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Our previous studies have revealed that a ”hybrid” structure of the amorphous and crystalline phases is formed in the outermost surface region of the austenitic stainless steel tubes of steam generators (SGs) as an undesired consequence of the industrial application of the AP-CITROX (AP: alkaline permanganate; CITROX: citric and oxalic acid) decontamination technology. The formation of this mobile oxide-layer increased the amount of the corrosion products in the primary circuit significantly, resulting in magnetite deposition on fuel assemblies. Owing to the fact that there is no investigation method available for the in-situ monitoring of the inner surfaces of heat exchanger tubes, a research project based on sampling as well as on ex-situ electrochemical and surface analytical measurements was elaborated. Within the frame of this project, comprehensive investigation of the general corrosion state and metallographic features of 36 stainless steel specimens, cut out from various locations of the 21 steam generators of the Paks NPP in the time period of 2000-2007 has been performed. The present work gives a brief overview on the general corrosion state of the heat exchanger tubes of SGs, concerning the long-term effects of the AP-CITROX procedure on the chemical composition and structure of the protective oxide-layer.

Nanoscroll formation by casacade intercalation–exfoliation method was investigated for a high iron-content kaolin and after the removal of its iron-bearing mineral constituents (goethite, hematite) by 11 M HCl treatment. Hindered kaolinite nanoscroll formation was observed by TEM in both cases, where the 11 M HCl treatment only slightly improved the occurrence of nanoscrolled shapes. The presence of minor amounts of well-dispersed, resilient Fe was observed after the exfoliation of 11 M HCl-treated sample, which was identified as structural Fe3+/Fe2+ in the octahedral sheet of kaolinite by Mössbauer and X-ray absorption spectroscopy. Iron substitution in the nanokaolinite TO layers was probed by computational chemistry. The computational results indicate inner coordination changes and elongation of bonds in the iron-substituted TO structure, and the increased curvature values offer an explanation for the observed experimental results for hindered nanoscroll formation. Graphical abstract

A highly efficient photo-Fenton catalyst iron silicate glass was successfully prepared by a simple sol–gel method. The characterization results (XRD, Mössbauer spectroscopy, TEM, and FT- IR) showed that fayalite, clinoferrosilite and hematite nanoparticles were precipitated in the glass system. The catalytic activity of the glass samples was evaluated by measuring the degradation efficiency for organic dyes as well as for a typical persistent organic pollutant phenol, under visible light irradiation, in the presence of hydrogen peroxide (H2O2). The chemical oxygen demand (COD) and total organic carbon (TOC) were measured to see the progress in degradation of phenol. The results showed that the catalyst containing 20% iron had good catalytic properties for the degradation of both types of organic contaminants with superior stability for the degradation of methylene blue dye even after six cycles. Finally, a possible photocatalytic mechanism was proposed.

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.

Pure and doped iron oxide and hydroxide nanoparticles are highly potential materials for biological, environment, energy and other technological applications. On demand of the applications, single phase as well as multiple phase of different polymorphs or composites of iron oxides with compatible materials for example, zeolite, SiO

Chemical stability and good biocompatibility under physiological conditions render nanoparticles made of the spinel oxide magnetite a favorable choice in biomedical diagnostic and therapeutic applications that benefit from high levels of magnetization and superparamagnetism. Under ambient atmosphere, however, magnetite nanoparticles are prone to undesired oxidation leading to an at least partially oxidized form of magnetite. In the present work Fe3-xO4 nanopowders (with a particle size of 10–50 nm) were prepared under different conditions via chemical co-precipitation method, resulting in samples with different oxidation levels. The effect of oxidation of the prepared samples on their morphological, structural, electronic and magnetic properties is followed, respectively, by the means of transmission electron microscopy (TEM), powder X-ray diffractometry (PXRD), 57Fe Mossbauer spectroscopy (MS) and electron magnetic resonance (EMR) spectroscopy measurements. A novel method is applied to decompose the heavily broadened room-temperature 57Fe Mossbauer spectra of the nanoparticles into signals of intermediate valence Fe2.5+ and that of Fe3+ iron species. The results indicate that the cubic lattice parameter of non-stoichiometric magnetite nanoparticles depends on the concentration as well as on the mean oxidation level of the intermediate valence iron species. At the same time, EMR spectra of the samples indicate that oxidation influences the magnetic anisotropy of the nanoparticles, with the magnitude of the nanoparticles' magnetic anisotropy field being correlated with the concentration of the intermediate valence iron species. Malic acid, used as coating agent for several of the samples, is shown to hinder the oxidation of magnetite nanoparticles.

Sn-Fe-Ni-Co quaternary alloys, in the composition range of 37–44 at% Sn, 35–39 at% Fe, 6–8 at% Ni and 13–17 at% Co, were prepared by direct current (DC) and pulse plating (PP) electrodeposition. The alloy deposits were characterized by XRD, 57Fe and 119Sn conversion electron Mössbauer spectroscopy, SEM-EDX and magnetization measurements. XRD revealed the amorphous character of the quaternary alloy deposits. The dominant ferromagnetic character of the deposits was shown by magnetization and Mössbauer spectroscopy measurements. Room temperature Mössbauer spectra showed minor paramagnetic phases, where their occurrences (~3–20%) are correlated to the electrodeposition parameters (Jdep from −16 to −23 mA/cm2 for DC, Jpulse from −40 to −75 mA/cm2 for PP), the composition and the saturation magnetization (~52–73 emu/g). A considerable difference was found in the magnetization curves applying parallel or perpendicular orientation of the applied fields, indicating magnetic anisotropy both in DC and pulse plated alloy coatings.

