YIG formation in annealed iron implanted YAG

YAG and YIG crystals implanted respectively with 100 keV⁵⁷Fe²⁺ ions (1 × 10¹⁷ ions.cm^?2) and 50 keV²⁷Al ions (1.1 × 10¹⁷ ions.cm^?2) have been studied by conversion electron Mössbauer spectroscopy (CEMS) directly after implantation and after annealings in air at temperatures up to 1100°C. In both as-implanted samples iron is found mainly in three states: Fe²⁺, Fe³⁺ and small metallic precipitates. Annealing behaviour is divided into two stages: (i) up to 400°C the iron has become completely oxidized and (ii) between 400 and 850°C the epitaxial regrowth of the implanted layer takes place. During this process a part of iron ions are incorporated into octahedral and tetrahedral sites, thus making a Y₃ (Al Fe)₅ O₁₂ compound. The remaining iron part precipitates in the form of Fe₂O₃ particles.     

Changes in the state of iron atoms in Zr alloys during corrosion tests in an autoclave

Mössbauerinvestigations were carried out on oxide films formed on specimens of zirconium alloys Zr-1.0 %wtFe-1.2 %wtSn-0.5 %wtCr subjected to corrosion in steam-water environment at a temperature of 360 °C and at a pressure of 16.8 MPa with lithium and boron additions, and on Zr-1.4 %wtFe-0.7 %wtCr corroded in steam-water environment at 350 °C and 16.8 MPa as well as in steam-water environment at 500 °C and 10 MPa. In the metal part of the samples, under the oxide film, the iron atoms are in form of intermetallic precipitates of Zr(Fe, Cr)₂. The corrosion process decomposes the intermetallic precipitates and particles are formed of metallic iron with inclusions of chromium atoms –Fe(Cr), α–Fe₂O₃ and Fe₃O₄ compounds. Part of the iron ions are in divalent and part in trivalent paramagnetic states. It is proposed that some part of the iron containing oxide precipitates in the oxide film may be in the form of nanoparticles which pass from the superparamagnetic to the ferromagnetic state with decreasing temperature.     

Heat treatment effects on spinel phase of Zn x Ni1 − x Fe2O4 and MnFe2O4 nanoferrites

We report the effects of heat treatment on Zn _x Ni_1???x Fe₂O₄ (x?= 0, 0.5 and 1.0) and MnFe₂O₄ ferrite nanoparticles. The as-prepared compounds were sintered from 400°C to 1100°C. Pure ZnFe₂O₄ (x?= 1.0) and MnFe₂O₄ could be obtained under low reaction temperature of 200°C. NiFe₂O₄ (x?= 0) and Zn_0.5Ni_0.5Fe₂O₄ (x?= 0.5) nanoferrites crystallized with single phase cubic spinel structure after annealing at 600°C. The single phase cubic spinel structure of these compounds was destroyed after annealing at temperature above 700°C. The magnetization measurements indicate superparamagnetic behavior of the nanosized compounds produced.     

NGR study of iron molybdates and iron-cobalt molybdates catalysts

Iron molybdates FM and cobalt-iron molybdates CF _x M (which means Co_1?y Fe _y MoO₄ withy=x/100 6≤x≤67), used as matrix of catalysts for propene mild oxidation, were studied by Mössbauer spectroscopy at 295 K and 4 K. All the spectra exhibit three Fe²⁺ doublets, two of them correspond to β-FeMoO₄ and the third one to α-FeMoO₄. Enhancement of quadrupole splittings of Fe²⁺ in the spectra of the CF _x M catalysts is ascribed to the occurrence of a solid solution of either iron in CoMoO₄ or cobalt in FeMoO₄. In each spectrum at 295 K one or several Fe³⁺ doublets were present, which low temperature spectra allow to be assigned to Fe₂(MoO₄)₃, small particles of Fe₂O₃, solid solution of Fe³⁺ in ferrous molybdates and even Fe₂MoO₄ in some cases. The behaviour of all the iron species of these solids during reduction by hydrogen is described.     

