Mössbauer study of oxo derivatives of iron in the Fe2O3-Na2O2 system

Various compositions of oxo derivatives of iron reacting with sodium peroxide have been studied by Mössbauer spectroscopy. We have examined several mathematical models of the measured spectra. The results obtained are inconsistent with hypotheses made previously that such conditions may lead to the formation of compounds of iron in oxidation states above (6+). We demonstrate that a large excess of an alkali peroxide leads, most likely, to the formation of at least two iron(V) derivatives in tetrahedral coordination. In their Mössbauer spectra, they have isomer shifts of ?0.45 and ?0.51 mm/s and unusually large quadrupole splittings: 1.32 and 1.94 mm/s (at room temperature).     

Polymorphism in Sr3Fe2O7−x

The compound Sr₃Fe₂O_7–x , with variable iron valence, was investigated by X-ray powder techniques, both at room and at high temperatures. If the material is examined in massive form, a single phase called -Sr₃Fe₂O_7–x appears as previously reported in the literature. This -phase is tetragonal and exhibits the lattice parameters: a=3.874 and c=40.314 Å. Two other phases, called and -Sr₃Fe₂O_7–x , respectively, can be obtained on heating the finely powdered material when laid on a flat platinum support. The form is stable up to 1275° C, while the form is revealed only above 1275° C and changes always into -Sr₃Fe₂O_7–x when quenched. Both and phases are tetragonal, with a=4.001 and c= 58.251 for the form and a=4.013, c=57.092 Å for the form. The transition involves a true phase equilibrium, while the transformation is possible only by means of a suitable mechanical treatment of the material.     

Dielectric properties of the system Ba1−xLaxTi1−xCo x O3

The dielectric behaviour of compositions withx=0.01, 0.05, 0.10 and 0.20 in the system Ba_1–x La _x Ti-_1-x Co _x O₃ was studied in the temperature range 300–473 K. The compositions withx = 0.01 and 0.05 show a diffuse ferroelectric-paraelectric phase transition, while other compositions do not show this transition in this temperature range. The frequency dependence of dielectric constant and dielectric loss in the samples withx0.05 indicates that spacecharge polarization contributes significantly to their observed dielectric parameters.     

Formation temperature of bosons in high-T c YBa2Cu3O7−y systems

At different equilibrium temperatures, a precise measurement of the electrical resistivity (R) is performed for high T _c polycrystalline YBa₂Cu₃O_7–y systems. T ² law is applied in the part of the R-T relationship far above the superconducting transition temperature. Since Landau and Pomeranchuk predicted the T ² law arising from electron-electron scattering, a higher critical temperature of T ² law is defined as a start point (T _es) of electron-electron scattering. On the other hand, we defined a lower critical temperature of T ² law as the formation temperature (T _ee) of an electron-electron pair, i.e. the formation temperature of boson. T _ee relates to the offset temperature of the superconducting transition .     

Reaction of the superconductive oxide BaPb1−xBixO3 (BPB) with La2O3

Semiconductive BPB of x=0.4 became superconductive after it had been sintered with La₂O₃, and the maximum T_C is about 11 K. X-ray phase analysis shows that all samples consist of two or three phases, one of which is of BPB structure. Calculation of a, b, c and a_o of the BPB phase reveals that they all decrease as the amount of La₂O₃ increases. The observed and calculated T_C values are semi-quantitatively consistent with each other. This indicates that BPB does not form a single phase solid solution with La₂O₃ over a wide range, but La₂O₃ changes the ratio of Bi/Pb in the phase.     

