Mössbauer study of SnO<Subscript>2</Subscript> powders doped with dilute <Superscript>57</Superscript>Fe prepared by a sol-gel method

SnO₂ powders, doped with various ⁵⁷Fe contents were prepared by a sol-gel method, and annealed finally at 500 °C and 650 °C. These samples were characterized by Mössbauer spectroscopy, vibrating sample magnetometer (VSM), scanning electron microscopy (SEM), and X-ray diffraction (XRD) to investigate the relationship of magnetic properties, grain sizes, annealing temperatures and Mössbauer parameters. The particle sizes of SnO₂ powders reduced to less than 100 nm with the increase of Fe contents up to 5%. Rutile SnO₂ was the only phase obtained for all samples. Room temperature Mössbauer spectra suggest the presence of two different paramagnetic iron sites for all samples and one magnetically relaxed species for those samples with the lowest iron concentrations. The magnetization increased with the Fe content, but was reduced for the samples annealed at 650 °C perhaps due to a segregation of α-Fe₂O₃ doped with tin.     

Hematite reaction with tar to produce carbon/iron composites for the reduction of Cr(VI) contaminant

In this work, highly reactive carbon–iron composites were prepared using a waste, i.e. tar, as carbon precursor and a simple iron oxide, i.e. hematite. Tar was impregnated on Fe₂O₃ with different tar/hematite weight ratios of 1:1; 2:1 and 4:1, and thermally treated under N₂ atmosphere (400°C, 600°C and 800°C). Mössbauer, XRD and magnetization measurements suggested that treatment at 400°C and 600°C produces Fe₃O₄ but treatment at 800°C produced mainly Fe°. Raman and TG analyses of the different composites suggested the formation of carbon contents of 18, 24 and 32 wt.% as amorphous and graphitic highly dispersed on the Fe surface. The composites obtained at 800°C showed high efficiency to reduce Cr(VI) as CrO $_{4}^{2-}$ in aqueous medium with much better results compared to finely ground commercial Fe°.     

Synthesis and characterization of hollow ��-Fe2O3 sub-micron spheres prepared by sol�Cgel

In this work we report the preparation of magnetic hematite hollow sub-micron spheres (??-Fe₂O₃) by colloidal suspensions of ferric nitrate nine-hydrate (Fe(NO₃)₃·9H₂O) particles in citric acid solution by following the sol?Cgel method. After the gel formation, the samples were annealed at different temperatures in an oxidizing atmosphere. Annealing at 180°C resulted in an amorphous phase, without iron oxide formation. Annealing at 250°C resulted in coexisting phases of hematite, maghemite and magnetite, whereas at 400°C, only hematite and maghemite were found. Pure hematite hollow sub-micron spheres with porous shells were formed after annealing at 600°C. The characterization was performed by X-ray diffraction (XRD), Mössbauer spectroscopy (MS) and scanning electron microscopy (SEM).     

Processing of gadolinium–iron garnet under non-equilibrium conditions

We have investigated the mechanosynthesis of gadolinium iron garnet (GdIG) by high-energy ball-milling of 3.(Gd₂O₃)?+?10.(α-Fe) followed by thermal annealing conducted at moderate temperatures (1100 °C). The samples were characterized by X-ray diffraction and Mössbauer spectroscopy in order to determine the influence of the milling time on the final products. For as-milled samples the results revealed the enlargement of the magnetic component belonging to iron and a discrete paramagnetic component. The formation of a garnet phase was observed in all as-annealed samples treated at 1100 °C for 6 h in quantities proportional to the time of grinding the precursors. Evidently, high-energy ball milling of Gd₂O₃?+?α-Fe powders is an important step in GdIG synthesis by a ceramic method. Single-phase garnet is observed for the samples milled for 12 and 24 h treated at 1100 °C for 6 h.     