Mössbauer studies in the spinel system coxfe3−xo4

Mössbauer spectra have been obtained for the cobalt-iron spinels having the general formula CO_xFe_3?xO₄ for the whole range of composition, materials from x = 0 to x = 2.76 having been studied. The spectra fall into three groups: (A) Those for spinels for which 0 < χ < 1 which show two six-peak sets of lines corresponding to exchanging Fe²⁺/Fe³⁺ and to Fe³⁺ iron; (B) those for spinels containing Fe³⁺ iron only which show magnetic splitting 1 < χ < 2; (C) those for spinels containing Fe³⁺ iron only which show quadrupole splitting but no magnetic splitting (x = 2.3, 2.5 and 2.8). The significance of the various spectra in relation to the structure of these mixed oxides is discussed.     

Hydrothermal synthesis and structural characterization of (1−x)α-Fe2O3-xSnO2 nanoparticles

Structural and morphological characteristics of (1−x)α-Fe₂O₃-xSnO₂ (x=0.0-1.0) nanoparticles obtained under hydrothermal conditions have been investigated by X-ray diffraction (XRD), transmission Mössbauer spectroscopy, scanning and transmission electron microscopy as well as energy dispersive X-ray analysis. On the basis of the Rietveld structure refinements of the XRD spectra at low tin concentrations, it was found that Sn⁴⁺ ions partially substitute for Fe³⁺ at the octahedral sites and also occupy the interstitial octahedral sites which are vacant in α-Fe₂O₃ corundum structure. A phase separation of α-Fe₂O₃ and SnO₂ was observed for x≥0.4: the α-Fe₂O₃ structure containing tin decreases simultaneously with the increase of the SnO₂ phase containing substitutional iron ions. The mean particle dimension decreases from 70 to 6 nm, as the molar fraction x increases up to x=1.0. The estimated solubility limits in the nanoparticle system (1−x)α-Fe₂O₃-xSnO₂ synthesized under hydrothermal conditions are: x≤0.2 for Sn⁴⁺ in α-Fe₂O₃ and x≥0.7 for Fe³⁺ in SnO₂.     

Studies of oxidation of iron nanowires encased in porous aluminium oxide template

The transformations of phase composition of iron nanowires deposited into porous alumina template when annealing in the air were studied. The samples of iron nanowires of different diameter (8, 13, 15, 30 nm) were annealed for 1.5 h at temperature up to 600°C. In addition, for nanowires of 15 nm diameter the dependence of phase composition on annealing time was investigated. The phases were determined by applying Mössbauer spectroscopy. New Fe(II) and Fe(III) contributions to Mössbauer spectra were found and those were indentified as caused by the formation of hercynite FeAl₂O₄ and (Fe _x Al_1???x )₂O₃ with small x values (x?≤?0.15). It has been found that though initially the Fe(II) compound forms rapidly, afterwards its formation rate becomes lower than that of Fe(III) and after longer annealing time the Fe(III) content exceeds Fe(II) one.     

Conductivite electrique des magnetites faiblement substituees a l'aluminium ou au chrome et faiblement oxydees au voisinage de la temperature de transition de Verwey

The electrical conductivity of aluminum or chromium slightly substituted and slightly oxidized magnetites (0 < x < 0.27; 0 < δ 0.040) whose formula is Fe³⁺[□_δFe_(1?3δ)²⁺Fe_(1?x) + 28³⁺M_x³⁺]O₄^2? over the temperature range 300-77°K is affected by the composition of octahedral sites. In particular the Verwey transition temperature and its magnitude decrease with x and δ while the electrical conductivity and activation energy evolve differently on either side of this discontinuity.     

An iron-57 Mössbauer spectroscopy and EXAFS study of the hydrogen pretreatment of titania-supported iron-ruthenium catalysts

The changes in composition and structure which are induced in a titania-supported iron-ruthernium catalyst following treatment in hydrogen have been investigated in situ by⁵⁷Fe Mössbauer spectroscopy and by EXAFS. The results show that ruthenium dioxide is readily reduced at temperatures below ca. 500°C to ca. 20 Å clusters of metallic ruthenium whilst α-Fe₂O₃ is partially reduced at 130°C to Fe²⁺ and Fe⁰. The Fe³⁺ which is formed by the reoxidation of Fe²⁺ under the reducing conditions at 500°C segregates to the interface of the bimetallic phase and the titania support. It is suggested that continued treatment at 700°C produces a high dispersion of iron which is coordinated to oxygen atoms of the support. The ca. 20 Å clusters of metallic ruthenium may be envisaged as being anchored to the support via iron-ruthenium bonds     

EPR and magnetic susceptibility studies of iron ions in ZnO-Fe2O3-SiO2-CaO-P2O5-Na2O glasses

