austenite is difficult to interpret because different Fe–C configurations give rise to different hyperfine interactions. Two competing models for the distribution of carbon atoms in the fcc austenite lattice have been proposed to account for Mössbauer spectra. Both models assume a repulsive C–C interaction of different magnitude and different Fe–C configurations. From the Mössbauer spectra, the abundance of the different iron sites could be determined. That abundance may also be calculated with Monte Carlo simulations. In this work, using the two controversial models, we compare the relative fractions of the Fe–C configurations obtained from Mössbauer spectra of vermicular austempered cast iron with Monte Carlo simulation.     

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.     

Effect of particle size and alloying with different metals on 57Fe Mössbauer spectra

Iron nanoparticles of various sizes have been synthesized using the chemical route which involves the preparation of iron bipyridine complexes in presence of different capping agents followed by thermal decomposition at 450°C in inert atmosphere. The bimetallic nanoalloys of Fe with Mg and Pd have also been prepared by following the same route. The resulting nanoparticles have been characterized by EDX-RF, XRD, AFM and ⁵⁷Fe Mössbauer spectroscopy. The appearance of quadrupole doublets in the Mössbauer spectra of Fe nanoparticles indicates the absence of magnetic interaction and variation in parameters is due to the varying particle size. The Mössbauer spectrum of Fe–Mg₂ bimetallic nanoalloy shows two doublets indicating the presence of superparamagnetism. The two doublets can be attributed to change in s-electron density of iron resulting from its two neighboring magnesium atoms. Fe–Pd nanoalloy Mössbauer spectrum is characterized by having a superparamagnetic doublet and a ferromagnetic sextet.     

Artificial neural networks in Mössbauer material science

Mössbauer spectroscopy is a useful technique for characterizing the valencies, electronic and magnetic states, coordination symmetries and site occupancies of the cation. The Mössbauer parameters of isomer shift and quadrupole splitting are useful to distinguish paramagnetic ferrous and ferric iron in several substances, while the internal magnetic field provides information on the crystallinity. In recent years artificial neural networks have shown to be a powerful technique to solve problems of pattern recognition of a mineral from its Mössbauer spectrum, Mössbauer parameters data bank, crystalline structure and magnetic phases of soil from Mössbauer parameters. A computer software named Mössbauer Effect Assistant has been developed. It uses learning vector quantization neural network linked to a Mössbauer data bank that contains Mössbauer parameters of isomer shift, quadrupole spliting, internal magnetic field and the references of the substances. The program identifies the substance under study and/or its crystalline structure when fed with experimental Mössbauer parameters. It can also list the references from the literature by feeding the name of the substance or the author of the publication. Typical application of Mössbauer Effect Assistant in iron-bearing materials Mössbauer spectroscopy is present in user friendly Microsoft Windows environment.     

Mössbauer spectroscopy of magnetic minerals in basalt on Earth and Mars

Mössbauer spectroscopy of iron–titanium containing spinel phases is reviewed. New techniques are presented for determination of their composition using room-temperature Mössbauer spectroscopy. An example of thermal alteration processes is described. The speciality of olivine-containing basalt is briefly discussed with regard to its magnetic properties.