Characterization of Iron Oxides Commonly Formed as Corrosion Products on Steel

For fundamental studies of the atmospheric corrosion of steel, it is useful to identify the iron oxide phases present in rust layers. The nine iron oxide phases, iron hydroxide (Fe(OH)₂), iron trihydroxide (Fe(OH)₃), goethite (α-FeOOH), akaganeite (β-FeOOH), lepidocrocite (γ-FeOOH), feroxyhite (δ-FeOOH), hematite (α-Fe₂O₃), maghemite (γ-Fe₂O₃) and magnetite (Fe₃O₄) are among those which have been reported to be present in the corrosion coatings on steel. Each iron oxide phase is uniquely characterized by different hyperfine parameters from M?ssbauer analysis, at temperatures of 300K, 77K and 4K. Many of these oxide phases can also be identified by use of Raman spectroscopy. The relative fraction of each iron oxide can be accurately determined from the M?ssbauer subspectral area and recoil-free fraction of each phase. The different M?ssbauer geometries also provide some depth dependent phase identification for corrosion layers present on the steel substrate. Micro-Raman spectroscopy can be used to uniquely identify each iron oxide phase to a high spatial resolution of about 1 μm. This revised version was published online in August 2006 with corrections to the Cover Date.     

M?ssbauer study of carbon coated iron magnetic nanoparticles produced by simultaneous reduction/pyrolysis

Magnetic iron nanoparticles immersed in a carbon matrix were produced by a combined process of controlled dispersion of Fe^3?+? ions in sucrose, thermal decomposition with simultaneous reduction of iron cores and the formation of the porous carbonaceous matrix. The materials were prepared with iron contents of 1, 4 and 8 in %wt in sucrose and heated at 400, 600 and 800°. The samples were analyzed by XRD, Mössbauer spectroscopy, magnetization measurements, TG, SEM and TEM. The materials prepared at 400° are composed essentially of Fe₃O₄ particles and carbon, while treatments at higher temperatures, e.g. 600 and 800° produced as main phases Fe⁰ and Fe₃C. The Mössbauer spectra of samples heated at 400° showed two sextets characteristic of a magnetite phase and other contributions compatible with Fe^3?+? and Fe^2?+? phases in a carbonaceous matrix. Samples treated at temperatures above 600° showed the presence of metallic iron with concentrations between 16?C43%. The samples heated at 800° produced higher amounts of Fe₃C (between 20% and 58%). SEM showed for the iron 8% sample treated at 600?C800°C particle sizes smaller than 50 nm. Due to the presence of Fe⁰ particles in the carbonaceous porous matrix the materials have great potential for application as magnetic adsorbents.     

Mössbauer spectroscopy study of mechanically alloyed Fe2O3–(Al, Co and WC) systems

Mössbauer spectroscopy revealed that a central hyperfine interaction doublet and an additional sextet characterized the appearance of new phases in the mechanically alloyed Fe₂O₃–Al and Fe₂O₃–Co systems. In the Fe₂O₃–Al system, the intensity of the central super paramagnetic doublet which represents small particles of iron, increased with increasing milling time from 5 to 30 h of mechanical alloying. The magnetic sextet characterizing hematite vanished in the room temperature Mössbauer spectra of samples produced after 25 h of mechanically alloying the 50% Fe₂O₃ and 50% Al system. In general XRD peak broadening was observed as a result of extensive material structural distortion and formation of small particles. Fe, Al₂O₃ and mixed iron–aluminium oxide phases were identified in the XRD patterns with a small persistence of the iron oxide up to 20 h of mechanically alloying the 1:1 system Al–Fe₂O₃. In the 50% Co–50% Fe₂O₃ system, a 55% abundant new phase CoFe₂O₄ was observed, from the Mössbauer spectra of the system. The presence of this new phase was confirmed by the XRD analysis. The high energy ball milling of WC–Fe₂O₃ revealed a more effective grinding compared to hematite alone. The hematite particles were reduced to nanosized particles.     

Sol–gel synthesized powder and pulsed laser deposited film of amorphous indium zinc oxides doped with Fe

Chemical co-precipitation method was used to synthesize nano-structured α-Fe₂O₃-CeO₂ composite by calcination of the goethite–cerium hydroxide precursor. It was observed that the precursor contained goethite matrix doped with cerium. Calcination of the precursor at 400°C showed the formation of nanosize hematite. Mössbauer spectra show the presence of a paramagnetic component in the precursor but not in the samples calcined at 400°C to 800°C temperatures. Our study shows that Ce precipitated as CeO₂ and stuck on the surface of hematite particles. The precipitation of Ce as CeO₂ is independent of the concentration of Ce in the Ce–Fe–O composite.     

