Investigation of Glasses and Glaze Coats of Composition R2O–RO–Fe2O3(FeO)–Al2O3–B2O3–SiO2 by the EPR Method

The valence state and the coordination environment of the paramagnetic centers of iron ions in glasses and vitreous coats of composition R₂O–RO–Fe₂O₃(FeO)–Al₂O₃–B₂O₃–SiO₂ have been investigated by the EPR method. The tetrahedral and octahedral coordinations of Fe³⁺ ions have been revealed. The character of change in the EPR spectra of the materials studied in the vitreous and vitrocrystalline state has been determined. It is shown that the coordination number of iron ions is dependent on the crystallization processes.     

Supertransferred hyperfine interaction in magnetic insulators (II)

The important mechanisms of supertransferred hyperfine (STHF) interactions in N–O–M chains are briefly discussed: (i) spin polarization ofns states in the N-ion due to the s-d exchange interaction,H _STHF ^sd ; (ii) contributions of spin-polarized states of the intervening O-ion,H _STHF ^II ; (iii) transfer of d-electrons of the M-ion to emptyns states in the N-ion,H _STHF ^III . The dependence ofH _STHF upon the N–O–M bond configuration, electronic structure, and orbital state of the M-ion is presented in a convenient form. The STHF interactions in the chains Sn⁴⁺–O^2––Fe³⁺, Cr³⁺ in compounds with slightly distorted Perovskite structure are considered. The STHF field in the chain Sn⁴⁺–O^2––Cr³⁺ is shown to change the sign within the range of angles near 170°. This conclusion is in line with published data on the isoelectronic chain Sn⁴⁺–O²–Mn⁴⁺ in the compounds Ca_1–x Sr _x MnO₃. The results obtained for the N–O–Fe³⁺ chain are rationalized by the predicted angular dependence ofH _STHF=+ cos + cos². Features of the STHF interactions in N–O–M chains with an M-ion in an orbital degenerate state are examplified by a preliminary analysis of N–O^2––V³⁺ chains in orthovanadites.     

Oxygen nonstoichiometry of Sr(Co,Fe)O3−δ-based perovskites: I. Coulometric titration of SrCo0.85Fe0.10Cr0.05O3−δ by the two-electrode technique

The p(O₂)–T–δ diagram of perovskite-type SrCo_0.85Fe_0.10Cr_0.05O_3−δ was determined by the coulometric titration technique in the temperature range 770–1250 K at oxygen partial pressures from 8 10⁻¹⁰ to 0.5 atm. Stability of the cubic perovskite phase of SrCo_0.85Fe_0.10Cr_0.05O_3−δ, existing down to the oxygen pressures of 10⁻³–10⁻⁵ atm, was found to be slightly higher than that of SrCo_0.80Fe_0.20O_3−δ, probably due to stabilization of oxygen octahedra neighboring Cr⁴⁺ cations. When the oxygen nonstoichiometry of the Cr-containing perovskite decreases from 0.47 to 0.38, the partial molar enthalpy and entropy for overall oxygen incorporation reaction vary in the ranges −165 to −60 kJ mol⁻¹ and 90 to 150 J mol⁻¹ K⁻¹, respectively. Within the stability limits of the single perovskite phase, the p(O₂)–T–δ diagram can be adequately described by equilibrium processes of oxygen incorporation, cobalt disproportionation and interaction of cobalt and iron cations, with the thermodynamic functions independent of defect concentrations. Increasing grain size in SrCo_0.85Fe_0.10Cr_0.05O_3−δ ceramics from submicron size to 100–200 μm has no effect on the oxygen thermodynamics. The two-electrode coulometric titration technique, based on the alternate use of electrodes for oxygen pumping and e.m.f. measurements, is described and verified by studying oxygen nonstoichiometry of La_0.3Sr_0.7CoO_3−δ and PrO_x.     