Nanoparticles of e-Fe2O3 in an amorphous silica matrix were prepared by the sol–gel method without using a precursor. X-ray diffraction patterns reflect a completely amorphous state for the samples even after heat-treated up to 600 °C, while at higher temperatures the formation of crystalline iron oxide phases was observed. Transmission electron microscopy analysis showed a wide size distribution of nanoparticles from 3±0.5 to 46±0.8 nm. The occurrence of e-Fe2O3 particles depends on several factors like annealing temperature, particle size and iron concentration in initial chemicals. Based on the 57Fe Mossbauer spectra, three octahedral and one tetrahedral iron site were identified for e-phase. The optimized conditions for the preparation of e-Fe2O3 rich sample were confirmed and ~ 90% of the e-Fe2O3 phase was obtained with the particle size of 15±0.6 nm. The high coercivity of ~ 1.18 T at room temperature was confirmed for our nanoparticle system.

The research investigated three iron carbonate (siderite) sedimentary concretions from Nagykovacsi, Uri and Delegyhaza, Hungary. To identify possible source rocks and effects of the glaze-like exposed surface of the concretions, we carried on comparative petrological, mineralogical, geochemical and isotopic studies. The samples were microbially mediated siderite concretions with embedded metamorphous and igneous mineral clasts, and had specific rim belts characterized by semi-concentric outer Fe-oxide layers, fluffy pyrite-rich outer belts and siderite inner parts. We investigated the cross section of the Fe-carbonate concretions by independent methodologies in order to identify their rim effects. Their surficial oxide layers showed evidence of degassing of the exposed surface caused most probably by elevated temperatures. The inner rim pyrite belt in the concretions excluded the possibility of a prolonged wet surface environment. Microtextural and mineralogical features did not support desert varnish formation. 10Be nuclide values of the Nagykovacsi and Uri concretions were far above the level of terrestrial in-situ cosmogenic nuclides, but they were consistent with the lowest levels for meteorites. Though the data were not conclusive to confirm any kind of known origin, they are contradictary, and open possibilities for a scenario of terrestrial meteorite origin.

The interaction between Lanthanides (Ln) - ions and Ca-bentonite and the structural changes accompanying were studied. Ln -exchanged bentonites were prepared from Ca-bentonite (Istenmezeje, Hungary) by ion exchange in three consecutive washings with lanthanide solutions. Scanning Eletronmicroscopy Energy Dispersive X-ray spectroscopy (SEM-EDX) studies showed even distribution of Ln s and other components of bentonite. The natural bentonite and the lanthnide exchanged bentonites were characterized by X-ray diffraction (XRD), which revealed the same mineral composition, and the increase of the basal spacing of montmorillonite from 1.465 (Ca 2+ ) to 1.577 nm (REE 3+ ). The d 001 basal spacing of lanthanide montmorillonite increases as the ion radius of the lanthanide cation increases. The Fe 3+ , and Ln s 3+ amount on the bentonite were determined by X-ray-fluorescence spectrometry (XRF) elemental analysis. The amount of exchanged Ln s were determined by washing the Ln -bentonite with 1 M ammonium-acetate, and measuring the amount of Ln released, using inductively coupled plasma optical emission spectrometry (ICP-OES). In most Ln -bentonites, the quantity of the exchanged Ln ions was about 80–90% of the cation exchange capacity (CEC) of the bentonite. In case of some lanthanides bentonite (La 3+ , Ce 3+ , and Gd 3+ ), however, the sorbed quantity of lanthanum ions was higher than the cation exchange capacity. In case of lanthanum-bentonite, the lanthanide quantity is as high as 136% of CEC. Moreover, the iron(III) content of lanthanum bentonite is less than that of the original Ca-bentonite. Mossbauer spectra of the La-, Ce-, and Gd-exchanged samples at 78 K revealed an unexpected magnetically split component that was absent from the Ca-bentonite. This component may belong to interlayer Fe. This iron can be released from the octahedral positions crystal lattice.

Comparison of the Mossbauer spectra of the as-prepared native iron oxide nanoparticles (IONs) and the citrate-functionalized IONs demonstrates differences in the spectral shapes at room temperature and variations of the 57Fe hyperfine parameters at 80 K. The observed differences are claimed to result from capping the IONs with citrate, thus decreasing the particle-particle interaction while promoting interaction of the outer atomic layers of the IONs with the surface molecular coating.

Microbial cells are well known to be capable of remaining viable when desiccated, and a variety of beneficial microorganisms can thus be preserved for storage. For the ubiquitous widely studied soil bacterium Azospirillum brasilense (wild-type strain Sp7), which has a significant agrobiotechnological potential owing to its plant-growth-promoting capabilities perspective for its use in biofertilisers, Fourier transform infrared (FTIR) spectroscopy (in the diffuse reflectance mode, DRIFT) was used to control the state of biomass, together with 57Fe transmission Mossbauer spectroscopy to monitor intracellular iron speciation in live rapidly frozen cell suspension and in the lyophilised biomass (both measured at T = 80 K). It has been shown for the first time that a relatively large part of ferrous iron in live cells (22% of the whole cellular iron pool, represented by two high-spin Fe(II) forms, in the 18-h culture grown on 57Fe(III) complex with nitrilotriacetic acid as the sole source of iron) gets largely oxidised upon lyophilisation. The remaining part of iron(II) in the resulting dry biomass was found to be ca. 3% only. The major part of ferric iron in the dry biomass was shown to be comprised of ferritin-like ferric species (giving a typical magnetically split sextet at T = 5 K), while the iron(III) formed from cellular iron(II) by oxidation in air in the course of drying remained in a paramagnetic state even at T = 5 K. The possibility of intracellular iron(II) oxidation to iron(III) upon desiccation may be a specific natural strategy to avoid cell damage caused by Fenton-type reactions in dormant (frozen, dried) cells. The results obtained may have important implications related to iron speciation and redox transformations in dried bacterial preparations intended for long-term storage.