From Ore to Tool – Iron Age Iron Smelting in the Largest and Oldest Meteorite Crater in the World

The Vredefort Impact Structure in South Africa is the biggest and oldest remnant meteorite impact crater in the world where various ancient cultures thrived. In this paper some light will be shed on the Iron Age, iron smelting aspects of the people that inhabited the area and the results of a laboratory study of iron artefacts and a possible source of iron ore in the region is given. A sectional piece from a hoe manufactured in a small bloomery furnace was polished and etched and subsequently analyses with SEM and Mössbauer techniques were obtained. The hoe has a typical cast iron composition (2.9% C, 0.1% Mn, 0.4% Si, 0.4% P and 96.2% Fe, all wt.%) and contains many slag inclusions with wustite dendrites. The Mössbauer spectrum consisted of iron (86%), wustite (5%) and oxihydroxide (9%) and the thin (200 μm) corrosion layer consisted of hematite (55%) and oxihydroxides (45%). At a furnace site, various slag clumps (26.3% C, 24.8% SiO₂, 11.3% Al₂O₃, 1.3% P₂O₅, 1.0% K₂O, 0.4% CaO and 30.2 FeO, all wt.%, average of four samples) and iron nodules (7.6% C, 6.0% Mn, 4.3% Si, 1.4% Al, 80.7% Fe, all wt.%) were found. The Mössbauer spectrum of the slag consisted of iron (7%), magnetite (56%), fayalite (2%) and oxihydroxides (35%) and that of the iron nodules yielded iron (28%), wustite (12%), magnetite (20%) and oxihydroxides (40%). A possible ore source containing 84% FeO, 7% of Al₂O₃ and SiO₂ (all in wt.%) and minor impurities is located a few kilometers from the furnace site, yielding a Mössbauer spectrum consisting of hematite (70%) and oxihydroxides (30%).     

Hematite thin films: growth and characterization

We have grown hematite (α–Fe ₂ O ₃) thin films on stainless steel and (001)-silicon single-crystal substrates by RF magnetron sputtering process in argon atmosphere at substrate temperatures from 400 to 800°C. Conversion Electron Mössbauer (CEM) spectra of the sample grown on stainless steel at 400°C exhibit values for hyperfine parameter characteristic of bulk hematite phase in the weak ferromagnetic state. Also, the relative line intensity ratio suggests that the magnetization vector of the polycrystalline film is aligned preferentially parallel to the surface. The X-ray diffraction (XRD) pattern of the polycrystalline thin film grown on steel substrates also corresponds to α–Fe ₂ O ₃. The samples were also analyzed by Atomic Force Microscopy (AFM), those grown on stainless steel reveal a morphology consisting of columnar grains with random orientation, given the inhomogeneity of the substrate surface.     

Iron and chromium mixed-oxide nanocomposites

Mixed oxides nanocomposites of the type xCr₂O₃-(1-x)α-Fe₂O₃ (x = 0.0–1.0) were synthesized using hydrothermal technique and characterized by X-ray diffraction (XRD) and Mössbauer spectroscopy. The same characterization methods were applied to a set of samples annealed at 600°C for 2 h. High chromium content correlated with occurrence of amorphization effects and onset of superparamagnetism in the as-obtained samples. The structure and properties of the thermally annealed samples, however, are dominated by the equilibrium of two phases, Cr:Fe₂O₃ and Fe:Cr₂O₃. The final (x = 1.0) particle size of the nanocomposite is close to 19 nm.     