Room temperature electron paramagnetic resonance (EPR) spectra and temperature dependent magnetic susceptibility data have been obtained on bulk x(ZnO,Fe₂O₃)(65−x)SiO₂20(CaO, P₂O₅)15Na₂O (6≤x≤21 mole%) glasses prepared by melt quenching method. EPR spectra of the glasses revealed absorptions centered at g≈2.1 and 4.3. The variations of the intensity and line width of these absorption lines with composition have been interpreted in terms of the variation in the concentration of the Fe²⁺ and Fe³⁺ ions in the glass and the interaction between the iron ions. EPR and magnetic susceptibility data of the glasses reveal that both Fe²⁺ and Fe³⁺ ions are present in the glasses, with their relative concentration being dependent on the glass composition. The studies reveal superexchange type interactions in these glasses, which are strongly dependent on their iron content.     

On the Fe2+ ion contribution to induced anisotropy and magnetic after-effect in several Mn ferrites

After a brief survey of the relaxation phenomena of permeability in Mn mixed ferrites we present new results concerning induced anisotropy Ku and viscosity field in four samples of composition Mn_xFe_3?xO_{4 + y} with x = 0.2, 0.4, 0.6 and 0.8.The first important result shows that Ku is proportional to the iron content, the extrapolation giving Ku = 0 at x = 1.The other data obtained from more fundamental properties indicate that the elementary coupling energy of Fe²⁺ to the lattice, w, is of the order of 3 to $\text{4 × 10}{}^{\mathrm{?16}}\text{erg}\text{ion}\text{Fe}{}^{\mathrm{2+}}$ and seems to be related to the Curie point, that is to the exchange energy. Finally we can conclude that the Fe²⁺ ion is responsible first for the well-known ‘effect II” at 100–300°C in the thermal spectra of permeability disaccomodation and also for the strong induced anisotropy Ku created by magnetic annealing in this temperature zone. It is shown once more that Fe²⁺ plays an important role even above room temperature in spite of the Fe²⁺ ? Fe³⁺ hopping process.     

Dopant Spin States and Magnetic Interactions in Transition Metal (Fe3+)-Doped Semiconductor Nanoparticles: An EMR and Magnetometric Study

In this work, electron magnetic resonance (EMR) spectroscopy and magnetometry studies were employed to investigate the origin of the observed room-temperature ferromagnetism in chemically synthesized Sn_1?x Fe _x O₂ powders. EMR data clearly established the presence of two different types of signals due to the incorporated Fe ions: paramagnetic spectra due to isolated Fe³⁺ ions and broad ferromagnetic resonance (FMR) spectra due to magnetically coupled Fe³⁺ dopant ions. EMR data analysis and simulation suggested the presence of high-spin (S = 5/2) Fe³⁺ ions incorporated into the SnO₂ host lattice both at substitutional and at interstitial sites. The FMR signal intensity and the saturation magnetization M _s of the ferromagnetic component increased with increasing Fe concentration. For Sn_0.953Fe_0.047O₂ samples, well-defined EMR spectra revealing FMRs were observed only for samples prepared in the 350–600°C range, whereas for samples prepared at higher annealing temperatures up to 900°C, the FMRs and saturation magnetization were vanished due to diffusion and eventual expulsion of the Fe ions from the nanoparticles, in agreement with data obtained from Raman and X-ray photoelectron spectroscopy.     

Mossbauer, infrared and magnetic susceptibility studies of iron sodium borate glasses doped by sulphur

The affect of sulphur on the structural properties of iron sodium diborate glasses having the composition {(100−x)Na₂B₄O₇+xFe₂O₃}+yS, where x=0.05, 0.15 and 0.25 mol% and Y=0, 2.5 and 5 wt% was studied by infrared, Mossbauer spectroscopy and magnetic susceptibility measurements. It was found that, for samples having 5 mol% Fe₂O₃ and free from sulphur, the iron ions are present in both Fe²⁺ and Fe³⁺ states and also 92% of the total iron enters the glass network as a glass former. The ratio of Fe³⁺/Fe²⁺ increases with increasing the iron content for sulphur-free samples and others containing sulphur. This ratio also decreases with increasing the sulphur content. The magnetic susceptibility was found to decrease with increasing the sulphur content. Also, the increase of Fe₂O₃ content led to a less symmetrical environment of Fe³⁺ ions and vice versa for the Fe²⁺ environment.     

