Search

Potassium ferrate(VI) (K2FeO4) as a particularly strong oxidant represents an effective and environmentally friendly waste water treatment material. When produced by anodic oxidation in highly alkaline aqueous solution, the K2FeO4 product is separated and sealed in inert plastic bags with the retention of some liquid phase with high pH. This method proved to be excellent for long-term storage at moderately low temperature (5 °C) for industrial applications. It is still imperative to check the ferrate(VI) content of the product whenever it is to be used. Fe-57 Mössbauer spectroscopy is an excellent tool for checking the ratio of ferrate(VI) to the degradation product iron(III) in a sample. For this purpose, normally the spectral areas of the corresponding subspectra are considered; however, this approximation neglects the possible differences in the corresponding Mössbauer–Lamb factors. In this work, we have successfully determined the Mössbauer–Lamb factors for the ferrate(VI) and for the most common iron(III) degradation products observed. We have found superparamagnetic behavior and low-temperature phase transformation for another iron(III) degradation product that made the determination of the Mössbauer–Lamb factors impossible in that case. The identities of a total of three different iron(III) degradation products have been confirmed.

The effect of swift heavy ion irradiation on sol–gel-prepared maghemite nanoparticles was studied by 57Fe transmission Mössbauer spectroscopy and X-ray diffractometry (XRD). The room temperature Mössbauer spectra of the non-irradiated nano-maghemite showed poorly resolved magnetically split, typical relaxation spectra due to the superparamagnetic state of the nanoparticles. Significant changes in the line shape, indicating changes in the superparamagnetic state, were found in the Mössbauer spectra upon irradiation by 160 MeV and 155 MeV 132Xe26+ ions with fluences of 5 × 1013 ion cm−2 and 1 × 1014 ion cm−2. XRD of the irradiated maghemite nanoparticles showed a significant broadening of the corresponding lines, indicating a decrease in the crystallite size, compared to those of the non-irradiated ones. The results are discussed in terms of the defects induced by irradiation and the corresponding changes related to the change in particle size and consequently in the superparamagnetic state caused by irradiation.

In this paper, a relationship between the structure and the electrical properties of a nanocrystalline composite ceramics xNa2O·(100 − x)V2O5 with ‘x’ of 5, 15, 25, 35, and 45 mol%, abbreviated as xNV, was investigated by X-ray diffractometry (XRD), X-ray absorption spectroscopy (XAS), Cyclic Voltammetry (CV), Electrochemical impedance spectroscopy (EIS), and cathode active performance in Na-ion battery (SIB). For the expected sodium vanadium bronzes (NaxV2O5) precipitation, the preparation of xNV was performed by keeping the system in the molten state at 1200 °C for one hour, followed by a temperature decrease in the electric furnace to room temperature at a cooling rate of 10 °C min−1. XRD patterns of the 15NV ceramic exhibited the formation of Na0.33V2O5 and NaV3O8 crystalline phases. Moreover, the V K-edge XANES showed that the absorption edge energy of ceramics 15NV recorded at 5479 eV is smaller than that of V2O5 at 5481 eV, evidently indicating a partial reduction from V5+ to V4+ due to the precipitation of Na0.33V2O5. In the cyclic voltammetry, reduction peaks of 15NV were observed at 1.12, 1.78 V, and 2.69 V, while the oxidation peak showed up only at 2.36 V. The values of the reduction peaks were related to the NaV3O8 crystalline phase. Moreover, the diffusion coefficient of Na+ (DNa+) gradually decreased from 8.28 × 10−11 cm2 s−1 to 1.23 × 10−12 cm2 s−1 with increasing Na2O content (x) from 5 to 45 mol%. In the evaluation of the active cathode performance of xNV in SIB, ceramics 15NV showed the highest discharge capacity 203 mAh g−1 at a current rate of 50 mA g−1. In the wider voltage range from 0.8 to 3.6 V, the capacity retention was maintained at 50% after 30 cycles, while it was significantly improved to 90% in the narrower voltage range from 1.8 to 4.0 V, although the initial capacity decreased to 56 mAh g−1. It is concluded that the precipitation of the Na0.33V2O5 phase improved the structural and electrical properties of 15NV, which provides a high capacity for the Na-ion battery when incorporated as a cathode active material.