A relationship between the local structure and the visible-light activated photocatalytic effect was investigated in the glass and glass ceramics prepared by recycling waste slag, which was discharged from a Tokyo Household Garbage Combustion Plant. For the preparation of a homogeneous sample of waste slag recycled glass, (WSRG), 10 wt% of Na2CO3 and 10–50 wt% of Fe2O3 were added. 57Fe-Mössbauer spectra of WSRG recorded at liquid nitrogen temperature showed three types of magnetic hfs; one due to FeII(O h) with δ of 1.21 mm s−1 and H int of 46.7 T, one due to FeIII(O h) with δ of 0.46 mm s−1 and H int of 44.1 T, and the other due to FeIII(T d) with δ of 0.38 mm s−1 and H int of 47.8 T. They were superimposed on a relaxation spectrum due to superparamagnetic hematite. Methylene blue (MB) degradation test with 40 mg of the heat treated WSRG (50 wt% Fe2O3), under the visible-light irradiation for 6 h showed a marked decrease in the concentration of MB from 20 to 7.7 μmol L−1 with a rate constant (k) of 2.7×10−3 min−1 which was close to the k, 9.26×10−3 min− 1, recently obtained in 15Na2O⋅15CaO⋅40Fe2O3⋅ 11Al2O3⋅19SiO2 glass.

The effect of coating with nine different carboxylic acids (glycolic, propionic, lactic, malic, tartaric, citric, mandelic, caproic and caprylic) on nanostructured magnetite (D ~ 10 nm) was studied by Raman and photoacoustic, magnetic and 57Fe Mossbauer measurements. Mossbauer spectra of frozen suspensions showed dominantly magnetically split envelopes at lower temperatures, which were evaluated by hyperfine field distribution method. Mossbauer and Raman spectroscopy indicated similar variation of relative occurrence of magnetite and maghemite phases. These results are discussed on the basis of the hypothesis that different carboxylic acids can promote either the oxidation or reduction of iron oxide nanoparticles.

In the emission (57Co) variant of Mossbauer spectroscopy (EMS), the 57Co radionuclide (with a half-life of 9months) is used that undergoes a nuclear decay 57Co→57Fe via electron capture followed by the emission of a γ-quantum, the energy of which is modified by the chemical state and the close coordination environment of the parent 57Co atom. While EMS has been used largely in materials science and nuclear chemistry, its high sensitivity can also be of great advantage in revealing fine structural features and for speciation analysis of biological complexes, whenever the 57Co2+ cation can be used directly as the coordinating metal or as a substitute for native cobalt or other metal ions. As such EMS applications are yet rare, in order to reliably interpret emission spectra of sophisticated 57Co2+-doped biosystems, model EMS studies of simple cobalt biocomplexes are necessary. In this work, EMS spectroscopic data are analysed and discussed for 57Co2+ complexes with a range of small biomolecules of different structures, including 4-n-hexylresorcinol, homoserine lactone and a few amino acids (spectra measured in rapidly frozen dilute aqueous solutions or in the dried state at T=80K). The EMS data obtained are discussed with regard to the available literature data related to the coordination modes of the biocomplexes under study.

Magnetic interaction of the magnetite (Fe3O4) nanoparticles grown on zeolite has been studied. XRD patterns show that in the presence of 25–75 mg of zeolite the average particle size of Fe3O4 decreases to ≈6 nm, but with the increase of zeolite content (75 mg

57 Fe conversion electron Mossbauer spectroscopy was used to study the effect of swift heavy ion irradiation on electrochemically deposited metallic pure α-iron. We succeeded in preparing superparamagnetic iron by irradiating the electrochemically prepared thin α-iron films using 247 MeV Kr ions with a fluence of 1×10 13 ion cm −2 which converted 50% of crystalline α-iron into amorphous and superparamagnetic phases, the latter being >20%. The results are discussed in terms of the thermal spike model for the formation of the amorphous phase which could be essential for the formation of superparamagnetic iron.

We report the hydrothermal synthesis and structure of FexCo1−x alloy nanoparticles with considerable stability against oxidation under ambient atmosphere. Powder X-ray diffractometry (XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), inductively coupled plasma mass spectrometry (ICP-MS), 57Fe Mossbauer spectroscopy and magnetization measurements are applied to characterize the composition, morphology, crystal structure, atomic order and magnetic properties of the nanoparticles. As-prepared samples are composed mainly of the bcc FexCo1−x alloy phase. TEM images of heat-treated samples confirm the nanoparticle nature of the original alloys. A consistent analysis of the experimental results leads to x ≈ 53% and x ≈ 62% Fe atomic ratio respectively in two analogous alloy samples, and suggests that the atomic level structure of the nanoparticles corresponds to that of a fully disordered (A2-type) alloy phase. Exploration of the effect of cobalt on the 57Fe hyperfine parameters of iron microenvironments suggests that in these alloys the electronic state of Fe atoms is perturbed equally and in an additive manner by atoms in their first two coordination spheres.