Lithium ion conductive glass–ceramics with Li3Fe2(PO4)3 and YAG laser-induced local crystallization in lithium iron phosphate glasses

The glasses with the composition of 37.5Li₂O–(25 − x)Fe₂O₃–xNb₂O₅–37.5P₂O₅ (mol%) (x = 5,10,15) are prepared, and it is found that the addition of Nb₂O₅ is effective for the glass formation in the lithium iron phosphate system. The glass–ceramics consisting of Nasicon-type Li₃Fe₂(PO₄)₃ crystals with an orthorhombic structure are developed through conventional crystallization in an electric furnace, showing electrical conductivities of 3 × 10^− 6 Scm^− 1 at room temperature and the activation energies of 0.48 eV (x = 5) and 0.51 eV (x = 10) for Li⁺ ion conduction in the temperature range of 30–200 °C. A continuous wave Nd:YAG laser (wavelength: 1064 nm) with powers of 0.14–0.30 W and a scanning speed of 10 μm/s is irradiated onto the surface of the glasses, and the formation of Li₃Fe₂(PO₄)₃ crystals is confirmed from XRD analyses and micro-Raman scattering spectra. The crystallization of the precursor glasses is considered as new route for the fabrication of Li₃Fe₂(PO₄)₃ crystals being candidates for use as electrolyte materials in lithium ion secondary batteries.     

57Fe Mössbauer spectroscopy on disordered crystalline media with Ca-gallogermanate type structure. I. In the paramagnetic range

Polycrystalline strontium iron germanates of the type Sr_3–y Ln _y Fe_2+y Ge_4–y O₁₄(Ln=La, Nd;y=0, 1) were investigated by⁵⁷Fe Mössbauer spectroscopy in the temperature range 4.2–300 K. The crystal chemistry and the distribution of Fe³⁺ ions in the structure, as well as the crystallographic inequivalence of the oxygen polyhedra occupied by iron, were studied over the whole paramagnetic temperature region. A correlation of the experimental data with a local environment computation is given.     

Hybrid system of iron porphyrin on aminosilanized c-Si

Adsorption of iron porphyrin (Fe^IIITPPS₄) Fe(III)meso-tetra(4-sulfonatophenyl) porphine on aminosilanized surface of crystalline Si (c-Si) was investigated. Formation of nanometric structures of Fe^IIITPPS₄ on c-Si, the surface of which has been modified by various silanization procedures, was studied. Aqueous, ethanol and acetone solutions of 3-aminopropyltrietoxysilane (APTES) were prepared for deposition on c-Si by spinning or immersion techniques. Smooth homogeneous APTES films of thickness 100–500 nm were produced by multiple spin coating procedure. Thin APTES films of thickness 2.5 nm were fabricated by dipping technique followed by washing procedure. Hybrid system of Fe^IIITPPS₄/APTES/Si was prepared from a drop of Fe^IIITPPS₄ aqueous solution put on aminosilanized Si surface or by dipping the Si wafer in Fe^IIITPPS₄ aqueous solution. Nanostructures of size 50–250 nm were formed along with large rings of Ø50–100 μm which have been observed at chemisorption of highly concentrated (1 mM) Fe^IIITPPS₄ aqueous solution. Spectroscopic ellipsometry was used to characterize the APTES layer and to investigate the aggregation state of Fe^IIITPPS₄. The studies provided allowed one to presume that covalent bonds were formed between amino-groups of APTES and functional groups of sulfonic acid in porphyrin leading to immobilization of Fe^IIITPPS₄ on Si substrate.     

Giant Hall effect in (GaAs)Fe granular films

A series of (GaAs)_1 − xFe_x (x: volume fraction) films with Fe granules embedded in GaAs matrix were prepared by magnetron sputtering. Hall Effect of the films was characterized. The largest saturated Hall resistivity of was observed in (GaAs)₃₀Fe₇₀ film at room temperature, which is over 2 orders larger than that of pure Fe, about 1 order larger than that of (NiFe)–(Al₂O₃) and (NiCo)–(SiO₂) granular films prepared under the same preparation conditions, and 150% larger than that of Ge₃₀Fe₇₀.     

Mössbauer and magnetic studies on the spin states of diiron(III)-porphyrin dicopper(II) complexes

Several biological model complexes of cytochrome c oxidase analogues, such as X₂(TPP)₂Fe₂(Apen)Cu₂Cl₄, where TPP=5, 10, 15, 20-tetraphenylporphine, Apen=bis(acetylpyrazine)-ethylenediimine, X=Cl^–, N ₃ ^– , Im, 1-Me-Im, 2-Me-Im, 4-Me-Im and OCH ₃ ^– , were prepared. The electronic spin states of these complexes in solid state were studied by means of Mössbauer and EPR spectroscopies and magnetic susceptibility measurements. The iron(III) atom of these complexes is present in different spin states, depending upon the nature of the axial ligand X of Fe(III)-porphyrin; the N ₃ ^– , Cl^–, OCH ₃ ^– , 2-Me-Im axial groups lead to complexes in a pure high-spin state independent of temperature. In contrast, the imidazole axial groups (e.g. Im, 4-Me-Im) behave differently and all show a temperature dependence of the⁶A₁ ²T₂ spin transition. The magnetic exchange behavior between Fe and Cu atoms in the present complexes is also discussed.     

