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.     

An investigation of FeCoCrO4 by Mossbauer spectroscopy

The spinel FeCoCrO₄ has been studied between 4.2 and 538°K. Characteristic Mossbauer spectra of paramagnetic, magnetic and electronic relaxation types have been observed. The Mossbauer parameters for Fe³⁺ ions situated at tetrahedral (A) and octahedral (B) sites have been calculated. The cation distribution in magnetic and paramagnetic phases is found to be approximately Fe_0.5³⁺Co_0.5²⁺[Co_0.5²⁺Fe_0.5³⁺Cr³⁺]O₄. The Neel temperature been determined by the temperature scanning method to be 310±5°K.     

Synthesis and laser patterning of Bi-doped Y3Fe5O12 crystals in germanosilicate glasses

New germanosilicate glasses giving the crystallization of yttrium iron garnet Y₃Fe₅O₁₂ (YIG) and Bi-doped YIG, 23Na₂O-xBi₂O₃-(12−x)Y₂O₃-25Fe₂O₃-20SiO₂-20GeO₂ (mol%), are developed, and the laser-induced crystallization technique is applied to the glasses to pattern YIG and Bi-doped YIG crystals on the glass surface. It is clarified from the Mössbauer effect measurements that iron ions in the glasses are present mainly as Fe³⁺. It is suggested from the X-ray diffraction analyses and magnetization measurements that Si⁴⁺ ions are incorporated into YIG crystals formed in the crystallization of glasses. The irradiations (laser power: 32-60 mW and laser scanning speed: 7 μm/s) of continuous wave Yb:YVO₄ fiber laser (wavelength: 1080 nm) are found to induce YIG and Bi-doped YIG crystals, indicating that Fe³⁺ ions in the glasses act as suitable transition metal ions for the laser-induced crystallization. It is suggested that YIG and Bi-doped YIG crystals in the laser irradiated part might orient. The present study will be a first step for the patterning of magnetic crystals containing iron ions in glasses.     

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.     

Magnetic behavior of the oxide spinels: Li0.5Fe2.5−2x Al x Cr x O4

In order to study the effect of substitution of Fe³⁺ by Al³⁺ and Cr³⁺ in Li_0.5Fe_2.5O₄ on its structural and magnetic properties, the spinel system Li_0.5Al _x Cr _x Fe_2.5?2x O₄ (x=0.0, 0.2, 0.4, 0.5, 0.6 and 0.8) has been characterized by X-ray diffraction, high field magnetization, low field ac susceptibility and ⁵⁷Fe Mossbauer spectroscopy. Contrary to the earlier reports, about 50% of Al³⁺ is found to occupy the tetrahedral sites. The system exhibits canted spin structure and a central paramagnetic doublet was found superimposed on magnetic sextet in the Mössbauer spectra (x>0.5).     

Structural characterization and ferromagnetic behavior of Fe-doped TiO2 powder by high-energy ball milling

Fe-doped TiO₂ powder was prepared by high-energy ball milling, using TiO₂ Degussa P-25 and α-Fe powders as the starting materials. The structure and magnetic properties of the Fe-doped TiO₂ powder were studied by X-ray diffraction, ⁵⁷Fe Mossbauer spectroscopy and vibrating sample magnetometer. The Reitveld refinement of XRD revealed that ball milling not only triggered incorporation of Fe in TiO₂ lattice but also induced the phase transformation from anatase to rutile in TiO₂ and consequently the milled Fe-doped TiO₂ powder contained only rutile.⁵⁷Fe Mössbauer effect measure showed that Fe atoms existed in Fe²⁺ and Fe³⁺ state, which were assigned to the solid solution Fe_xTi_1−xO₂. The magnetization measurements indicated that the milled Fe-doped TiO₂ powder was ferromagnetic above room temperature. The ferromagnetism in our milled Fe-doped TiO₂ powder seemingly does not come from Fe and iron oxides particles/clusters but from the Fe-doped TiO₂ powder matrices.     