Iron sulfide (troilite) inclusion extracted from Sikhote-Alin IIAB iron meteorite was examined for its composition, structure and magnetic properties by means of several complementary analytical techniques such as: powder X-ray diffractometry, scanning electron microscopy combined with energy-dispersive X-ray spectroscopy, magnetization measurements, ferromagnetic resonance spectroscopy and 57 Fe Mossbauer spectroscopy with a high velocity resolution. The applied techniques consistently indicated the presence of daubreelite (FeCr 2 S 4 ) as a minority phase beside troilite proper (FeS). As revealed by 57 Fe Mossbauer spectroscopy, the Fe atoms in troilite were in different microenvironments associated with either the ideal FeS structure or that of a slightly iron deficient Fe 1– x S. Phase transitions of troilite were detected above room temperature by ferromagnetic resonance spectroscopy. A novel analysis of 295 and 90 K 57 Fe Mossbauer spectra was carried out and the hyperfine parameters associated with the ideal structure of troilite were determined by considering the orientation of the hyperfine magnetic field in the eigensystem of the electric field gradient at the 57 Fe nucleus.

The relationship between the local structure and magnetic properties of iron phosphate glass xFe2O3 • (100-x) P2O5 abbreviated as xFeP prepared by a sol-gel method has been investigated. From the Mossbauer spectroscopy results, it was found that iron ions are present in FeIII(distorted octahedral) and FeII(octahedral) coordination. HAADF-STEM images and elemental mapping results revealed that iron and phosphorus are uniformly dispersed in the system. It is clear from the magnetic susceptibility results that only 50FeP glass heat-treated at 200°C shows spin glass behavior and all other glasses are superparamagnetic at low temperatures. The Weiss temperatures (θw) obtained for all the glasses were negative, suggesting that the interaction between the magnetic moments is antiferromagnetic. In these samples, the higher the proportion of FeIII ions, the higher the frustration of the entire system is. The [FeIII] / [Fetotal] molar ratio decreases as the heat-treatment temperature increased.

Iron-oxide nanoparticles were prepared by chemical coprecipitation method in inert gas atmosphere and also in air atmosphere in order to use them as possible nutrition source for plants. The samples were characterized by 57Fe Mossbauer spectroscopy, electron ¨ microscopy and PXRD measurements. The presence of considerable FeII contributions were indicated by 57Fe Mossbauer spectra. Furthermore TEM and XRD reflected nanomagnetite ¨ in washed and lyophilized samples prepared in inert gas atmosphere while the samples prepared in air atmosphere contained much higher amount of FeIII than characteristic of magnetite. In the case of samples prepared in inert gas, it was also shown that the immediate washing after the coprecipitation has a crucial influence on the FeII content of the nanomagnetites.

For the ubiquitous diazotrophic rhizobacterium Azospirillum brasilense, which has been attracting the attention of researchers worldwide for the last 35 years owing to its significant agrobiotechnological and phytostimulating potential, the data on iron acquisition and its chemical speciation in cells are scarce. In this work, for the first time for azospirilla, low-temperature (at 80 K, 5 K, as well as at 2 K without and with an external magnetic field of 5 T) transmission Mössbauer spectroscopic studies were performed for lyophilised biomass of A. brasilense (wild-type strain Sp7 grown with (57)Fe(III) nitrilotriacetate complex as the sole source of iron) to enable quantitative chemical speciation analysis of the intracellular iron. In the Mössbauer spectrum at 80 K, a broadened quadrupole doublet of high-spin iron(III) was observed with a few percent of a high-spin iron(II) contribution. In the spectrum measured at 5 K, a dominant magnetically split component appeared with the parameters typical of ferritin species from other bacteria, together with a quadrupole doublet of a superparamagnetic iron(III) component and a similarly small contribution from the high-spin iron(II) component. The Mössbauer spectra recorded at 2 K (with or without a 5 T external field) confirmed the assignment of ferritin species. About 20% of total Fe in the dry cells of A. brasilense strain Sp7 were present in iron(III) forms superparamagnetic at both 5 and 2 K, i.e. either different from ferritin cores or as ferritin components with very small particle sizes.

A relationship between structure and visible light-activated photocatalytic activity of iron-containing soda lime aluminosilicate (15Na2O⋅15CaO⋅40Fe2O3⋅xAl2O3⋅(30−x)SiO2) glass (xNCFAS) was investigated by means of 57Fe-Mossbauer spectroscopy, X-ray diffractometry (XRD) and UV–visible light absorption spectroscopy (UV–VIS). The 57Fe-Mossbauer spectrum of 11NCFAS glass measured after heat-treatment at 1000 °C for 100 min was composed of a paramagnetic doublet due to FeIII(Td) and two magnetic sextets due to regular hematite (α-Fe2O3) and hematite with larger internal magnetic field. X-ray diffraction patterns of heat-treated xNCFAS samples resulted in decrease of α-Fe2O3 and increase of Ca2Fe22O33 or CaFe2O4 with alumina content. A quick decrease in methylene blue (MB) concentration from 15.6 to 4.7 μmol L−1 was observed in the photocatalytic reaction test with 40 mg of heat-treated 11NCFAS glass under visible light-exposure. The largest first-order rate constant of MB decomposition (k) was estimated to be 9.26 × 10−3 min−1. Tauc’s plot yielded a band gap energy (Eg) of 1.88 eV for heat-treated 11NCFAS glass, which is smaller than previously reported Eg of 2.2 eV for α-Fe2O3. These results prove that addition of Al2O3 into iron-containing soda lime silicate glass is favorable for the preparation of improved visible light-photocatalyst with ‘ubiquitous’ elements.

Frozen aqueous solution of hyperalkaline tin(II)-hydroxide was analysed by 119Sn Mossbauer spectroscopy at low temperature in order to determinate the structure of the hydroxo complex formed under hyperalkaline (pH > 13) conditions. Interestingly, the quadrupole doublet characteristic of this complex in the 119Sn Mossbauer spectrum exhibited asymmetry in the line intensities. Analysis of the temperature dependence of the Mossbauer spectra demonstrated that this phenomenon can be rationalised by the Goldanskii–Karyagin effect. The effect emerges due to the vibrational anisotropy of bonds in the tin complex formed in hyperalkaline solution, similarly to what has been found earlier for SnF2 with analogous Sn bond structure.

