Mössbauer spectroscopic studies on mixed-valence states in trinuclear iron carboxylates

Mixed-valence states of iron atoms in newly synthesized mixed-valence trinuclear iron carboxylate complexes with -bonding ligands, such as acrylate, diphenylacetate, 1-naphthylacetate, and cyclohexylacetate which has no -bonding, were studied by means of Mössbauer spectroscopy. The cyclohexylacetate complex shows a temperature-dependent valence delocalization, while the 1-naphthylacetate complex shows temperature-independent mixed-valence states. The acrylate and diphenylacetate complexes show temperature-dependent mixed-valence states, although they do not reach an averaged-valence state at room temperature.     

Uses and perspectives of Mössbauer spectroscopic studies of iron minerals in coal

The processes involved in the utilization of coal are affected by the minerals contained in it. Due to the presence of iron as a major constituent of coal mineral matter, and to the fact that the iron minerals, especially pyrite, and their transformation products play an important role in coal uses, ⁵⁷Fe-Mössbauer spectroscopy appears as an attractive tool in coal research. Mössbauer studies related to the characterization of iron phases, coal oxidation and quantitative determination of pyritic sulphur are discussed in this work.     

Electron hopping in the Mössbauer spectrum of mixed valence freudenbergite

Samples of pure ferric, ferrous and mixed valence freudenbergite were prepared by different techniques. The ⁵⁷Fe Mössbauer spectra of the single valence samples showed poorly resolved quadrupole splittings for the ferric sample, two well-resolved quadrupole splittings for the ferrous sample and electron hopping at, and above, room temperature for the mixed valence sample, which disappeared on lowering the temperature to 50 K.     

Mössbauer spectroscopic study of ferrocene derivatives in the adsorption and liquid-crystalline states

Mössbauer spectra of ferrocene derivatives in the solid, adsorption and liquidcrystalline states were measured at temperatures ranging from 78 to 423 K. The peak intensities of the Mössbauer spectra of ferrocene derivatives adsorbed on silica gel decreased markedly with an increase in temperature. The Mössbauer absorption of [4-(4-methoxyphenoxycarbonyl)-phenoxycarbonyl]alkyl 4-ferrocenylbenzoate at 295 K during the cooling process was observed in what was assumed to be the liquid-crystalline state.     

Mössbauer spectroscopic studies of ferrocene adsorbed on silica gel

Mössbauer spectra of ferrocene adsorbed on silica gel were measured in order to study the state of adsorption. Ferrocene adsorbed on silica gel tended to oxidize in air and form ferricenium ion. It is assumed that the oxidation of adsorbed ferrocene was caused by surface hydroxyls on the silica gel and O₂ in air. It was observed that ferrocene adsorbed weakly at 293 K, although the ferricenium ion adsorbed strongly at 293 K. Thus the adsorption states of ferrocene depend on the experimental condition.     

Mössbauer studies of baotite and bafertisite

The Mössbauer effect was used to study silicate minerals of baotite and bafertisite at 298 K and 95 K. Each spectrum of baotite at 298 K and 95 K consists of two doublets, and they are contributed from Fe²⁺ and Fe³⁺ in the octahedral Tisites, respectively. Each spectrum of bafertisite at 298 K and 95 K is composed of two doublets, and they are mainly caused by Fe²⁺ in the octahedral Fe(I) and Fe(II)sites, respectively. The average effective ionic radii of the Ti sites in baotite and the Fe(I) and Fe(II)sites in bafertisite were estimated based on the correlation of the isomer shifts with the average effective ionic radii in silicates, and they are 0.56 , 0.73 and 0.73 , respectively.     

Structural and Mössbauer spectroscopic studies of Fe0.7−xCrxAl0.3 alloys

Fe_0.7−xCr_xAl_0.3 alloys with x=0, 0.1, 0.2, 0.3 and 0.35 have been synthesized by arc melting and studied by X-ray diffraction and Mössbauer spectroscopy. All the samples studied were found to have single phase with body center cubic structure. The lattice parameter a, and hence the volume, were obtained from the X-ray diffraction patern and found to increase with increasing the chromium concentration. At room temperature Mössbauer studies show magnetic ordering for small values of x and paramagnetic behavior for large values of x under investigation. The Mössbauer spectra were analyzed considering a distribution of magnetic hyperfine fields for small values of x and two singlets were added for large values of x. During the fitting procedure, the relation between the hyperfine field and the isomer shift in the hyperfine field distribution was linear relation. The average hyperfine field and isomer shift as a function of chromium content x were found to decrease with increasing x. The results are explained in terms of local environmental effects on the hyperfine interactions.     

