57Fe Mössbauer spectroscopic study of nanostructured zinc ferrite

Nanosize zinc ferrite particles, prepared by nitrate method, were investigated by XRD, TEM, ⁵⁷Fe Mössbauer spectroscopy and VSM. The average particle size in this system varies from 10 to 62 nm as the sintering temperature increases from 300°C to 1,000°C. The lattice parameters in this system are almost constant at a value of ～8.41 Å. The Mössbauer spectra of all the sintered samples show a single doublet. The Mössbauer hyperfine parameters show little change with the change of sintering temperature. The doublets are ascribed to the presence of superparamagnetism in this system, which is also corroborated by the VSM measurements.     

Mössbauer study of phase separation in Ni80 57Fe1P19 amorphous alloys

Mössbauer spectroscopy, X-ray diffractometry, scanning calorimetry and electrochemical measurements were used to study the crystallization process of Ni₈₀ ⁵⁷Fe₁P₁₉ amorphous alloys kept in melt at different temperatures before quenching. Samples were heated up to 430°C and 720°C at a rate of 20°C/min, in order to reach characteristically different stages of crystallization. Even at the same crystallization, stage the room temperature Mössbauer spectra and the X-ray differactograms were different depending on the temperature (1050°C or 1400°C) at which the samples were kept before quenching the melt. The Mössbauer spectra showed a paramagnetic component and two sextets (H=267 kOe and H=245 kOe) at 430°C while at 720°C there was only one sextet (H=267 kOe) besides the paramagnetic component. The changes in the Mössbauer spectra of different samples due to crystallization are consistent with the explanation that phase separation occurs in Ni₈₀ ⁵⁷Fe₁P₁₉ rapidly quenched from the melting temperature of 1050°C.     

Sol-gel synthesis and dilute magnetism of nano MgO powder doped with Fe

Mg oxides doped with 1 % ⁵⁷Fe were prepared by a sol-gel method, and annealed at various temperatures. Nano-size Mg oxides were characterized by Mössbauer spectrometry, magnetization and XRD measurements. The crystalline size of MgO increases with increase of annealing temperature. Samples annealed at 600 °C and 800 °C gave only doublet peaks of paramagnetic Fe³⁺ in Mössbauer spectra although Fe³⁺ doping into MgO induced a distorted structure and showed weak ferromagnetism. It is considered that the magnetic property is due to defect induced magnetism by doping Fe³⁺ into MgO. For a sample heated at 1000 °C, it is found from low temperature Mössbauer spectra that Fe³⁺ species are located at the core and shell of fine MgFe₂O₄ grains and diluted in MgO matrix.     

Mössbauer study of illitic clays containing iron-rich impurities

The iron mineralogy of nineteen illitic clays from eastern Bavaria was studied by Mössbauer spectroscopy and X-ray powder diffraction. Mössbauer spectra of the <2 μm fraction were taken at RT, 120 K and 4.2 K. The clays contain both paramagnetic Fe³⁺ and Fe²⁺. Superparamagnetic oxides are frequently present. The Fe²⁺ quadrupole splitting and the ratio of Fe³⁺ at 4.2 K to Fe²⁺ at 120 K are correlated and define two groups distinguished by their mineral content. The samples were heated systematically for 48 h up to 1250°C in steps of 50°C. One clay which is rich in chlorite and Fe(II) was studied in detail after firing in air and following a reduction for 3 h at 800°C with charcoal. The transformations of the mineral phases with temperature as shown by X-ray diffraction are also evident in the Mössbauer spectra.     

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.     

Mössbauer study of turbine blade steels

Mössbauer investigations were carried out on low carbon steels containing 12–13.5% Cr and 3–5% Ni in order to get information about the reason of cracking and fracture which take place during the use of turbine blade wheels. The quantity of retained austenite determined from the Mössbauer spectra of steels was low (<1%) in the cracked and fractured basic materials. Comparing this value with those being considerable in quenched (≈11%) as well as in annealed state (≈5%) of the same sample, we can conclude that the transformation of the austenite taking place during the working of turbine blade wheel can be associated with the cracking and the fracture. We found an anomalous increase of the quantity of the austenite in steel samples (quenched from different temperature between 700 and 1000 °C and aged at 450–600 °C) aged again at 450–550 °C. On the basis of the evaluation of Mössbauer spectra of the steels, information can be obtained about the changes in the concentration of alloying elements being in martensite at the various heat treatments.     