A new method is developed to synthesize magnetic carbon microspheres decorated with carbon nanofibers and iron nanoparticles (nanofurry microspheres) for separation techniques in chemistry and biology. Microspheres are synthesized by carbonizing polystyrene–divinylbenzene-based, iron-loaded ion exchange resins. The phase composition, magnetic properties, and surface area and morphology of these materials are characterized by various techniques. It is detected that superparamagnetic (SPM) magnetite is present in microspheres exclusively upon carbonization at 400–500 °C, elemental iron, both α- and γ-Fe, is the major component at 600 °C, and cementite dominates between 700 and 1000 °C. Nanofiber formation is observed to be pronounced at high temperatures. The synthesized carbon microspheres have high surface area (100–300 m2 g−1) and can be separated easily by a magnet or by filtration. Saturation magnetization of selected samples is obtained between 5 and 28 emu g−1, depending on the phase composition. The novel microcomposites are expected to be effective adsorbents or support materials in various chemical processes, for example in water and air cleaning, catalysis, and biotechnological separations. Preliminary experimental studies for Cr(VI) removal from water and for platinum deposition are provided.

In spite of numerous investigations on the various processes of the thermal decomposition and rehydration of layered double hydroxides (LDHs) by a variety sophisticated experimental means, many details are still unexplored and some contradictions are still unresolved. In this work, our efforts were focussed on clarifying the composition, structure and properties of thermally decomposed metaphases originating from CaFe–LDH, heat treated in the 373–973 K temperature range. The structure reconstruction ability of mixed metal oxide phases obtained after heat treatments was also investigated, mainly concentrating on the changes in the microenvironment of Fe(III), in the presence of controlled amount of water vapour (i.e., at different relative humidities). All samples were characterised by X-ray diffractometry, and the iron-containing phases were studied by 57 Fe Mossbauer spectroscopy.

Iron–polygalacturonate complexes have been synthesized from polygalacturonic acid by applying a novel preparation method in order to develop medicine suitable for the effective iron supplementation of the human body in the case of anemia. Since the iron uptake depends on the oxidation state of iron, 57Fe Mossbauer spectroscopy was used to study the occurrence of different valence states in the iron–polygalacturonate complexes prepared under different circumstances. The Mossbauer-spectra indicated the presence of iron both in FeII and FeIII states in the investigated iron–polygalacturonate compounds, the occurrence of which varied with the preparation parameters. A correlation of the relative occurrence of iron valence states with the pH has been found. The relative occurrence of FeIII was found to increase with increasing pH. The knowledge of this correlation can help find optimum preparation conditions of iron–polygalacturonates to cure human anemia.

A relationship between the photocatalytic effect and the local structure of 50Fe2O3⋅ (50−x)SiO2⋅xTiO2 glass abbreviated as 50FSxTi prepared by sol-gel method was investigated by 57Fe-Mossbauer spectroscopy (FeMS), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FT-IR) and ultraviolet-visible diffuse reflectance spectroscopy (UV-VIS). Mossbauer spectra of 50FSxTi glass before annealing showed a doublet with the isomer shift (δ) and quadrupole splitting (Δ) of 0.41±0.01 mm s−1 and 0.75±0.02 mm s−1, indicating that Fe3+ formed FeO6 octahedra (O h). A comparable δ of 0.36±0.02 mm s−1 and the larger Δ of 0.92±0.02 mm s−1 values were confirmed for 50FSxTi after annealed at 400 ∘ C for 3 h. These results indicates that the coordination number of iron polyhedra decreases from 6 to 4 due to annealing. UV-VIS diffuse reflectance spectra of 50FS10Ti yielded two optical band gap energies (E g’s) of 2.05 eV and 3.55 eV. This result implied that 50FS10Ti has two optical band gaps in the visible area and UV area. A bleaching test performed by 10 mL of MB aqueous solution and 40 mg of powder 50FS10Ti glass sample showed that MB absorbance decreased from 3.16 to 0.43 after UV-visible light irradiation for 2 h with the first order rate constant (k) of $1.6\times 10^{-2}~ \min ^{-1}$ . These results prove that titanium containing iron silicate glass with the composition of 50Fe2O3⋅40SiO2⋅10TiO2 has the UV and visible light responsive photocatalytic effect.

Constant current electrochemical deposition technique was used to obtain quaternary alloys of Sn-Fe-Co-Ni from a gluconate electrolyte, which to date have not been reported in the literature. For the characterization of electroplated alloys, 57Fe and 119Sn Conversion Electron Mossbauer Spectroscopy (CEMS), XRD and SEM/EDAX were used. XRD revealed the amorphous character of the novel Sn-Fe-Co-Ni electrodeposited alloys. 57Fe Mossbauer spectrum of quaternary deposit with composition of 37.0 at% Sn, 38.8 at% Fe, 16.8 at% Co and 7.4 at% Ni displayed a magnetically split sextet (B = 28.9T) with broad lines typical of iron bearing ferromagnetic amorphous alloys. Magnetically split 119Sn spectra reflecting a transferred hyperfine field (B = 2.3T) were also observed. New quaternary Sn-Fe-Co-Ni alloys were successfully prepared.