Visible light activated photo-catalytic effect and local structure of iron silicate glass prepared by sol-gel method

A relationship between methylene blue (MB) decomposition ability under visible light and local structure of xFe₂O₃·(100-x)SiO₂ glass abbreviated as xFS prepared by sol-gel method was investigated by ⁵⁷Fe-Mössbauer spectroscopy, X-ray diffractometry (XRD) and ultraviolet-visible light absorption spectroscopy (UV-Vis). Mössbauer spectra of xFS glass with x of 10, 30 and 50 annealed at 1000 °C for 3 h were mainly composed of a paramagnetic doublet due to fayalite (Fe₂SiO₄), and magnetic sextets due to magnetite (Fe₃O₄) or hematite (α-Fe₂O₃). The absorption area (A) of α-Fe₂O₃ gradually increased from 0.0 to 10.3 and 100 % with the increasing Fe₂O₃ content (x) of annealed xFS glass. A leaching test performed by 20 mL of MB aqueous solution and 40 mg of annealed 50FS glass showed that MB concentration decreased from 16.2 to 4.7 μmol L^?1 after 2 h with the first order rate constant of 1.8 × 10^?4 s^?1. These results prove that annealed iron silicate glass containing α-Fe₂O₃ can decompose MB effectively under visible light irradiation.     

An in situ iron-57 Mössbauer spectroscopic investigation of the reduction of ironcerium oxide catalysts in different gaseous reducing agents

The formation of iron-cerium oxide catalysts by the treatment in hydrogen or carbon monoxide of air-dried precipitates has been monitored in situ by⁵⁷Fe Mössbauer spectroscopy. The results show that the initial calcination of the precipitates in air induces phase segregation and the formation of small concentrations of large particle α-iron(III) oxide in combination with cerium dioxide. Treatment of the solid in hydrogen at 450°C results in the facile reduction of α-Fe₂O₃ to metallic iron which is unaffected by exposure to a reactant gaseous mixture of carbon monoxide and hydrogen. Exposure of the biphasic material formed in air to carbon monoxide at similar temperatures induces the reduction of α-Fe₂O₃ to Fe₃O₄ and metallic iron and the subsequent formation of iron carbide. The carbided catalyst is not changed by exposure to a mixture of carbon monoxide and hydrogen. In distinct contrast the cerium orthoferrite of composition CeFeO₃ suffers only slight reduction when treated in hydrogen and shows a very limited amenability to carbide formation when treated in carbon monoxide.     

Electrical properties of GdBaCo2O5+x for ITSOFC applications

In order to develop a cathode that can be used in intermediate temperature solid oxide fuel cells (ITSOFC), the double perovskite material GdBaCo₂O_5+x has been prepared and its electrode performance investigated at temperatures below 700 °C by AC impedance spectroscopy. Preliminary results show that the ASRs of GdBaCo₂O_5+x cathode materials are as low as 0.53 Ω cm² at 645 °C. This encouraging data identifies GdBaCo₂O_5+x as a potential cathode material for ITSOFCs.     

XRD and EPR structural investigation of some zinc borate glasses doped with iron ions

Glasses in the system xFe₂O₃·(100?x) [45ZnO·55B₂O₃] (0≤x≤10 mol%) have been prepared by melting at 1200 °C and rapidly cooling at room temperature. The obtained samples were submitted to an additional thermal treatment at 570 °C for 12 h in order to relax the glass structure as well as to improve the local order. The as cast and heat treated samples were investigated using X-ray diffraction (XRD) and electron paramagnetic resonance (EPR) measurements. The XRD patterns of all the studied samples show their vitreous nature. Structural modifications occurring in the heat treated samples compared to the untreated ones have been pointed out. EPR spectra of untreated and heat treated samples revealed resonance absorptions centered at g≈2.0, g≈4.3 and g≈6.4. The compositional variation of the line intensity and linewidth of the absorptions from g≈4.3 and g≈2.0 have been interpreted in terms of the variation in the concentration of the Fe³⁺ ions and the interaction between the iron ions. The EPR spectra of the untreated samples containing 5 mol% Fe₂O₃ have been studied at different temperatures (110–290 K). The line intensity of the resonance signals decreases with increase in temperature whereas the linewidth is found to be independent of temperature. It was also found that the temperature variation of reciprocal line intensity obeys the Boltzmann law.     