The mechanism of color center production in iron doped photochromic sodalites

Bromide sodalites doped with iron (0.75 mg/cm³) have been studied by the Mossbauer technique, before and after heat treatment in hydrogen atmosphere and after coloration by u.v. light and by electron bombardment. The measurements show that u.v. or electron irradiation causes Fe²⁺ ions to convert to Fe³⁺. The number of converted ions (? 10¹⁷/cm³ for u.v. irradiation, and 5 × 10¹⁷/cm³ for electron irradiation) agrees with the expected number of F centers estimated from optical measurements. The thermal recovery time at room temperature of the Fe³⁺ ions back to their Fe²⁺ state was found to be several months.     

Electricity and Magnetism,Volume 1: Third Edition,Electricity and Magnetism,Volume 2: Third Edition,by B.I. Bleaney and B. Bleaney

During the last decade the term ‘spin glass’ has become prominent in the literature on magnetism. It refers to magnetic alloys where the spins on the impurities become locked or frozen into random orientations below a characteristic temperature T ₀. In this article the properties of spin glasses are described with particular reference to the two archetypal examples AuFe and CuMn. Interest in spin glasses was mainly stimulated by some a.c. susceptibility measurements which showed sharp, cusp-like peaks, accurately defining T ₀ and suggesting that some type of phase transition was occurring. The Mossbauer effect and the anomalous Hall effect also showed clear features at T ₀ supporting this viewpoint. But measurements of the electrical resistivity and ‘specific heat’, here usually meaning the molar heat capacity, also the remanence, magnetic hysteresis and time-dependent effects observed in spin glasses were difficult to reconcile with a phase transition approach. This article discusses the results obtained from the very wide variety of experimental techniques which have been used to investigate spin glasses, and also deals with some of the important theoretical concepts which have arisen out of these studies. Then follows a short account of the many systems which have been found to exhibit spin glass behaviour and which suggest that it is a widespread magnetic state of matter. Lastly, an example is given which shows that some of the ideas of spin glasses are applicable to problems outside the sphere of magnetic alloys.     

Dielectric relaxation and a.c. conduction phenomena of PbO-PbF2-B2O3 glasses doped with FeO

PbO-PbF₂-B₂O₃ glasses containing different concentrations of FeO have been prepared. The glasses are characterized by X-ray diffraction and differential thermal analysis. The dielectric properties viz., dielectric constant, loss, conductivity, over a moderately wide range of frequency and temperature and dielectric breakdown strength have been investigated. The results of these studies have been analyzed in the light of different oxidation states of iron with the aid of the data on IR, ESR, optical absorption and magnetic susceptibility measurements. The analysis shows that iron ions exist mainly in Fe³⁺ state, occupy tetrahedral positions and increase the insulating strength of the glass if FeO is present in smaller concentrations. However, if FeO is present in higher concentrations in the glass matrix, (i) the dielectric relaxation intensity has been observed to increase, (ii) the intensity and the half width of the ESR signal has been observed to decrease and (iii) the value of magnetic moment (evaluated from magnetic susceptibility) has been observed to drop to a value of 4.6 μ_B from 5.7 μ_B. From these results it has been concluded that in this concentration range, iron ions exist mainly in divalent state.     

Mössbauer study of iron sodium borosilicate glasses

Mössbauer effect and susceptibility measurements have been performed from 1.4 K up to 300 K on Na Borosilicate glasses with 4, 8, 12, 20% by weight of Fe₂O₃ content. Besides some small isolated paramagnetic Fe²⁺ species, two Fe³⁺ particle distributions coexist with some isolated Fe³⁺ ions. Attempts have been made to give a chart of the particle size distribution in all samples.     

EPR study of the low temperature charge density wave state of o-TaS3

We report an EPR study of the chain conductor o-TaS₃ in the low temperature charge density wave (CDW) state. The EPR spectrum is attributed to Fe³⁺ (S=5/2) impurities. A power law for the temperature dependence of the EPR intensity, (T^−α with an exponent α∼0.8) found below ∼30 K is very close to that previously found in magnetic susceptibility measurements. The possible role of these impurities in the susceptibility data are discussed.     