Study of [Fe(pyim)3] complexes: dynamic spin equilibrium on encapsulation in zeolite Y

Tris complex of Fe^II2(2′-pyridyl)imidazole has been encapsulated in the supercages of zeolite Y and characterized by using powder XRD, FTIR, Mössbauer spectroscopy, variable temperature magnetization and MAS NMR techniques and results have been compared with those obtained for this complex with ClO₄⁻ and SO₄²⁻ as anions. At room temperature, the [Fe(pyim)₃](ClO₄)₂ complex exhibited low spin state, while [Fe^II(pyim)₃]SO₄ exhibited the existence of both low and high spin states. The encapsulated [Fe^II(pyim)₃]²⁺ complex exhibited a broad quadrupole doublet characterized by isomer shift, δ=+0.55 mm/s and quadrupole splitting ΔE_q=1.26 mm/s. The magnetization measurements carried out for the encapsulated [Fe^II(pyim)₃]²⁺ complex showed a systematic decrease in its values with decreasing temperature down to 75 K with no indication of thermal hysteresis effects. These results suggest the existence of a dynamic spin state equilibrium between the high and low spin states for the encapsulated [Fe^II(pyim)₃]²⁺ complex with time constant comparable to the characteristic Mössbauer time scale of ⁵⁷Fe nuclei.     

Sono-enhanced degradation of dye pollutants with the use of H2O2 activated by Fe3O4 magnetic nanoparticles as peroxidase mimetic

Sono-enhanced degradation of a dye pollutant Rhodamine B (RhB) was investigated by using H₂O₂ as a green oxidant and Fe₃O₄ magnetic nanoparticles (MNPs) as a peroxidase mimetic. It was found that Fe₃O₄ MNPs could catalyze the break of H₂O₂ to remove RhB in a wide pH range from 3.0 to 9.0 and its peroxidase-like activity was significantly enhanced by the ultrasound irradiation. At pH 5.0 and temperature 55 °C, the ultrasound-assisted H₂O₂–Fe₃O₄ catalysis removed about 95% of RhB (0.02 mmol L⁻¹) in 15 min with a apparent rate constant of 0.15 min⁻¹ for the degradation of RhB, being 6.5 and 37.6 folds of that in the simple catalytic H₂O₂–Fe₃O₄ system, and the simple ultrasonic US-H₂O₂ systems, respectively. The beneficial synergistic behavior between Fe₃O₄ catalysis and ultrasonic was demonstrated to be dependent on Fe₃O₄ dosage, H₂O₂ concentration, pH value and temperature. As a tentative explanation, the observed significant synergistic effects was attributed to the positive interaction between cavitation effect accelerating the catalytic breakdown of H₂O₂ over Fe₃O₄ nanoparticles, and the function of Fe₃O₄ MNPs providing more nucleation sites for the cavitation inception.     

Relation between the fine structure of the vibrational spectrum of the crystal lattice and the cation distribution in Co1+2xFe2−3xSbxO4 ferrites

The infrared reflection spectra in the region of lattice vibrations (1500–200 cm^–1) of ferrite spinels Co_1+2xFe_2–3xSb_xO₄ with x=0.0–0.4 are investigated. The permittivity spectra are calculated using the Kramers-Kronig relations. A dispersion analysis of the ₁(v); ₂(v) spectra, carried out using the multiscintillator model, enabled the fine structure of the bands of the spectra to be determined. It was found that for CoFe₂O₄ ferrite the short-wave band (v=590 cm^–1) consists of two components, while the long-wave band (v=375 cm^–1) consists of fur components. Since cobalt ferrite is inverted spinel, in which there are only Fe³⁺ ions in the tetra positions, the doublet structure with v=590 cm^–1 must obviously belong to vibrations of the ion groups FeO₆ and CoO₆, while the second band may belong to vibrations of the ion complexes consisting of the tetra-cation (Fe³⁺), oxygen and the three closest octa-cations [3Fe], [2Fe1Co], [2Co1Fe] and [3Co]. The replacement of some of the iron ions with antimony leads to the appearance of additional lines from the short-wave edge of both bands. The intensity of these lines increases as the value of the diamagnetic substitution increases, which enables the highest-frequency component to be uniquely related to the vibrations of the complex formed by the tetra-cations Fe³⁺ or Co²⁺, the anion and the three octa-cations Sb⁵⁺.V. I. Ul'yanov-Lenin Kazan State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 105–109, July, 1995.     

