Conversion electron Mössbauer and XPS study on the effect of polishing of a stainless steel sample

Conversion electron Mössbauer spectroscopy (CEMS) and XPS has been used for the surface analysis of an X10CrNiTi 18/9 (DIN 1.7440)-type stainless steel in order to determine the supposed structural and/or chemical changes in the surface layer caused by polishing. Both, CEMS and XPS results can be associated with the appearance of Fe nitride in the outer layer of steel samples after polishing, while no sign of nitrogen was detected in the bulk material.     

Influence of surface treatment on microstructure of stainless steels studied by Mössbauer spectrometry

Examination of surface microstructure of stainless steels is presented. Transmission Mössbauer spectrometry and Conversion Electron Mössbauer Spectrometry which provide information from the bulk and surface regions, respectively, were used. We concentrate on structural modifications that were caused by surface treatments including grinding, polishing, and electrolytic etching. Scanning Electron Microscopy with Energy Dispersive Spectrometry was adopted for visualization of surface differences. Formation of magnetic phases was revealed in the surface regions of X6CrNiTi1810 steel while no substantial effect of surface treatment was found in the ATABOR steel. Bulk regions in both steels are not affected by surface treatment.

     

Emission (57Co) Mössbauer spectroscopy as a tool for probing speciation and metabolic transformations of cobalt(II) in bacterial cells

The emission (⁵⁷Co) variant of Mössbauer spectroscopy, rarely used in biology-related studies, was applied to study binding and possible transformations of ⁵⁷Co^II traces in live and dead (hydrothermally treated) cells of the rhizobacterium Azospirillum brasilense (strain Sp7) at T?=?80 K in frozen aqueous suspensions and as their dried residues. The Mössbauer parameters calculated from the spectra were compared with the similarly obtained data reported earlier for another A. brasilense strain, Sp245 (which differs from strain Sp7 by the ecological niche occupied in the rhizosphere and was found earlier to exhibit different metabolic responses under similar environmental conditions). Similarly to strain Sp245, live cells of strain Sp7, rapidly frozen 2 min and 1 h after their contact with ⁵⁷Co²⁺ (measured in frozen suspensions), showed marked differences in their Mössbauer parameters, reflecting metabolic transformations of ⁵⁷Co²⁺ occurring within an hour. However, the parameters for strains Sp7 (this work) and Sp245 (reported earlier), obtained under similar conditions, were found to significantly differ, implying dissimilarity in their metabolic response to Co²⁺. This is in line with their different metabolic responses to several heavy metals, including Co²⁺, detected earlier using Fourier transform infrared spectroscopy.     

Mössbauer investigation of 57Fe-doped TlSr2CoO5

The thallium cobaltite TlSr₂CoO₅ undergoes a metal—insulator transition near room temperature. Mössbauer investigation of a ⁵⁷Fe-doped sample shows that iron actually enters into the lattice and that a long range antiferromagnetic order sets in below 150 K explaining the origin of a peak previously observed in the temperature dependence of the magnetic susceptibility. An unexpected complex behaviour is found for the high temperature phase for which previous electron diffraction and X-ray diffraction studies revealed a single site for Co atoms. The results are interpreted in terms of a dynamical formation of two types of structural domains characterized by a fluctuation of Co-O bond lengths inducing a fluctuation of Co spin state.     

Investigation on the magnetic and Mössbauer spectroscopy of 57Fe doped LiMnPO4

Journal of Radioanalytical and Nuclear Chemistry - The 57Fe doped LiMnPO4 cathode with potential applications in Li-ion batteries was prepared by solid-state reaction. The magnetic susceptibility...     

57Fe Mössbauer spectroscopy on multiwalled carbon nanotubes with metal filling

M?ssbauer measurements at different temperatures are reported for MWCNTs with metallic encapsulations ("nanowires"). The spectra can reasonably be refined with two subpatterns: one providing clear evidence of an iron carbide Fe(3)C (cementite) phase as the main nanowire component and the other yielding a relaxation doublet most probably belonging to the same phase. Whereas the former one displays a well resolved magnetic hyperfine spectrum with Brillouin type temperature dependence, the latter one gains importance with rising temperature or onset of an inhomogeneous external magnetic field. The comparably large incoherent scattering is attributed to the graphene layers of the tube walls. The experimental results are discussed on the background of an interpretation model trying to explain unusual magnetometric results published elsewhere.     

57Fe Mössbauer spectroscopic studies of electron-hopping processes in vesuvianites

Room temperature and liquid-nitrogen temperature ⁵⁷Fe Mössbauer spectra of a number of vesuvianite crystals are reported. Certain of the spectra contain doublets whose parameters are intermediate between those normally associated with Fe²⁺ and Fe³⁺ ions in oxide environments. These doublets are attributed to electron-hopping processes between Fe²⁺ ions and adjacent Fe³⁺ or Ti⁴⁺ ion.     