A series of novel [Fe(MeiPrGlyoxH)2(amine)2] complexes have been synthesized [(MeiPrGlyoxH2 = methylisopropylglyoxime, amine = 3,5-dimethylpyridine, 4-(dimethylamino)pyridine, 4-(phenylamino)phenol, 2-imidazolidone)] and characterized by 57Fe Mossbauer, FTIR, UV–Vis spectroscopy, mass spectrometry, AFM and thermoanalytical methods. Quantum chemical (DFT) computations of [Fe(MeiPrGlyoxH)2(3,5-dimethyl-Py)2] (Py = pyridine) complex were also performed. The square-planar structure of [Fe(MeiPrGlyoxH)2] moiety is similar to that of [Fe(MeEtGlyoxH)2]. The incorporation of branching alkyl chains (isopropyl) in the complexes alters the Fe–N bond length and results in high-spin iron(II) state.

Liquids trapped in the pores of certain silicate glasses (such as Corning Vycor ‘thirsty’ glass) were found to display frozen solutions like behavior at temperatures much higher than their actual freezing point. For example, recoilless γ-resonance absorption was observed for Mossbauer active solutes such as 119Sn and 57Fe salts at room temperature (i.e., without the need of quenching). Thus capillary Mossbauer spectroscopy (CMS) proved to be a new and useful experimental tool with great potential in solution chemistry. As part of a research project concerned with the hydrolysis of SnII salts, we attempted to perform 119Sn CMS measurements for solutions containing stannous ion in a range of aqueous environments. Somewhat surprisingly, we found that under ambient conditions, SnII aqueous liquid solutions, both the acidic and the basic systems, are essentially CMS-silent. This can be attributed to the strong temperature dependence of Lamb–Mossbauer factor of SnII species, which may result in the complete disappearance of Mossbauer pattern well below room temperature. These observations can also explain why previous publications concerned with the use of CMS dealt exclusively with SnIV and not with SnII containing liquids.

Magnetization and low temperature in-field 57Fe Mossbauer spectroscopy measurements have been performed on a Fe[C(SiMe3)3]2/ferrihydrite hetero-mixture. The results indicate the presence of ferromagnetic coupling of magnetic moments involving Fe[C(SiMe3)3]2 with a hyperfine magnetic field of about 151 T, attributable mainly to the non-frozen atomic orbital contribution. The present findings show the sensitivity of single-ion molecular magnets to local alterations of their lattice-environment and might explain and reconcile some of the differences found in the literature for the observed bulk magnetic properties of the title Fe[C(SiMe3)3]2 compound.

The identity of the predominating tin(II)-hydroxide complex formed in hyper-alkaline aqueous solutions (0.2

The effects of firing conditions on the microstructure and physical properties of clay roofing tiles are studied. This research presents the effects of oxidizing and reducing atmosphere on Kanjiža clay material with carbonate content up to 22% by weight and the characterization of the final products. The firing was done both in the laboratory and under industrial conditions. The Fe2+/Fetotal ratio played a decisive role in the sintering process under a reducing atmosphere. The formed glassy phase, with the presence of Fe2+, attacked the earth-alkali oxides after the carbonate decomposition and more effectively filled smaller pores. The obtained results justified the benefits of the reducing firing atmosphere with 5% CO, lower porosity, higher frost resistance values, and changed microstructural characteristics

Iron(III)-containing aqueous solutions of 5-methylresorcinol (5-MR), 5-n-propylresorcinol (5-n-PR) and 4-n-hexylresorcinol (4-n-HR) at pH ~ 3 were studied by means of 57Fe transmission Mossbauer spectroscopy. Kinetic considerations were applied to the redox reactions. Density Functional Theory (DFT) calculations were performed for the alkylresorcinol (AR) molecules and their non-alkylated analogue (resorcinol). Mossbauer spectra consisted of quadrupole doublets assigned to high-spin Fe(III) and Fe(II) species. From changes in their relative spectral areas, a gradual reduction of Fe(III) by all the ARs studied was observed. However, significant differences were found for the reduction rates among the ARs. The following series of the reduction rates was established by means of Mossbauer spectroscopy: 4-n-HR ≫ 5-MR > 5-n-PR, supplemented by rate constants calculated using a kinetic model. DFT calculations resulted in the following series: 4-n-HR ≫ 5-n-PR > 5-MR ≫ resorcinol (the latter is not oxidised under the conditions applied). The reversed order of the experimentally observed 5-MR and 5-n-PR oxidation rates may be explained in terms of their different kinetic parameters related to their structure.

A relationship between physical properties and local structure of 20Li2O·10Fe2O3·xWO3·(70–x)V2O5 glass, abbreviated as xLFWV glass (x = 0 − 25 in mol%), was investigated by 57Fe-Mossbauer spectroscopy, Fourier transform infrared spectroscopy (FT-IR), differential thermal analysis (DTA), leaching test using 20 vol% HCl and DC two- or four-probe method. 57Fe-Mossbauer spectra of xLFWV glass showed an increase of quadrupole splitting (Δ) from 0.67 to 0.73±0.02 mm s − 1 and a constant isomer shift (δ) of 0.39±0.01 mm s − 1 with an increase of ‘x’ from 0 to 25. This suggests that FeIIIO4 tetrahedra gradually increase their local distortion along with a substitution of WO3 for V2O5. DTA of xLFWV glass showed an increase in glass transition temperature (T g) from 252 to 298 $_{\pm 5}^{\circ}$ C with an increase of ‘x’. Composition dependency of T g and Δ indicates that FeIII atoms occupy substitutional sites of WO6 octahedra as network former (NWF), since a large slope of 680 K (mm s − 1) − 1 was obtained in T g − Δ plot. Comparable electrical conductivities (σ) of 2.5 × 10 − 6, 1.9 × 10 − 6, 8.4 × 10 − 7 and 2.9 × 10 − 6 S cm − 1 obtained for xLFWV glasses with ‘x’ of 0, 10, 20 and 25, respectively increased to 2.4 × 10 − 2, 2.4 × 10 − 3, 3.5 × 10 − 4 and 8.8 × 10 − 5 S cm − 1 after annealing at 400 °C for 100 min. Smaller Δ values of 0.58 and 0.67±0.02 mm s − 1 obtained in annealed xLFWV glasses with ‘x’ of 0 and 10, respectively indicate that structural relaxation occurs in VO4 units of vanadate glass units, as had been observed in other vanadate glasses.