Superconductivity Enhancement in Fe3O4 Doped YBa2Cu3O7−δ

Flux pinning can lead to the enhancement of J _c in superconductor. In order to study the effect of magnetic particles on superconductivity, the composites of (YBa₂Cu₃O_7?δ )_0.98(Fe₃O₄)_0.02 and (YBa₂Cu₃O_7?δ )_0.98(α-Fe₂O₃)_0.02 are synthesized with former sintered at different temperatures. The field-cooling measurements show that the T _c of the samples has not changed. The superconducting properties are enhanced when the samples are sintered at high temperature (750 ^°C), but suppressed for the samples without sintering or sintered at low temperature (350 ^°C). Scanning electron microscopy images show that the doped Fe₃O₄ are diffused into intergrain sites. With the increase of sintering temperatures, the grain size of the sample grows up and the flux pinning, which leads to the enhancement of J _c is formed by the addition of Fe₃O₄ nanoparticles. The extended X-ray absorption fine structure and X-ray absorption near edge structure experiments prove that after sintered at high temperatures the addition of Fe₃O₄ can induce disorder of local structures of YBa₂Cu₃O_7?δ . Also, the transition from the tetragonal phase to the orthorhombic phase is observed by the X-ray diffraction spectra. By the above analysis of experimental data, the enhancement of diamagnetic signal, which represents the superconducting properties can be attributed to the disorder enhancement of local structures and structural phase transition of the cuprates induced by the addition of Fe₃O₄.     

Investigations of Sr3Fe2−xMnxO7−δ the n=2 Ruddlesden–Popper phases with d3/d4 interactions

We have prepared a series of Mn substituted strontium ferrates, Sr₃Fe_2−xMn_xO_7−δ where x=2/3, 1 and 4/3, and investigated their properties with X-ray diffraction, X-ray absorption near edge spectroscopy (XANES), Mössbauer spectroscopy, variable-temperature resistivity and magnetic susceptibility. These compounds are metastable and have to be prepared at high temperatures, >1250°C, with solid state techniques followed by quenching in air to room temperature. As a consequence the compounds are oxygen deficient and contain some Fe³⁺. They are insulators and exhibit spin-glass like behavior at low temperatures due to frustrated magnetic interactions between the disordered array of transition metal ions on the B site. Mössbauer and XANES spectra show that the B cations are not fully oxidized and that the Fe⁴⁺ in these compounds are charge-disproportionated into Fe³⁺ and Fe⁵⁺ at low temperature.     

Two distinct structural phases in Sr3−x Ca x Ru2O y

Non-cuprate layered perovskite Sr₂RuO₄, which is an analogue of (La,Sr)₂CuO₄, exhibits superconductivity below T_c1K. We have synthesized a new system Sr_3–xCa_xRu₂O_y and found the solubility of Ca to be at least as much as x = 2. These samples are not superconductive down to 2K but magnetically ordered. The x dependence of the lattice parameters and that of T_mag clearly indicate that there are at least two distinct structural phases in Sr_3–xCa_xRu₂O_y.On leave from Hiroshima University.     

Doping of Nb to the Ba and Cu Sites in the Y0.6Gd0.4Ba2Cu3O7−δ

Polycrystalline samples of Y_0.6Gd_0.4Ba_2?x Nb _x Cu₃O_7?δ and Y_0.6Gd_0.4Ba₂Cu_3?x Nb _x O_7?δ with different Nb contents (x=0.025, 0.075, 0.125, 0.175 and 0.225) were prepared using the solid state reaction method. Structural and electrical properties of new compounds were investigated with optical microscope, scanning electron microscopy (SEM), X-ray diffraction (XRD), Four Point Probe (FPP). The results indicated that Nb constituted YBa₂NbO₆ structure instead of substituting to the Y_0.6Gd_0.4Ba₂Cu₃O_7?δ structure. YBa₂NbO₆ structures gathered between grains. Transition temperature did not change significantly, but critical current (J _c) values decreased with increase of Nb concentration. The underlying reason is that the oxygen concentration of compounds remained unchanged due to Gd; thus, T _c values did not change significantly.     

Novel approaches in the melt-texturing of YBa2Cu3O7−y

Electrochemically pre-textured samples have been subjected to melt-processing in order to produce dense and highly textured bulk samples of YBa₂Cu₃O_7–y (YBCO). Full oxygenation of these samples has been achieved at high processing temperatures of 720 °C by electrochemical titration, in order to increase the superconducting transition temperature to > 89 K. These samples show a large magnetic hysteresis, and the value of J _c calculated using the Bean model is in the range 4000–6000 A cm^–2 at 77 K and 1 tesla magnetic field, and is independent of the applied field in that range. In another variation of the melt-processing technique — referred to as isothermal melt-textured growth — highly textured samples have been produced by the movement of the solidification front at a constant temperature in an oxygen activity gradient.     