Preparation and study of magnetic properties of silico phosphate glass and glass-ceramics having iron and zinc oxide

The magnetic properties of 25SiO₂–50CaO–15P₂O₅–(10−x)Fe₂O₃−xZnO (where x=0, 2, 5 mol%) glass and glass-ceramics have been studied. These glasses are prepared by melt quench technique and heat treated at 800 °C for 6 h. Electron Spectroscopy for Chemical Analysis (ESCA) revealed that the fraction of non-bridging oxygen decreases with the increase in zinc oxide content. Evolution of crystalline phases in glass-ceramics has been studied by X-ray diffraction (XRD). The microstructure as seen by scanning electron microscopy (SEM) exhibits formation of nanosize particles. Effect of controlled heat treatment on magnetic properties was studied by means of a Superconducting Quantum Interference Device (SQUID) magnetometer. Mössbauer spectroscopy at room temperature was also carried out to determine the state of iron ions in glasses and glass-ceramics. Isomer shift values of the glasses suggest that Fe³⁺ and Fe²⁺ are in tetrahedral coordination. The analysis of the glass without ZnO shows about 58 wt% of total iron ions is in the Fe³⁺ state. The samples on heat treatment show improved magnetic properties due to the formation of magnetic nanoparticles. Magnetic studies revealed the relaxation of magnetic particles and the increase in saturation magnetization with addition of 2 mol% ZnO. Increase in ZnO content results in decrease in the strength of dipolar interactions.     

Magnetic properties of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> surface

The magnetic properties of the magnetite Fe₃O₄(110) surface have been studied by spin resolved Auger electron spectroscopy (SRAES). Experimental spin resolved Auger spectra are presented. The results of calculation of Auger lines polarization carried out on the basis of electronic state density are presented. Problems related to magnetic moments of bivalent (Fe²⁺) and trivalent (Fe³⁺) ions on the Fe₃O₄(110) surface are discussed. It is established that the deposition of a thin bismuth film on the surface results in significant growth of polarization of iron Auger peaks, which is due to additional spin-orbit scattering of electrons by bismuth atoms.     

The magnetic anisotropy of manganate ferrites

The anisotropy constants K₁ for systems Mn_xFe_3–xO₄, with 1x 1·8, are calculated on the basis of the one-ion model and it is shown that the anomalous temperature dependence of the constant K₁ can be explained by the presence of Mn³⁺ ions in octahedral positions. The influence of the spin order on the magnetic anisotropy and the uniaxial anisotropy in systems Mn_xFe_3–xO₄ are discussed.     

A Spectroscopic Study of Polynuclear Complex of Iron(III) with Inuline Oligomers

The infrared spectra of the hydrates of inuline oligomers and the complex of iron(III) with inuline oligomers and their partial deuterated analogs were studied. From the appearance and frequencies of the bands in the range of OH and OD vibrations it was concluded that these crystalohydrates have one type of H₂O molecule, and relatively weak hydrogen bond (estimated O_w…O distances are 280 and 283 pm for inuline and its complex, respectively). From the FTIR spectra of the complex the β₂-form for iron(III) oxihydroxide (FeOOH) was determined. On the basis of the electron spin resonance spectra it was concluded that Fe⁺³ ions of octahedral configuration (g-value 2.03 ± 0.01) were present in the complex. From the measured ESR line width (ΔH = 100 ± 5 mT) the approximate Fe inter atomic distance of 0.21 nm was calculated, indicating a dense packing of Fe atoms in the cluster.     