N-containing fully saturated (L-prolinate) or aromatic (indole-2-carboxylate) heterocyclic anions were immobilised in CaFe-layered double hydroxide with the dehydration-rehydration method from aqueous ethanol or acetone. The structure of the resulting organic-inorganic hybrids was characterised mainly with powder X-ray diffraction and 57Fe Mossbauer spectroscopy, and as supplementary analysis scanning electron microscopy, energy dispersive X-ray spectroscopy with elemental mapping and molecular modelling were also applied. It was found that the solvent mixture used for the synthesis caused enormous difference in the interlayer spacings of the obtained inorganic-organic hybrids.

Preliminary 57 Fe transmission Mossbauer spectroscopic data were ob- tained for the first time for live cells of the plant-growth-promoting rhizobacterium Azospirillum brasilense (wild-type strain Sp245) grown aerobically with 57 Fe III - nitrilotriacetate (NTA) complex as a sole source of iron. The results obtained have shown that live cells actively reduce part of the assimilated iron(III) to iron(II), the latter amounting up to 33 % of total cellular iron after 18 h of growth, and 48 % after additional 3 days of storage of the dense wet cell suspension in nutrient-free saline solution in air at room temperature (measured at 80 K). The cellular iron(II) was found to be represented by two quadrupole doublets of different high-spin forms, while the parameters of the cellular iron(III) were close to those typical for bacterioferritins.

A relationship between local structure, thermal endurance, chemical durability and electrical conductivity of alkaline iron tungsten vanadate glass, 20R 2 O•10Fe 2 O 3 • x WO 3 •(70 − x )V 2 O 5 , R = Na and K, x = 0–50 mol.%, abbreviated as RFWV was investigated by 57 Fe-Mossbauer spectroscopy, X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FT-IR), differential thermal analysis (DTA), leaching test using 20 vol.% HCl and dc-probe method. Mossbauer spectra of 20Na 2 O•10Fe 2 O 3 • x WO 3 •(70 − x )V 2 O 5 glass (NFWV) consisted of one paramagnetic doublet with a stable isomer shift ( δ ) of 0.40 mm s − 1 and an increasing quadrupole splitting ( Δ ) from 0.68 to 0.82 mm s − 1 with the increase of “ x ” from 0 to 50 mol.%, indicating that local distortion of Fe III O 4 tetrahedra increased with WO 3 content. After isothermal annealing at 500 °C for 100 min, Δ decreased to 0.62, 0.59, 0.67 and 0.67 mm s − 1 for NFWV glass with “ x ” of 0, 10, 20 and 30, showing that local distortion of Fe III O 4 tetrahedra was reduced due to the structural relaxation. Original NFWV glass exhibited a slightly decreasing electrical conductivity ( σ ) from 2.9 × 10 − 6 to 5.5 × 10 − 8 S cm − 1 with the increase of “ x ” from 0 to 50. The isothermal annealing of NFWV glass caused a remarkable increase in σ of 4.5 × 10 − 3 , 6.2 × 10 − 4 and 9.8 × 10 − 4 S cm − 1 with “ x ” of 0, 10 and 20, all of which showed a small activation energy for electron hopping ( W H ) of 0.21, 0.20 and 0.15 eV, respectively. On the other hand, increases in glass transition temperature ( T g ), crystallization temperature ( T c ) and activation energy for crystallization ( E a ) were observed for NFWV glass with WO 3 content, proving that the tungsten ion contributes to enhancement of chemical bond strength of NFWV glass. Similar results of an increase in σ and a decrease in dissolution rate due to annealing were observed for KFWV glass. It is concluded that structure, physical and chemical properties of RFWV glass can be controlled by introduction of WO 3 .

Mn x Zn 1− x Fe 2 O 4 ( x = 0.05…0.9) nanoparticles prepared via sol–gel hydrothermal process were investigated by X-ray powder diffractometry (XRPD), transmission electron microscopy (TEM), 57 Fe Mossbauer spectroscopy (MS), electron paramagnetic resonance spectroscopy (EPR), X-ray absorption near edge structure spectroscopy (XANES) and magnetic hysteresis measurements. XRPD measurements revealed a non-monotonic dependence of the cubic lattice parameter on the Mn concentration, which is interpreted as being the result of a corresponding variation in the inversion degree (concentration of Fe ions on the occupied tetrahedral lattice sites) of the studied spinels. XANES measurements indicated that the average oxidation state of Mn ions decreases with the applied Mn concentration, in contrast with Fe ions that were found to be exclusively in the 3+ oxidation state by MS measurements. EPR spectra recorded as a function of temperature enabled the determination of the characteristic anisotropy energy barrier of the superparamagnetic particles, and contributed to the clarification of peculiarities of the corresponding 57 Fe Mossbauer spectra. On the basis of the observed results the interdependences among the sample stoichiometry, the cubic cell parameter, the particle size, the inversion degree, the magnetic ordering temperature and the effective magnetic anisotropy are discussed.

The effect of swift heavy ion irradiation in novel electrodeposited ternary amorphous alloys was studied by 57 Fe and 119 Sn conversion electron Mossbauer spectroscopy. Irradiation of Sn3Co3Fe with 246 MeV Kr ions induces partial segregation and rearrangement of the constituent elements from the amorphous state toward an ordered state. The Sn3Ni3Fe irradiated with 600 MeV Xe ions exhibits transformation from the as-deposited amorphous toward a slightly more disordered state due to the swift heavy ion irradiation.