Phase transformation in the Al2O3–ZrO2 system

Co-precipitation methods have been used to produce 20 mol% Al2O3–80 mol% ZrO2 mixed oxides, from aqueous solutions of zirconium oxychloride and aluminium chloride, followed by precipitation with ammonia. The resulting gel was calcined at increasing temperatures, and X-ray diffraction confirmed that the structure remained amorphous up to 750°C and then crystallized as a single-phase cubic zirconia solid solution, but with a reduced unit-cell dimension. At higher temperatures, the unit-cell dimension increased and, above 950°C, this phase started to transform to a tetragonal zirconia (t-ZrO2) phase, again of reduced cell dimensions compared with t-ZrO2, with simultaneous appearance of small amounts of -Al2O3. Above 1100°C, the tetragonal phase transformed to monoclinic zirconia on cooling, and the amount of -Al2O3 increased. Above 1200°C, the -Al2O3 transformed to the stable -Al2O3. These results confirm that aluminium acts as a stabilizing cation for zirconia up to temperatures of about 1100°C. © 1998 Chapman & Hall     

Phase Relations in the SrO–Bi2O3–Fe2O3 System

The phase relations in the composition region SrFeO_{3 –} –Fe₂O₃–BiFeO₃ are studied in air by x-ray diffraction and electron microscopy. The 1000°C phase compatibility diagram is constructed. Sr_{1 – x} Bi _x FeO_{3 –} solid solutions are prepared in the range 0 < x 0.8. Their lattice parameter is found to vary nonlinearly with x. Two new phases were identified: (Sr,Bi)₃Fe₄O _y (tetragonal lattice, a= 3.907(2) Å, c= 27.30(2) Å) and Sr_0.6Bi_0.4FeO_{3 –} (tetragonal lattice,a = 5.555(2) Å, c= 11.848(5) Å).     

Powder X-ray diffraction identification of some new phases in the Na2SAl2S3 system

Four new phases in the Na₂SAl₂S₃ system have been identified by powder X-ray diffraction analysis. All four phases have Na₂S:Al₂S₃ ratios greater than 1:1. Analysis with X-ray diffraction and energy dispersive spectroscopy with a scanning electron microscope indicated provisional stoichiometries of α-Na₃AlS₃, β-Na₃AlS₃, and Na₅AlS₄ for three of the new phases. The fourth phase has yet to be identified.     

High-T c superconductivity in theRBa2−xSrxCu3O7 system forR ≡ Y,Gd, Sm and Nd

RBa_2–x Sr_xCu₃O₇ samples whereRY, Gd, Sm and Nd were synthesized in oxygen between 930 and 1070 °C. The effect of the Ba substitution by Sr on the sample optimum synthesis temperature, microstructure and electrical properties was investigated for 0x1.0. The magnitude of the resistivity increase and of theT _c decrease due to the Ba substitution by Sr is found to depend on theR ionic radius. Moreover, the Sr addition has a decreasing effect onJ _c for allR elements.     

High temperature thermoelectric properties of the Ca3−xBxCo4O9 system

The Ca_3?xB_xCo₄O₉ system (x = 0.0, 0.05, 0.75 and 1.0) has been prepared using the solid-state reaction technique. Structural, microstructural, transport properties (temperature dependence of resistivity, thermoelectric power) of the samples fabricated were investigated in details. The structural/microstructural investigations showed that complex and multiphase crystallographic structure was formed with the B-substitution. A decrease in the grain size was observed in the B-substituted samples. The resistivity increased with the substitution due to decrease in the grain size and weak-link among the grains. It is found that that the thermoelectric power is insensitive to the B-substitution. The highest power factor value was obtained in the x = 0.0 sample, however, it decreased in the B-substituted samples.     

Fabrication and characterization of high permittivity ceramics in the Ba(Ti1−x−ySnxZry)O3 system

Ceramics of solid solution compositions in the system BaTi_1–x–ySn_xZr_yO₃ have been fabricated using conventional mixed oxide processing routes. Samples with y = 0 or 0.01 exhibited maximum relative permittivities, _r ^max of ~ 65000 and ~ 62000 respectively. The Curie peaks became broader and _r ^max decreased with increasing zirconium substitutions. The Curie temperature decreased linearly from 35°C for y = 0 to –40°C for y = 0.11: for the latter, _r ^max was equal to ~ 20000. The results are interpreted on the basis of microstructural features and on the degree of compositional inhomogeneity in the system.