Application of conversion electron Mössbauer spectrometry to the study of reactive sputtered iron oxide films

The reactive sputtered iron oxide films were investigated by conversion electron Mössbauer spectrometry. The film deposited under controlled oxygen concentration and deposition rate was composed of a non-stoichiometric Fe_3?xO₄, deposited on Al₂O₃ heated at 150°C. This value of x was estimated to be 0.12 and the easy axes of magnetic spin tended to be oriented perpendicular to the surface. The Fe_3?xO₄ film was transformed into γ?Fe₂O₃ by oxidation in air at the temperature range between 205 and 355°C.     

Characterization of the Calcination Products of the Precipitates Obtained from the Bio-Oxidation with Thiobacillus Ferrooxidans of Sulphuric Water Pickling Liquors

The characterization of the calcination products of the precipitates obtained from the bio-oxidation with Thiobacillus ferrooxidans of sulphuric water pickling liquors has been carried out by means of Mössbauer spectroscopy, x-ray powder diffraction, infrared spectroscopy and transmission electron microscopy. The results show that a full transformation of the precipitates into α-Fe₂O₃ is achieved at temperatures higher than 850°C. Calcination at 700°C during two hours results in the formation of α-Fe₂O₃, ζ-Fe₂O₃ and Fe₁₂O₃(SO₄)₁₅. The Mössbauer parameters of ζ-Fe₂O₃ and Fe₁₂O₃(SO₄)₁₅ at 298 and 17K are reported.     

Local structure and water cleaning ability of iron oxide nanoparticles prepared by hydro-thermal reaction

Nanoparticles (NPs) of Fe₃O₄ and γFe₂O₃ synthesized by hydrothermal reaction were characterized by X-ray diffractometry (XRD), ⁵⁷Fe-Mössbauer spectroscopy and field emission scanning electron microscopy (FE-SEM). A decrease in concentration of methylene blue (MB) aqueous solution due to bulk Fe⁰-NP γFe₂O₃ mixture with the mass ratio of 3:7 was measured by ultraviolet-visible light absorption spectroscopy (UV-Vis). The Mössbauer spectrum of NP Fe₃O₄ prepared from hydrothermal reaction was composed of two sextets with absorption area (A), isomer shift (δ) and internal magnetic field (H _int) of 56.3 %, 0.34_±0.03 mm s^???1 and 49.0_±0.30 T for tetrahedral (T _d) Fe^III, and 43.7 %, 0.66_±0.11 mm s^???1 and 44.0_±0.71 T for octahedral (O _h) Fe^II?+?III. The Fe^II/Fe^III ratio was determined to be 0.280 for NP Fe₃O₄, giving ‘x’ of 0.124 in Fe_3???xO_4. These results show that NP Fe₃O₄ prepared by hydrothermal reaction was not regular but nonstoichiometric Fe₃O₄. Consistent results were observed for XRD patterns of NP Fe_3???xO₄ indicating sharp intense peaks at 2Θ of 30.2, 35.7 and 43.3° with a large linewidth of 0.44°, yielding the crystallite size of 29–37 nm from the Scherrer’s equation. Iso-thermal annealing of NP Fe_3???xO₄ at 250 °C for 30 min resulted in the precipitation of NP γFe₂O₃ with δ of 0.33_±0.03 mm s^???1 and H _intof 46.4_±0.27 T due to magnetic tetrahedral Fe^III. The Debye temperature of NP Fe_3???xO₄ was respectively estimated to be 267_±5.45 K for Fe $^{\mathrm{III}}(T_{\mathrm{d}})$ and 282_±7.17 K for Fe $^{\mathrm{II+III}}(O_{\mathrm{h}})$ , both of which were smaller than that obtained for bulk Fe₃O₄ of 280_±4.15 K and 307_±5.70 K, indicating that the chemical environment of iron of NPs is less rigid than that of the bulk compounds. A leaching test using methylene blue (MB) and mixture of bulk Fe⁰-NP γFe₂O₃ (3:7) showed a remarkable decrease in MB concentration from 1.90 × 10^???2 to 9.49 × 10^???4 mM for 24 h with the first order rate constant (k _MB) of 2.1 × 10^???3 min^???1. This result verifies that MB decomposing ability is enhanced by using NP γFe₂O₃ compared with the k _MB of 1.1 × 10^???4 min^???1 previously obtained from the leaching test using MB and bulk mixture of Fe⁰???γFe₂O₃ (3:7).