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 and X-Ray studies of MgO-Fe nanocomposite

XRD phase analysis and Mössbauer spectroscopy are used to study the structure of magnesiowustite (Mg_0.9Fe_0.1) obtained via the decomposition of mixed iron-magnesium oxalate in different atmospheres, the structure of MgO-α-Fe composite after reduction by hydrogen in Ar + 5% H₂ gas mixture at 800°C and 1000°C, and the structure of iron at every stage. It was shown that fine particles of α-Fe are obtained upon the decomposition of iron-magnesium oxalate in vacuum at 1000°C. If a precursor is decomposed in high purity Ar, α-Fe particles form during reduction at lower temperature (800°C) due to the partial decomposition of one of the phase components—magnetite.     

Mössbauer and susceptibility studies of FeMoVO7

The oxidic phase FeMoVO₇ of the Fe₂O₃-V₂O₅-MoO₃ system has been synthesized. Susceptibility measurements from 4.2 K to room temperature display an antiferromagnetic behaviour with an effective magnetic moment of 5.80 _b . This value, and the measured Mössbauer isomer shift of 0.40±0.02 mm/s, are characteristic of high-spin Fe(III). The lowT _n value of 15 K suggests a weak interaction among the Fe-O polyhedra. The relative small QS=0.28±0.02 mm/s found in this compound shows that the Fe-O polyhedra symmetry is close to octahedral and almost undistorted.     

Mössbauer spectroscopic investigation of tin-doped thiospinels

The tin-doped sulphur-containing compound of composition Fe_1.05Cr_1.90Sn_0.05S₄, in which tin is located on the octahedral sites as Sn^4?+? in the spinel-related structure, has been examined by ¹¹⁹Sn Mössbauer spectroscopy. The data complement results obtained by ⁵⁷Fe Mössbauer spectroscopy and show that tin increases the magnetic ordering temperature of pure FeCr₂S₄.     

Mössbauer studies of magnetite nanoparticles

Magnetite Fe₃O₄ samples with different levels of dispersion (“bulk” and nanoscale particles with an average diameter of 24, 14 and 7 nm) are studied using Mössbauer spectroscopy. It is shown that this method of analysis makes it possible to obtain important information about the features of magnetic states of iron-containing nanoparticles and, more specifically, about the distinction in effective magnetic fields for iron nuclei located in different regions within them. The obtained results are fully consistent with known theoretical data and allow estimation of the thickness of the surface region of the nanoparticles.     

Mössbauer studies of subfossil oak

With the PANDA experiment at the FAIR facility in Darmstadt, Germany it will be possible to investigate antiproton-nucleus reactions in an energy range not explored so far. This provides opportunities for unique measurements of which some are outlined in this article. Possible modifications of hadron properties in nuclear matter is subject of extensive theoretical and experimental studies. With PANDA it will be possible to extend this kind of studies to the charm sector. A study of particular interest will be to measure the J/Ψ-nucleon dissociation cross-section. This cross-section is relevant for the interpretation of the J/Ψ suppression observed in high energy heavy ion reactions. Further topics include the study of antibaryons in nuclei and short-range nucleon-nucleon correlations.     

Advantages of Mössbauer polarimetric methods in material studies

Mössbauer spectroscopic methods combined with the use of circularly polarized radiation offer element selective, unambiguous measurements of the orientation of hyperfine magnetic field at the nucleus. The paper presents applications of the method in investigations of antiferromagnets and distribution of magnetization inside iron-based nanoparticles. Selected examples showing development of Mössbauer conversion electron polarimetric methods are also reported.     