The present review describes our long experience in the application of Mössbauer spectroscopy with a high velocity resolution (a high discretization of the velocity reference signal) in the studies of various nanosized and nanostructured iron-containing materials. The results reviewed discuss investigations of: (I) nanosized iron cores in: (i) extracted ferritin, (ii) ferritin in liver and spleen tissues in normal and pathological cases, (iii) ferritin in bacteria, (iv) pharmaceutical ferritin analogues; (II) nanoparticles developed for magnetic fluids for medical purposes; (III) nanoparticles and nanostructured FINEMET alloys developed for technical purposes. The results obtained demonstrate that the high velocity resolution Mössbauer spectroscopy permits to excavate more information and to extract more spectral components in the complex Mössbauer spectra with overlapped components, in comparison with those obtained by using conventional Mössbauer spectroscopy. This review also shows the advances of Mössbauer spectroscopy with a high velocity resolution in the study of various iron-based nanosized and nanostructured materials since 2005.

57Fe transmission and conversion electron Mössbauer spectroscopy as well as XRD were used to study the effect of swift heavy ion irradiation on stress-annealed FINEMET samples with a composition of Fe73.5Si13.5Nb3B9Cu1. The XRD of the samples indicated changes neither in the crystal structure nor in the texture of irradiated ribbons as compared to those of non-irradiated ones. However, changes in the magnetic anisotropy both in the bulk as well as at the surface of the FINEMET alloy ribbons irradiated by 160 MeV 132Xe ions with a fluence of 1013 ion cm−2 were revealed via the decrease in relative areas of the second and fifth lines of the magnetic sextets in the corresponding Mössbauer spectra. The irradiation-induced change in the magnetic anisotropy in the bulk was found to be similar or somewhat higher than that at the surface. The results are discussed in terms of the defects produced by irradiation and corresponding changes in the orientation of spins depending on the direction of the stress generated around these defects.

In this mini-review of our research group’s activity, the application of 57Fe Mössbauer spectroscopy in studies of electronic structure, coordination environment, and magnetic interactions in an interesting series of Fe(II/III) compounds selected is discussed. We selected two prominent phenomena that arose during investigations of selected groups of compounds carried out at different periods of time: (1) very high magnetic hyperfine fields observed at low temperatures; (2) changes in the oxidation state of the central iron atom of complexes in the solid state during interactions with gaseous O2/H2O mixtures, resulting in spin crossover (SCO).

Interactions of a series of indole-3-alkanoic acids (with n-alkanoic acid side-chains from C1 to C4) with iron(III) in acidic aqueous solutions have been shown to comprise two parallel processes including complexation and redox transformations giving iron(II) hexaaquo complexes. The structure and composition of the reaction products are discussed, as analysed using a combination of instrumental techniques including 57Fe Mössbauer, vibrational and HNMR spectroscopies.

Low-alloy 42CrMo4 steels were studied by 57Fe Mössbauer spectroscopy (MS), X-ray diffractometry (XRD), and Energy Dispersive X-ray Spectroscopy (EDS) measurements. The investigations were performed on metallographic samples, which were subjected to a series of successive grinding and polishing with a progressively finer grit. Conversion X-ray Mössbauer spectroscopy (CXMS) was used to determine the occurrence of austenite in steel samples. It is a unique method detecting the austenite content very sensitively. Six samples with different surface preparation were investigated, starting with 4.8% of austenite on an as-cut sample, and a large decrease in the retained austenite to 2.6% was observed after the first grinding of a hardened cut sample. Additionally, an unexpectedly large decrease in the austenite content to 2.3% was found due to the final polishing. A second time applied successive grinding and polishing of all samples resulted in identical austenite content determined by CXMS of approx. 5%, which proved the applicability of the CXMS method. Generally, the result calls attention to the importance of preparation of metallurgical samples by grinding and polishing where the results can vary significantly on the level of surface processing.