Mössbauer spectroscopy of corrosion products of mild steel due to microbiologically influenced corrosion

Corrosion products of mild steel exposed to four different cultures of sulfur reducing bacteria (SRB) grown in a synthetic medium have been studied by transmission Mössbauer spectroscopy (TMS). Cultures of SRB studied are two hydrogenase positive strains,Desulfovibrio desulfuricans (DD) andDesulfovibrio vulgaris (DV) and two hydrogenase negative strainsDesulfotomaculum orientis orientis (DO) andDesulfotomaculum nigrificans (DN). The corrosion products generated on the coupons as well as in the broth were studied. In all the cases, the corrosion products removed from coupons showed the presence of green rust 2 (GR2), ferrous sulfides, γ-FeOOH and superparamagnetic (SPM) α-FeOOH in different proportions. The corrosion products from the broth showed a symmetrical central doublet, which indicates the presence of γ-FeOOH and SPM α-FeOOH along with ferrous sulfides. The corrosion products from coupons suspended in sewage water also showed the presence of GR 2 and ferrous sulfides together with oxyhydroxides. FTIR spectrum supports the presence of these phases in corrosion products. The formation of GR 2 on coupons seems to be the first step for the SRB induced corrosion. The corrosion rate has been found in the order of DO>DN>DV>DD.     

Mössbauer study on the crystallization of IR-transmitting aluminate glasses

Heat treatment of 60CaO·10BaO·17Al₂O₃·13Fe₂O₃ glass causes a precipitation of the nanoparticles of antiferromagnetic Ca₂Fe₂O₅ and ferromagnetic BaFe₂O₄. Mössbauer spectra of these glass-ceramics show a magnetic relaxation spectra superimposed on doublets. A Kissinger plot in the DTA method reveals that simultaneous cleavage of Ca-O and Fe-O bonds and that of Ba-O and Fe-O bonds cause the precipitation of Ca₂Fe₂O₅ and BaFe₂O₄, respectively. Introduction of Fe(III) promotes the crystallization of aluminate glass. In the case of iron-free 60CaO·10BaO·30Al₂O₃ glass, Ca₂Al₂O₅ and BaAl₂O₄ particles precipitate instead of Ca₂Fe₂O₅ and BaFe₂O₄ particles, respectively.     

Theoretical Study on Mössbauer Isomer Shift of Layered Compounds

Using the expended chemical bond dielectric theory of complex crystals, we have calculated chemical bond parameters and Mössbauer isomer shift of LnOFeAs as well as AFe₂As₂ which had been chosen due to their layered structures. Results are in good agreement with available experimental data, demonstrating the accuracy of our calculations and theories. The relationship between chemical bond parameters and Mössbauer isomer shift is discussed.     

Mössbauer study of the corrosion of mild steel due to prolonged immersion in deionized water

The corrosion of mild steel as a result of 3 years of immersion in deionized water, using Mössbauer results, indicates that -FeOOH, -FeOOH and Fe₃O₄ are formed as corrosion products. This study shows that purified water will produce -FeOOH only when the exposure time is long. It is proposed that ferrihydrite, which is formed as an intermediate corrosion product, is converted to -FeOOH, which in turn is converted to -FeOOH and Fe₃O₄.     

Mn–Co spinel protective–conductive coating on AL453 ferritic stainless steel for IT-SOFC interconnect applications

This paper presents research on the synthesis and properties of the Mn_1.5Co_1.5O₄ (MC) spinel powder, as well as its application for the preparation of a MC thick film on the AL453 steel to be used for metallic interconnect material in IT-SOFCs. In order to prepare the MC micropowder with excellent homogeneity of the chemical and phase compositions, EDTA gel processes were utilized. In order to improve the contact electrical resistance between an AL453 steel interconnect and the La_0.8Sr_0.2FeO₃ (LSF) cathode and protect the cathode from Cr poisoning, the surface of the AL453 steel was coated with a protective manganese cobaltite spinel matrix using screen printing in combination with an appropriate heat treatment. The oxidation of the AL453/MC composite layer carried out in the air–H₂O gas mixture at 1,073 K for 55 h showed that the spinel coating may serve as an effective barrier against outward Cr diffusion from the AL453 steel and, therefore, significantly inhibit the formation of volatile Cr vapors from the chromia scale. The contact ASR study of the interconnect–cathode interface in the AL453/MC/LSCM/LSF/LSCM/MC/AL453 system carried out in the range of 723?1,073 K in air showed a very large drop in ASR compared to the resistance of the AL453/LSCM/LSF/LSCM/AL453 system without the spinel coating.     

Mn doping on Mössbauer spectroscopy of maricite-NaFePO4 as cathode material

Journal of Radioanalytical and Nuclear Chemistry - Transition metal ion substitution in sodium phosphate is effective in enhancing the performance of a cathode material. The...     