Correlation between the atomic and electronic structure of metallic glasses

⁵⁷Fe Mössbauer and photoemission measurements were performed on meltquenched amorphous Fe(Zr, B) and (Fe, Ni)B alloys. The atomic and electronic structure of Fe₉₀Zr₁₀ and Fe₈₈B₁₂ glasses were found to be different. Half of the Zr content could be replaced by B in the Fe₉₀Zr₁₀ glass without changing its structure. Mossbauer investigation of the amorphous (Fe_1?xNi_x)_100?yB_y (0<=x<=0.80, 12<=y<=40) system indicates preferential arrangement of Fe and Ni atoms on the transition metal sites. According to the present XPS measurements there is a remarkable shift of 0.5 eV to higher binding energies of the B ls core level energy in the Ni rich glasses compared to Fe₈₈B₁₂ corresponding to a stronger binding between the Ni and the B atoms than that of Fe and B.     

Mössbauer studies of phosphate glasses for the immobilisation of toxic and nuclear wastes

Various iron-containing phosphate glasses were investigated by Mössbauer spectroscopy. Iron was found to occur predominantly as Fe³⁺ in all glasses, and largely occupied sites with distorted octahedral coordination for both redox states. Using a base glass of nominal composition 60 P₂O₅–40 Fe₂O₃ (mol%), stepwise molar replacement of Fe₂O₃ by (0.67 Na₂O?×?0.33 Al₂O₃) increased the redox ratio, Fe²⁺/ΣFe, from 0.13 at 40% Fe₂O₃ to 0.25 at 10% Fe₂O₃. The centre shift increased and quadrupole splitting decreased by up to ～20% over this range, interpreted as a decrease in the average distortion of Fe sites from cubic symmetry, and an increase in average iron coordination. Literature revealed that recoil-free fraction ratio f (Fe³⁺)?/?f (Fe²⁺)?≈?1.3 in iron phosphate glasses, and this was considered when assessing redox. Mössbauer parameters of these and other glasses demonstrated a combination of structural stability and compositional flexibility which makes them so suitable for waste immobilisation.     

Magnetic,electrical transport and electron spin resonance studies of Fe-doped manganite LaMn0.7Fe0.3O3+δ

We have investigated the magnetic, electrical transport and electron spin resonance (ESR) properties of polycrystalline Fe-doped manganite LaMn_0.7Fe_0.3O_3+δ prepared by sol–gel method. A typical cluster-glass feature is presented by DC magnetization and AC susceptibility measurements and a sharp but shallow memory effect was observed. Symmetrical Lorentzian lines of the Mn/Fe spectra were detected above 120 K, where the sample is a paramagnetic (PM) insulator. When the temperature decreases from 120 K, magnetic clusters contributed from ferromagnetic (FM) interaction between Mn³⁺ and Mn³⁺/Fe³⁺ ions develop and coexist with PM phase. At lower temperature, these FM clusters compete with antiferromagnetic (AFM) ones between Fe³⁺ ions, which are associated with a distinct field-cooled (FC) effect in characteristic of cluster-glass state.     

Magnetic characterization of the non centrosymmetric Ba3NbFe3Si2O14 langasite

The potential relevance of the Ba₃NbFe₃Si₂O₁₄ langasite in the field of multiferroism was investigated. Interesting properties were expected, in particular in view of the frustrating stacking of its magnetic Fe³⁺ cations into triangular planes of triangle units. We hereafter report results of specific heat and magnetic measurements, Mössbauer spectroscopy and neutron diffraction. A peculiar magnetic structure is found out at low temperature. The Fe³⁺ magnetic moments adopt a triangular 120° configuration within each triangle, which is in-phase propagated in each triangular plane and is helically modulated from plane to plane.     