A CEMS study of surface oxidation of Fe--Ni alloys

A study by Conversion Electron Mössbauer Spectroscopy (CEMS) carried out by using a Parallel Plate Avalanche Counter with samples of Fe--Ni alloys (50 and 65 at.% Fe) is reported. Each sample was analyzed without oxidation and after heating it under an oxygen atmosphere at 200°C. All CEMS measurements were carried out at room temperature. In both samples (50 and 65 at.% Fe), without oxidation and after oxidation, the Mössbauer spectra showed a six line magnetic spectrum according to their ferromagnetic character, with a broad Hyperfine Field Distribution (HFD), according to the disordered character of the alloys. The obtained Mean Hyperfine Field (MHF) for the sample 50 at.% Fe was 30.9 T, meanwhile for the invar composition (65 at.% Fe) was 25.5 T, which is close to values previously reported by Transmission Mössbauer Spectroscopy (TMS). Results from the treated samples (with oxidation at 200°C) showed a difference in the surface composition as a result of this process. In the 50 at.% Fe sample, additionally appeared a doublet that could be assigned to an oxihydroxide of Fe³⁺. Otherwise, the 65 at.% Fe sample (invar) presented ferromagnetic oxides (α-Fe₂O₃ and Fe₃O₄) with a large relative area (82.5%).     

High temperature stability of maghemite in partially oxidized basalt lava

Mössbauer spectroscopy of basalt lava samples, exhibiting reversible thermal magnetization (J_S-T) curves with Curie temperatures of about 580°C, has revealed considerable amounts of maghemite (γ-Fe₂O₃) in many samples. In view of the expected instability, of maghemite at temperatures above 350°C, this reversibility is rather surprising. Here we report Mössbauer studies on heated lava samples, showing high content of maghemite. The samples were kept at 600°C in oxidizing, reducing, and inactive atmospheres, respectively, for different lengths of time, and then analyzed with Mössbauer spectroscopy at room temperature. The Mössbauer spectra showed that maghemite is stable in the oxidizing atmosphere for at least several hours. In the inactive atmosphere a considerable amount of maghemite still exists after two hours heating. In the reducing atmosphere maghemite had transformed to magnetite after only 30 minutes.     

Reduction of hematite with ethanol to produce magnetic nanoparticles of Fe3O4, Fe1 − x O or Fe0 coated with carbon

The production of magnetic nanoparticles of Fe₃O₄ or Fe⁰ coated with carbon and carbon nanotubes was investigated by the reduction of hematite with ethanol in a Temperature Programmed Reaction up to 950°C. XRD and Mössbauer measurements showed after reaction at 350°C the partial reduction of hematite to magnetite. At 600°C the hematite is completely reduced to magnetite (59%), wüstite (39%) and metallic iron (7%). At higher temperatures, carbide and metallic iron are the only phases present. TG weight losses suggested the formation of 3–56 wt.% carbon deposits after reaction with ethanol. It was observed by SEM images a high concentration of nanometric carbon filaments on the material surface. BET analyses showed a slight increase in the surface area after reaction. These materials have potential application as catalyst support and removal of spilled oil contaminants.     

Size dependence of the magnetic and hyperfine properties of nanostructured hematite (α-Fe 2 O 3 ) powders prepared by the ball milling technique

In this work we present the study of hematite (α-Fe₂O₃) nanostructures synthesized by the ball milling technique. The structural characterization and the crystallite size estimation have been carried out using the X-ray diffraction (XRD) technique. Data analyses indicate that the hematite phase (space group, R-3C) is preserved after the milling process. As the milling time is increased, a second phase (α-Fe) appears. The mean crystallite size shows a decreasing tendency as the milling time is increased. High-resolution transmission electron microscopy (HRTEM) images show the formation of grains composed of crystallites with irregular shapes. Mössbauer spectra of milled powders carried out at 297 and 77 K are well modeled with a histogram distribution of hyperfine fields. The presence of one additional sextet which corresponds to the ∝-Fe phase is also determined in agreement with XRD data analysis. Magnetic measurements suggest the suppression of the Morin transition in the milled samples and the absence of thermal relaxation effects in agreement with the Mössbauer spectroscopy results.     

Behaviour of Ca2Fe2O5 with Nb substitution and sintering temperatures seen by Mössbauer spectroscopy

Mössbauer spectroscopy of samples of Ca₂Fe_2?xNb_xO_5+x with x values ranging from 0 to 0.8 and sintering temperatures of 1200°C and 1300°C shows the presence of two magnetic fields and a paramagnetic signal. The behaviour of the parameters as a function of x and of the sintering temperatures are discussed and compared with XRD results.     