Development and application of parallel-plate avalanche counter for in-beam Mössbauer spectroscopy

For Mössbauer -rays in the in-beam Mössbauer experiments using various beams such as heavy ion, secondary short-lived isotope, and neutron beams, it is important to develop a detector. A parallel-plate avalanche counter (PPAC) is the most suitable gas counter for on-line measurements, because PPAC collects the internal conversion electrons emitted by the Mössbauer effect even under high -background. We evaluated the influences of the pressure and flow rate of the counter gas against the counting efficiency of PPAC, and determined the optimum conditions for use in the in-beam Mössbauer experiments.     

Mössbauer Spectroscopy and Preparation of Hg-1223, Tl-1223 and Tl-1212 Superconductors

Introduction of the Mössbauer nuclei ⁵⁷Fe into Hg-1223 phase and that of ⁵⁷Fe and ¹⁵¹Eu into Tl-1212 and Tl-1223 superconductors were investigated. Samples of high phase purity were obtained. Scanning electron microscopy and optical microscopy in normal and polarized light were employed to study the microstructure of the specimens. Energy dispersive X-ray analysis showed that ⁵⁷Fe in the Hg-based samples and ⁵⁷Fe as well as ¹⁵¹Eu in the Tl-based compounds, entered superconducting phases. Incorporation of Eu³⁺ into the superconducting phase favored the formation of the Tl-1212 phase. Mössbauer spectroscopy showed that Eu³⁺ entered the Ca-site. Two doublets found in the ⁵⁷Fe Mössbauer spectra in both the Hg-1223 and the Tl-1223 phase referred to two different micro-environments of Fe³⁺. The assignment of the ⁵⁷Fe Mössbauer spectra was made under the assumption that Fe favored the 1223 phase. Fe³⁺ may replace Cu in both the square pyramidal, five-fold oxygen coordinated Cu sites between the Ca and Ba-(Sr)-O layers, and in the square planar, four-fold oxygen coordinated Cu sites the Ca layers in the superconducting phases in both the Hg- and the Tl-based materials. From the relative areas of the two doublets, we concluded that the Fe³⁺ preferred the square planar Cu site.     

Study of the dependence of Mössbauer parameters on the outer cation in nitroprussides

The Mössbauer spectra of 29 nitroprussides have been measured and the parameters and correlated with the polarizing power Z/r² of the outer cations. There is no overall correlation but there are limited groups in which a trend can be ascertained. In isoelectronic sequences such as Li⁺, Be²⁺; Mn²⁺, Fe³⁺, where the outer electronic shell remains fixed, while Z/r² increases, a definite trend of decreasing and with increasing Z/r² is observed.     

Influence of heme periphery on the electronic structure and Mössbauer parameters of hemoglobin

For the five-coordinated complexes of ferroprotoporphynynn with imidazole, a quantum-chemical analysis of the electronic structure and Mossbauer spectral parameters has been canied out. Peripheral substituents (CH3, Cf13, C₂H₄COOH) were introduced into the porphynin macrocycle to model the real chemical structure of protopo'phynynn in the heme group of desoxyhemoglobin. The calculations have shown that near the occupation border in the complaes there are MO which are due to the -systems of the CH= CM₂ and CH₂CH₂COOH substituents. The orientalion of the vinyl fragments has a considerable effect on the populations of the Fe d-orbitals and the quadrupole splitting E_Q for the⁵B₁ and⁵B₂ terns.Institute of Biophysics, Ministry of Health, Russian Federation. Translated fromZhurnal Strukturmoi Khimii, Vol. 34, No. 5, pp. 90–93, September–October, 1993.Translated by L. Smolina     

DFT Calculations for Mössbauer Properties on Dinuclear Center Models of the Resting Oxidized Cytochrome c Oxidase

Mössbauer isomer shift and quadrupole splitting properties have been calculated using the OLYP-D3(BJ) density functional method on previously obtained (W.-G. Han Du, et al., Inorg Chem. 2020 , 59, 8906–8915) geometry optimized Fe_a3³⁺−H₂O−Cu_B²⁺ dinuclear center (DNC) clusters of the resting oxidized ( O state) “as-isolated” cytochrome c oxidase (CcO). The calculated results are highly consistent with the available experimental observations. The calculations have also shown that the structural heterogeneities of the O state DNCs implicated by the Mössbauer experiments are likely consequences of various factors, particularly the variable positions of the central H₂O molecule between the Fe_a3³⁺ and Cu_B²⁺ sites in different DNCs, whether or not this central H₂O molecule has H-bonding interaction with another H₂O molecule, the different spin states having similar energies for the Fe_a3³⁺ sites, and whether the Fe_a3³⁺ and Cu_B²⁺ sites are ferromagnetically or antiferromagnetically spin-coupled.