Spectroscopic properties of Ni and rare-earth codoped Ge-Ga-Sb-S glass

The infrared emission properties of rare-earth (i.e., Dy³⁺, Pr³⁺ or Sm³⁺) and nickel-codoped Ge-Ga-Sb-S glasses were investigated by photoluminescence measurements. It was found that the emission intensities of the rare-earth doped glasses were significantly weakened even with very few amount of nickel (i.e., 500 at. ppm). On the other hand, the nickel-doped glasses show larger indices of refraction, which property will be desirable in nonlinear optics. Our results, however, suggest that to obtain rare-earth doped chalcogenide glasses of better infrared emission property it is necessary to keep the nickel dopant as low as possible.     

Synthesis and characterization of CaLaFe11O19

A new ferrimagnetic compound with the chemical formula CaLaFe₁₁O₁₉ has been synthesized by solid state reaction between the respective oxides and their structural, electrical and magnetic properties have been studied. One magnetic Fe³⁺ ion in CaLaFe₁₂O₁₉ is replaced by La³⁺ ion. The crystallographic results show the compound is hexagonal magnetoplumbite. The electrical conductivity has been measured from 300 to 800 K. The activation energy changes at Curie temperature (653 K). The compound is ferrimagnetic from 300 to 653 K and above T_c it acts as a paramagnetic. Variation of inverse molar susceptibility has been measured at various temperature in paramagnetic region and Curie molar constant (C_m) is calculated. AC susceptibility measurements are made at room temperature. The Seebeck coefficient (S) measurements show that the compound is n-type.     

Structure and magnetic properties of nanocrystalline cobalt ferrite powders synthesized using organic acid precursor method

Nanocrystalline octahedra of cobalt ferrite CoFe₂O₄ powders were synthesized using the organic acid precursor route. The effect of the calcination temperature, Fe³⁺/Co²⁺ molar ratio, calcination time and type of organic acid (oxalic, benzoic and tartaric acids) on the formation, crystallite size, microstructure and magnetic properties was studied systematically. The Fe³⁺/Co²⁺ molar ratio was varied from 2 to 1.739 while the annealing temperature was controlled from 400 to 1000 °C for various periods from 0.5 to 2 h. The resulting powders were investigated using X-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). XRD results indicate that a well crystallized, single spinel cobalt ferrite phase was formed for the precursors annealed at 600-800 °C for 2 h, using oxalic and tartaric acids as precursors for Fe³⁺/Co²⁺ molar ratio 1.818. The crystallite size of as-formed powders was in the range of 38.0-92.6 nm at different operating conditions. The calcination temperature and Fe³⁺/Co²⁺ molar ratio have a significant effect on the microstructure of the produced cobalt ferrite. The microstructure of the produced powders was found to be octahedra-shaped. The crystalline, pure cobalt ferrite powders with magnetic properties having a maximum saturation magnetization (76.1 emu/g) was achieved for the single phase at Fe³⁺/Co²⁺ molar ratio 1.818 and annealing temperature of 600 °C for 2 h using tartaric acid precursor.     

Mössbauer emission spectroscopy of doped 57Co1−xO—I. Acceptor impurities: 57Co1−xO:Li

Mossbauer emission studies on Li-doped ⁵⁷Co_1?xO have been carried out It is shown that the number of Co vacancies as well as the number of L1⁺ impurities entering the lattice determine the Fe³⁺ fraction in the emission spectra A recombination model based on the acceptor character of the defects existing in the lattice is proposed This model reproduces well all the Mossbauer data.     

Magnetization and electron spin resonance of Fe impurities in (TMTSF)2AsF6: magnetic-field-dependent interaction between impurity spins and spin-density waves

A new spin-density-wave (SDW) system with magnetic impurities (TMTSF)₂(AsF₆)_1−x(FeCl₄)_x was prepared and its magnetic properties were studied by means of magnetization and electron-spin-resonance measurements. The anisotropic g-value and comparison of the Fe concentration with the Curie constant indicate that the Fe³⁺ ions are in a low-spin state. We also found that the magnetization curve of the impurity spins in this compound shows an anomalous behavior. This behavior can be explained if one assumes a field-dependent magnetic interaction between the Fe³⁺ spins and the SDW moment. We suppose that the field dependence of the SDW pinning potential is responsible for this phenomenon.