To establish the structure of ferric ions in strongly alkaline (pH > 13) environments, aqueous NaOH solutions supersaturated with respect to Fe(iii) and the solid ferric-hydroxo complex salts precipitating from them have been characterized with a variety of experimental techniques. From UV measurements, in solutions of pH > 13, only one kind of Fe(iii)-hydroxo complex species was found to be present. The micro crystals obtained from such solutions were proven to be a new, so far unidentified solid phase. Mössbauer spectra of the quick-frozen solution and that of the complex salt indicated a highly symmetrical ferric environment in both systems From the EXAFS and XANES spectra, the environment of the ferric ion in these solutions (both native and quick-frozen) and in the complex salt was found to be different. In the complex salt, the bond lengths are consistent with an octahedral coordination around the ferric centres. In solution, the coordination geometry of Fe(iii) is most probably tetrahedral. Our results demonstrate that in strongly alkaline aqueous solutions, ferric ions behave very similarly to other structurally related tervalent ions, like Al(iii) or Ga(iii). [ABSTRACT FROM AUTHOR]

Abstract  The corrosion properties of the passive layers formed on iron-nickel-chromium electrodeposits of Fe29Ni51Cr20 were investigated in 0.3 M borate solution at a‘ pH of 8.4. On the basis of measurements by cyclic voltammetry, chronopotentiometry and electrochemical impedance spectroscopy, a low passive dissolution/corrosion rate was identified for the electrodeposited Fe-Ni-Cr alloys due to the nature of the established corrosion layer. The stability of this passive layer was further enhanced after corrosion under oxidizing conditions. M�ssbauer spectroscopic measurements confirmed the existence of a thin passive layer on the amorphous electrodeposits. [ABSTRACT FROM AUTHOR]

The chemical reactions between iron(III) and indole-3-acetic (IAA), -propionic (IPA), and -butyric (IBA) acids were studied in acidic aqueous solutions. The motivation of this work was that IAA is one of the most powerful natural plant-growth-regulating substances (phytohormones of the auxin series). Mössbauer spectra of the frozen aqueous solutions of iron(III) with indole-3-alkanoic acids as ligands (L), showed parallel reactions between Fe3+ and the ligands. Partly, it resulted in a complex formation which precipitated in aqueous solution and partly, in a redox process with iron(II) and the oxidised indole-3-alkanoic acids as products. The Mössbauer parameters of the Fe2+ species suggested a hexaaquo coordination environment. The chemical composition and coordination structure of the precipitated complexes were investigated using elemental analysis, Mössbauer spectroscopy, Fourier transform infrared (FTIR) and Raman spectroscopic techniques. The complexes were soluble in some organic solvents. So, Mössbauer, FTIR and solution X-ray diffraction measurements were carried out on the solution of complexes in acetone, hexadeutero acetone and methanol, respectively. The data obtained supported the existence of the μ-dihydroxo-bridging structure of the dimer: [L2Fe<(OH)2>FeL2] (where L is indole-3-propionate, -acetate or -butyrate). [ABSTRACT FROM AUTHOR]

Abstract: Transport and magnetic properties of LaCoO3-based compounds, doped with 20% Sr and 2.5, 5, 10, 15, 20 and 30% Fe, were investigated by means of magnetization, resistivity and magnetoresistance measurements as well as by 57Fe Mössbauer spectroscopy. While the temperature dependence of the dc and ac magnetic susceptibilities reveals the presence of magnetic phase separation accompanied by spin-glass and cluster-glass behavior, the electrical resistivity and magnetoresistance characteristics indicate that the mesoscopic structure of the present compounds is rather well described as consisting of ferromagnetic, metallic grains embedded in an insulating matrix. The effect of the partial Co→Fe substitution on the bulk magnetic and transport properties, as well as on the local state of Co and Fe ions is discussed. [Copyright &y& Elsevier]