Hyperfine fields in iron dilute alloys and internal oxidation

AnFe-V 2.5 at% foil was annealed at various temperatures in the range from 120°C to 1000° \(\bar C\) for 10 min and analysed by Transmission Mössbauer Spectroscopy (TMS) and Conversion Electron Mössbauer Spectroscopy (CEMS) after each thermal process. A computational method to fit the spectra to obtain a parameter related to the concentration of the alloy was studied and applied to the data. No surprising effects were found on the bulk measurements (TMS), but there is a clear decrease of the alloy concentration in the 550°C to 700°C annealing temperature range, observed for the surface analysis (CEMS measurements). The phenomenon was attributed to the preferential internal oxidation of vanadium atoms in this range of temperature. Probably some vanadium oxide decomposition occurs at higher temperatures, recovering the original state of the sample.     

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.     

Mössbauer investigation of Fe−Zr amorphous alloys hydrogenated after annealing

Transmission and conversion electron Mössbauer spectroscopy were used in order to get further information bout thé effect of hydrogenation in Fe₈₉Zr₁₁ amorphous alloys in connection with the observation that the magnetically split spectrum appearing at room temperature due to a moderate hydrogenation gradually collapses with increasing hydrogen content. The Mössbauer measurements were performed on differently hydrogenated amorphous samples aged at 150 °C 300 °C and 600 °C before the hydrogenation. The time dependence of hydrogenation has also been measured. From the changes of Mössbauer parameters depending on the annealing temperature as well as on the cathodic potential of hydrogenation (compared with the hydrogen concentration measured by gas chromatography) we can conclude that relaxation processes and structural changes, taking place in these amorphous alloys, influence the hydrogen uptake, already at relatively low temperatures.     

Low temperature 151Eu and 57Fe Mössbauer study of mechanically alloyed EuFeO3

Low temperature ⁵⁷Fe Mössbauer spectra of mechanically alloyed EuFeO₃ prepared by mechanical alloying depicts an interesting transformation in its hyperfine magnetic state, from a triple phase magnetic system at room temperature to a single phase ferromagnetic state at 20 K. The hyperfine magnetic field increased by 12% at 20 K from its room temperature. The isomer shift and quadrupole splitting values exhibit a peak around 200 K. Low temperature ¹⁵¹Eu Mössbauer measurements show that the line-width increased to its maximum value at 80 K which is 45% compared to its room temperature value not enough to suggest splitting.     

Hyperfine fields and magnetic properties of barium monoferrite

First we studied the kinetics of the formation of Ba monoferrite by means of Mössbauer spectroscopy. The most important result is the considerable portion of hexaferrite existing after treatment of the starting materials between 800 and 900°C, caused by a higher rate of diffusion of the Ba²⁺ ions in comparison to the Fe³⁺ ions. Second we report susceptibility measurements recorded in a temperature range of 4.3 K to 280 K and Mössbauer spectra at room temperature and at 4.2 K without and in the presence of an applied magnetic field of 6 T. The experimental data demonstrate that the magnetic behaviour of Ba monoferrite deviates to some extent from a simple antiferromagnetic.     

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.     

Observation and analysis of a glass transition in amorphous frozen solutions of iron-II chloride

This paper deals with Mössbauer investigations, X-ray diffraction studies and differential calorimetric measurements of the amorphous state of frozen solutions of FeCl₂ in water. This glassy state persists from at least ?180 °C until ?90 °C. All three experimental methods reveal the existence of a glass transition at ?110 °C from an amorphous state to a supercooled liquid. It is shown that for such transitions important conclusions can be drawn from a comparison between the Mössbauer and X-ray diffraction Debye-Waller factor respectively by determining the transmitted Mössbauer intensity far off resonance. Out of the analysis we conclude that the glassy state of quenched ice is due to the hexaquo complexes as implanted impurities which prevail their surrounding from a regular crystallisation. These impurities are also responsible for the glass transition into a supercooled liquid state by releasing new degrees of freedom as e.g. hindered rotational modes.     

Mössbauer study of phase transition caused by oxidation in the temperature region from 20 to 1000°C in almandine garnets

A Mössbauer investigation has been carried out on garnets from Měděnec and Kti? (Czech Republic). Changes of Fe²⁺ and Fe³⁺ crystallographic sites were observed in these silicate garnets after temperature processing under oxidising atmosphere. The temperature processes were realised from 200 to 1000°C by 100 degrees. The results of Mössbauer experiments are compared with the results of the chemical analysis, X-ray diffraction, infrared spectroscopy, and magnetic susceptibility measurements.     