Role of holes states on metal to insulator transition and collapse of magnetic ordering in LaFe1−xNixO3 (x = 0.0–0.5)

Polycrystalline LaFe_1?xNi_xO₃ (x = 0.0, 0.1, 0.3 and 0.5) have been prepared by the standard solid state reactions method. The phase formation has been confirmed by the powerful synchrotron X-ray diffraction experiment. In order to investigate the effects of Ni doping on the oxidation state, spin state and the magnetic ordering of the iron cations, ⁵⁷Fe Mössbauer Spectroscopy has been carried out at room temperature. Iron is present as Fe³⁺ in high spin state in LaFeO₃. Ni doping has no effect on the spin state of the Fe³⁺ cations. However, a progressive increase in the concentration of Fe⁴⁺ cations has been inferred. Relatively stronger covalent character of the Fe⁴⁺–O^?2 bond causes a progressive collapse in the magnetic ordering and delocalization of the hole states.     

57Fe Mössbauer study on some LiTi ferrites

⁵⁷Fe Mössbauer experiments have been performed on the Li_0.5+0.5t Fe_2.5–1.5t Ti _t O₄ ferrite system (t=0, 0.5, 0.8, 1.0) without and in external magnetic fields up to 6 T at 4.2 K and above. The samples up tot=0.8 exhibit collinear ferrimagnetic order and an iron distribution over the A and B sites according to the formula of Blasse. The sample LiFeTiO₄ exhibits spin canting. In contrast to other compounds, the canting angle increases with increasing applied field for both A and B sites. The iron distribution ratio differs from the expected value of 1.0.     

On the role of Fe2+ ions and cation vacancies in the disaccommodation of ferrites

A study was made of the disaccommodation spectrum of ferrites Mn _x Fe _3–x O _4+y , x>1, in a temperature range above 0°C. A comparison with analogous spectra of ferrites rich in iron (x<1), which contain Fe²⁺ ions in addition to cation vacancies, shows that the disaccommodation maximum around room temperature, observed in iron rich ferrites, is subject to the presence of Fe²⁺ ions. On the other hand, the processes taking place at higher temperatures seem to be substantially common to both types of ferrites and are dependent only on the presence of vacancies.     

Characterisation by Mössbauer Spectroscopy of the Forms of Iron in Sulfide-Rich Fulvic Acid Solutions

Variations in the nature of the bonding between iron and fulvic acid as a function of pH in sulfide-rich solutions have been investigated by ⁵⁷Fe Mössbauer spectroscopy. In all solutions iron was enriched to 95% in the ⁵⁷Fe isotope and ratios of Fe:fulvic acid were maintained at 1:100 on a weight basis for all measurements. When the pH was decreased below 5.0, there was a progressive change in the composition of the spectra, which contained three distinct components that were similar to those seen in the absence of sulfide; i.e., a sextet from magnetically-dilute Fe(III) and doublets from Fe(II) and Fe(III). There was, however, a higher proportion of the iron as Fe(II) in the sulfide-containing solutions and this represented the only form of iron at very low pH. Establishment of equilibria was slow as evidenced by considerable hysteresis between the compositions of the solutions with decreasing and increasing pHs. On increasing the pH, sulfide prevented the formation of magnetically dilute Fe(III) species and instead, in the range 3.5–6.0, compounds were generated with parameters consistent with sulfur being coordinated to the iron. One had parameters similar to those of pyrite and hence probably contains disulfide (S₂ ^2–) units, whilst a second, with poorly defined magnetic hyperfine splitting, may contain monosulfide (S^2–) units, with structures related to either pyrrhotite (Fe_1–x S) or greigite (Fe₃S₄). A third component probably corresponds to a mononuclear low spin Fe(II) complex, involving sulfur and fulvic acid in the iron coordination sphere. These species were oxygen-sensitive and decomposed to yield magnetically dilute Fe(III) complexes and Fe(III) oxyhydroxides on aeration of the solutions.     

Paramagnetic defects in BaTiO3 and their role in light-induced charge transport — Optical studies

On the basis of a previous identification of paramagnetic defects in nominally undoped as grown BaTiO₃ single crystals, we have investigated the changes of the concentrations of these centers and their optical absorptions under illumination with light of varying wavelengths. The most pronounced charge transfers occur by hole ionization of Fe⁴⁺ and — to a lesser extent — of Cr⁵⁺ and Cr⁴⁺. At low temperatures the created holes are trapped in the form of O^–-ions next to Al³⁺ or unknown acceptor defects. Corresponding Fe⁴⁺ and O^– absorptions have been identified.