Mossbauer spectroscopy has been used to investigate the nature of the Zinc-Iron alloys present within the Hot Dip Galvanized (HDG) layers of steel with a silicon content of 0.35 %. The investigation also studied the impact of the powder coating pretreatment on the nature of the alloy layers. The acid etching process within the pretreatment process in particular would be expected to have a significant impact on the HDG layer. This study utilized 57Fe Mossbauer spectroscopy to examine identically processed samples prior to and post pre treatment. XRD and 57Fe CEMS measurements were performed on hot galvanized S355J2 + N samples, forming sandwiched structure. Both XRD and CEMS reveal the presence of dominant steel phase in accordance with its estimated occurrence on the surface of the sandwiched samples. Minor Γ-Fe3Zn10, ζ-FeZn15 and solid solution Fe-Zn as well as minor Fe-Si phases could also be identified.

The research investigated three iron carbonate (siderite) sedimentary concretions from Nagykovácsi, Úri and Délegyháza, Hungary. To identify possible source rocks and effects of the glaze-like exposed surface of the concretions, we carried on comparative petrological, mineralogical, geochemical and isotopic studies. The samples were microbially mediated siderite concretions with embedded metamorphous and igneous mineral clasts, and had specific rim belts characterized by semi-concentric outer Fe-oxide layers, fluffy pyrite-rich outer belts and siderite inner parts. We investigated the cross section of the Fe-carbonate concretions by independent methodologies in order to identify their rim effects. Their surficial oxide layers showed evidence of degassing of the exposed surface caused most probably by elevated temperatures. The inner rim pyrite belt in the concretions excluded the possibility of a prolonged wet surface environment. Microtextural and mineralogical features did not support desert varnish formation.

The effects of the Mg(II)/Fe(III) ratio on the structure and Fe microenvironments in MgFe LDH substances were investigated. The LDHs were prepared by the co-precipitation method with Mg(II)/Fe(III) ratios from 2:1 to 6:1. The materials were characterized by 57Fe Mossbauer spectroscopy and powder X-ray diffractometry. The 57Fe Mossbauer spectra exhibited asymmetric doublet corresponding to high-spin Fe(III) microenvironments in all LDH structure. It was found that the quadrupole splitting decreased with increasing Mg(II)/Fe(III)ratio reflecting change in the electric field gradient due to the incorporation of different amounts of iron into the Mg-containing layers.

A relationship between electrical conductivity (σ) and local structure of 15Li2O·10Fe2O3·xSnO2·(70–x)V2O5·5P2O5 glass (x = 0–20 mol%), abbreviated as xLFSVP glass, was investigated by 57Fe- and 119Sn-Mossbauer spectroscopies, differential thermal analysis (DTA) and dc-four probe method. A small increase in quadrupole splitting (Δ) for FeIII was observed from 0.70 to 0.74± 0.02 mm s − 1 with an increase of “x”, whereas isomer shift (Δ) values of 0.40±0.01 mm s − 1 were independent of “x”. This result suggests that local distortion of FeIIIO4 tetrahedra was slightly increased in SnO2-containing vanadate glasses, which was reflected as an increase in glass transition temperature (Tg) from 266 to 285±5 °C. A slope of 675 K / (mm s − 1) obtained in ‘Tg vs. Δ plot’ proved that FeIII occupied the site of network former (NWF). An isothermal annealing of 10LFSVP glass at 500 °C for 100 min resulted in a marked decrease of Δ from 0.72 to 0.56±0.02 mm s − 1, indicating that local distortion of FeO4 tetrahedra was reduced by the structural relaxation of 3D-network. In contrast, identical δ and Δ values of 0.07±0.01 and 0.53±0.02 mms − 1, respectively, were observed in 119Sn-Mossbauer spectra of 10LFSVP glass before and after the annealing. These results indicate that SnIVO6 octahedra are loosely bound in the glass matrix as a network modifier (NWM). A marked increase in σ from 7.4 × 10 − 7 to 9.1 × 10 − 3 S cm − 1 was observed in 20LFSVP glass after the isothermal annealing, indicating that structural relaxation of 3D-network evidently causes a marked increase in σ.

A relationship between waste-water cleaning ability and local structure of iron-containing soda-lime silicate glass, 15Na2O·15CaO·xFe2O3·(70-x)SiO2 (x = 10–50 in mass%), abbreviated as NCFSx glass, was investigated by means of 57Fe-Mossbauer spectroscopy, redox titration with KMnO4 for the determination of chemical oxygen demand (COD) and inductively coupled plasma optical emission spectroscopy (ICP-OES). Mossbauer spectra of NCFSx glass with “x” of 10 and 30 were composed of two doublets: one due to FeIIIO4 tetrahedra (Td) with isomer shift (δ) of 0.23–0.26 mm s − 1 and quadrupole splitting (Δ) 1.01–1.04 mm s − 1, and the other due to FeIIO6 octahedra (Oh) with δ of 1.00–1.03 mm s − 1 and Δ of 2.03–2.05 mm s − 1. Absorption area for FeII(Td) was decreased from 9.7 to 6.5 and 0.0 % when “x” was increased from 10 to 30 and 50. A leaching test performed with 500 mL of artificial waste water and 2.0 g of NCFS50 revealed waste-water cleaning ability of soda-lime glass, e.g., COD was reduced from 280 to 55.2 mg L − 1 after 10 day-leaching. After 10 day-leaching, it proved that iron was dissolved into waste water to a level of 5.3\(_{7} \times 10^{-1}\) mg L − 1. These results prove that organic matter could be effectively decomposed with iron-containing soda-lime silicate glass.