Mössbauer and magnetization studies of iron oxide nanocrystals

Monodisperse iron oxide nanocrystals have been produced following non-hydrolytic, thermal decomposition routes. Spherically shaped particles with diameter of 4 and 12 nm and cubic shaped particles with an edge length of 9 nm have been studied. The particles have been shown to consist of mainly maghemite. A reduction of the saturation magnetic hyperfine field is observed for the 4 nm particles as compared to the corresponding bulk value. The anisotropy energy determined from the temperature variation of the magnetic hyperfine field was strongly enhanced for the 4 nm particles.     

Magnetic and Mössbauer spectroscopic studies of NiZn ferrite nanoparticles synthesized by a combustion method

The properties of nanocrystalline Ni_0.5Zn_0.5Fe₂O₄ synthesized by an auto-combustion method have been investigated by magnetic measurements and Mössbauer spectroscopy. The as-synthesized single phase nanosized ferrite powder is annealed at different temperatures in the range 673–1,273 K to obtain nanoparticles of different sizes. The powders are characterized by powder X-ray diffraction, vibrating sample magnetometer, transmission electron microscopy and Mössbauer spectroscopy. The as-synthesized powder with average particle size of ~9 nm is superparamagnetic. Magnetic transition temperature increases up to 665 K for the nanosized powder as compared to the transition temperature of 548 K for the bulk ferrite. This has been confirmed as due to the abnormal cation distribution, as evidenced from room temperature Mössbauer spectroscopic studies.     

Integral low-energy electron Mössbauer spectroscopic studies of the surfaces of carbon nanotube-nanocomposite powders

The surface state of CNTs-Fe-Al₂O₃ and CNTs-Fe-MgAl₂O₄ nanocomposite powders was studied by integral low-energy electron Mössbauer spectroscopy (ILEEMS). Several samples, prepared by reduction of α-(Al,Fe)₂O₃ or (Mg,Fe)Al₂O₄ precursors in a H₂-CH₄ atmosphere, were investigated, demonstrating that ILEEMS is a promising tool completing transmission Mössbauer spectroscopy for the investigation of the metal Fe and iron-carbide particles in the different carbon nanotube systems.     

Mössbauer spectroscopic properties of tin-doped iron oxides

The ⁵⁷Fe Mössbauer spectra recorded in situ from tin-doped Fe₃O₄ at elevated temperature in vacuo shows the Curie temperature to decrease with increasing concentrations of the dopant. Thermal treatment under oxidising conditions results in the initial formation of tin-doped γ-Fe₂O₃ which subsequently undergoes a phase transformation to tin-doped α-Fe₂O₃. ⁵⁷Fe Mössbauer spectroscopy at elevated temperatures shows the Néel temperature for tin-doped γ-Fe₂O₃ to be lower than that of pure γ-Fe₂O₃. The ¹¹⁹Sn Mössbauer spectra recorded from all the tin-doped iron oxides show the presence of a hyperfine magnetic field at the Sn⁴⁺ site which is more complex in the spectra recorded from tin-doped γ-Fe₂O₃ and α-Fe₂O₃.     

A Mössbauer spectroscopic study of cobalt-iron molybdates

Fe _x Co_1–x MoO₄ compounds prepared by coprecipitation were studied by XRD, electrical conductivity and mainly by absorption and emission Mössbauer spectroscopy. FeMoO₄ and CoMoO₄ samples were shown to contain Fe³⁺ and Co³⁺, respectively, in solid solution. Three kinds of Fe _x Co_1–x MoO₄ solids can be described. Forx0.16: one has a -Co(Fe²⁺, Fe³⁺)MoO₄ solid solution. For 0.17x0.25: one has the same solid solution with its surface rich in Fe³⁺. Forx0.26: one has the same solid solution with only bulk Fe³⁺, and ferric molybdate. Studies of reduction by hydrogen and of catalytic reaction of mechanical mixtures of CoMoO₄ and ferric molybdate support these statements.     

Mössbauer spectroscopic analysis of ancient Egyptian pottery

Ten pieces of Egyptian pottery ware and eleven silt samples collected at Hierakonopolis (Nile River, Egypt) were studied by Mössbauer spectroscopy. Three Nile silt samples and three pottery sherds were test fired and refired in an oxidized atmosphere up to 1100°C. Changes of the Mössbauer parameters depend upon the firing temperatures as well as the firing atmosphere. Three kinds of pottery were studied: Plum Red Ware, Straw Tempered Ware, and Orange Ware.