Influence of Cu and Ni on the morphology and composition of the rust layer of steels exposed to industrial environment

Four samples of steels with alloying elements were exposed to an industrial environment during 1,955 days, aiming to elucidate the effect of the alloying elements Cu and Ni on the resistance of weathering steels to corrosion processes. The samples were characterized with optical microscopy, scanning electron microscopy (SEM), powder X-ray diffraction (XRD), saturation magnetization measurements and with energy dispersive (EDS), infrared, Mössbauer and Raman spectroscopies. All the steels originated orange and dark corrosion layers; their thicknesses were determined from the SEM images. EDS data of such rust layers showed that the alloying element content decreases from the steel core towards the outer part of the rust layer. Moreover, in the dark rust layer some light-gray regions were identified in the W and Cu-alloy steel, where relatively higher Cr and Cu contents were found. XRD patterns, infrared, Raman and Mössbauer spectra (298, 110 and 4 K) indicated that the corrosion products are qualitatively the same, containing lepidocrocite (γFeOOH; hereinafter, it may be referred to as simply L), goethite (αFeOOH; G), feroxyhite (δ′FeOOH; F), hematite (αFe₂O₃; H) and magnetite (Fe₃O₄; M) in all samples; this composition does not depend upon the steel type, but their relative concentrations is related to the alloying element. Mössbauer data reveal the presence of (super)paramagnetic iron oxides in the corrosion products. Saturation magnetization measurements suggest that feroxyhite may be an occurring ferrimagnetic phase in the rust layer.     

Thermally Driven and Ball-Milled Hematite to Magnetite Transformation

In this work, a study on the dynamics of transformation from hematite (α-Fe₂O₃) to magnetite (Fe₃O₄) by following two solid-state reaction methods is carried out. One of the procedures consists of a thermal treatment under a 20% H₂ and 80% N₂ atmosphere at 375°C, whereas the second method involves a planetary ball mill to induce the transformation. The phases evolution as a function of the thermal treatment time ranging from 0 up to 25 min every 2.5 min, and from 0 up to 6 hours every hour in the case of the milling method, was followed by using room-temperature Mössbauer spectroscopy and X-ray diffraction analysis. Results evidence a well-behaved structural transformation for which highly stoichiometric Fe₃O₄ as a single phase was obtained for treatment times above 12.5 min in the case of the thermally treated samples. Differently from this a less stoichiometric magnetite characterized by a distribution of hyperfine fields for milling times above 3 hours in the case of the ball milled samples was obtained. For reaction times below 12.5 min, two interpretation models based on the presence of an anion-deficient magnetite Fe₃O_4?δ and the presence of maghemite accounting for the intermediate states during the thermal transformation are also presented and discussed.

     

Dzyaloshinskii–Moriya interaction: How to measure its sign in weak ferromagnets?

Three experimental techniques sensitive to the sign of the Dzyaloshinskii-Moriya interaction are discussed: neutron diffraction, Mössbauer γ-ray diffraction, and resonant x-ray scattering. Classical examples of hematite (α-Fe₂O₃) and MnCO₃ crystals are considered in detail.     

Mössbauer Study of Ferrite-garnets as Matrixes for Disposal of Highly Radioactive Waste Products

Mössbauer study of synthesized ferrite-garnet samples containing Zr, Th, Ce and Gd of the following composition: 1C – Ca_{2, 5} Ce_{0, 5} Zr₂ Fe₃ O₁₂, 2C – Ca_{1, 5} GdCe_{0, 5} ZrFeFe₃ O₁₂, 1T – Ca_{2, 5} Th_{0, 5}Zr₂ Fe₃ O₁₂ and 2T – Ca_{1, 5} GdTh_{0, 5} ZrFeFe₃ O₁₂ are carried out. As a result of ⁵⁷Fe Mössbauer study it is found that iron atoms in all investigated samples of garnets are in a trivalent state. The analysis of experimental Mössbauer spectra definitely specifies a various structural state of iron atoms in two investigated groups of samples: 1T, 1C and 2T, 2C. X-ray study have shown that 1T and 1C garnet samples crystallize in tetragonal space group I4₁/acd, but 2T and 2C samples crystallize in cubic space group Ia3d.