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%).     

Emission Mössbauer spectroscopic studies of57Fe atoms produced in57Co-labelled trinuclear cobalt-iron halogenoacetate complexes

Mixed-valence states of⁵⁷Fe atoms produced after EC-decay of⁵⁷Co in a series of trinuclear cobalt-iron halogenoacetate complexes, [Co^IIFe ₂ ^III O(CH_3?nX_nCO₂)₆(H₂O)₃] (0≤n≤3, X=Cl, Br, and I), were studied by comparing the results obtained by emission Mössbauer spectroscopy with those observed in absorption Mössbauer spectra of analogous trinuclear iron complexes, [Fe^IIFe ₂ ^III O(CH_3?nX_nCO₂)₆(H₂O)₃]. Some of the emission Mössbauer spectra show a temperature-dependent mixed-valence state as found in the absorption Mössbauer spectra. Others show a somewhat different temperature dependence compared with the absorption Mössbauer spectra. The results were interpreted in terms of after-effects of the EC-decay.     

Mössbauer study of biofilms formed at spring caves of Buda Karst,Hungary

Biofilms formed at spring caves of Buda Karst, Hungary, were investigated by ⁵⁷Fe Mössbauer spectroscopy. 78 K Mössbauer spectra were decomposed into a sextet and two doublets. The subspectra were assigned to goethite, hematite, ferrihydrite and siderite, according to their known Mössbauer parameters. The room temperature spectra indicated that goethite and/or hematite are in the superparamagnetic state at room temperature. The results can be interpreted in terms of karstification of hypogenic caves by the role of biofilms via discharge features.     

Mössbauer and mineral magnetic studies on archaeological potteries from Adhichanallur, Tamilnadu, India

Megalithic potteries collected from Adhichanallur, Tamilnadu, India (Lat. 8°44′ N; Long. 77°42′ E) have been subjected to various spectroscopic and rock magnetic studies. The type of clay, their origin, level of structural deformation due to firing, firing temperature and atmospheric condition followed during making the potteries are analyzed. The potteries were subjected to Mössbauer and X-ray diffraction studies to analyze the iron phases in them. It is found that the samples were made of local clay (red clay), fired above 600°C under open atmospheric and/or reduced atmospheric conditions and air has been allowed during cooling. The Mössbauer spectra reveal the presence of Fe^3?+?, Fe^2?+? and iron oxides of hematite and magnetite. The firing temperature and firing conditions established from Mössbauer studies are similar to the observation made from FT-IR studies. The magnetic mineral types, the mass fractions and the domain states of the constituent magnetic grains were elucidated from a range of rock magnetic measurements including variation of susceptibility with low field, frequency and temperature, hysteresis parameters and isothermal remanence acquisition data. The magnetic mineralogy of most pottery samples was dominated by magnetite/(titano) magnetite, while magnetic grain size spectrum varies from very fine (super paramagnetic) to fine (stable single domain, pseudo single domain). The reversible thermo magnetic behavior reflects no mineralogical transformations during reheating and all the samples show same Curie temperature 580°C due to magnetite. From the above information it is demonstrated that these samples are suitable for determining the reliable ancient geomagnetic field intensity values existed during that period.     

Cems characterization of SnO2 films obtained by sputtering and sol-gel route

Conversion electron Mössbauer spectroscopy (CEMS) has been used to study tin oxide films prepared by sol-gel dipping and sputtering. The spectra of films prepared by sol-gel route result close to that of crystalline SnO₂ after heat treatment at a temperature as low as 150°C. The Mössbauer parameters of as sputter deposited films indicate that the structure of the deposited stannic oxide has an amorphous character more pronounced for thinner samples. The structure becomes predominantly that of crystalline SnO₂ by heating at 550°C for 30 min provided the film thickness is higher than 10 nm.     

A Mössbauer and X-ray investigation of ξ-Fe2N

Mössbauer spectra of ξ-Fe₂N at 4·2°K, 78°K and room temperature are presented. The Mössbauer parameters are compatible with the nitrogen donor model previously found to be applicable to the lower iron nitrides. X-ray analyses of this phase confirm the structure previously reported. Mössbauer and X-ray spectra for partially nitrided iron foils containing γ′, ε and ξ iron nitrides are also discussed.