Standard Gibbs' energies of formation of BaCuO2, Y2Cu2O5 and Y2BaCuO5

The Gibbs' energies of formation of BaCuO₂, Y₂Cu₂O₅ and Y₂BaCuO₅ from component oxides have been measured using solid state galvanic cells incorporating CaF₂ as the solid electrolyte under pure oxygen at a pressure of 1.01×10⁵ Pa BaO + CuO BaCuO₂ G _f,ox ^o (± 0.3) (kJ mol^–1)=–63.4–0.0525T(K) Y₂O₃ + 2CuO Y₂Cu₂O₂ G _f,ox ^o (± 0.3) (kJ mol^–1)=18.47–0.0219T(K) Y₂O₃ + BaO + CuO Y₂BaCuO₅ G _f,ox ^o (± 0.7) (kJ mol^–1)=–72.5–0.0793T(K) Because the superconducting compound YBa₂Cu₃O_7– coexists with any two of the phases CuO, BaCuO₂ and Y₂BaCuO₅, the data on BaCuO₂ and Y₂BaCuO₅ obtained in this study provide the basis for the evaluation of the Gibbs' energy of formation of the 1-2-3 compound at high temperatures.     

EPR study of polycrystalline superconductors with YBa2Cu3O7 structure

Electron paramagnetic resonance (EPR) of Gd³⁺, Eu²⁺, and copper ions has been investigated in the high-T_c superconductor with YBa₂Cu₃O_7– structure. It has been established that the system is heterogeneous at 0.150.5 and consists of metallic and dielectric regions. The former arises due to oxygen enrichment while the later due to oxygen deficiency. The integral of exchange interaction between Gd³⁺ localized moments and conduction electrons J_sf=0.016 eV has been determined from the normal state temperature dependence of Gd³⁺ EPR linewidth for metallic regions. T_c depression by gadolinium-localized moments for GdBa₂Cu₃O_7– was estimated to be T_c–2K. Anomalies in linewidth temperature dependence upon transition from the normal to the superconducting state have given information about the value and temperature behavior of the superconductor's energy gap. The model, which gives the opportunity to understand some peculiarities of the EPR signal for YBa₂Cu₃O_7– samples, is proposed in terms of several bottlenecked spinsubsystems: spin-liquid in CuO planes and Cu²⁺-O^– and Cu²⁺-O^2– fragments in CuO chains.     

Low-temperature specific heat of YBa2Cu3O7, YBa2Cu3O6, Y2BaCuO5, YBa3Cu2O7, BaCuO2, and CuO

We have measured the low-temperature specific heat (1.3T20 K) and the dc magnetic susceptibility (100T250 K) of eight samples of the high-T _c superconductor Y _x Ba_3–x Cu₃O_7– (x=0.9, 1.0, 1.1) and of two samples of nonsuperconducting YBa₂Cu₃O₆₊. We have also performed specific heat measurements on the possible impurity phases: YBa₃Cu₂O₇, Y₂BaCuO₅, CuO, and BaCuO_2+x . The superconducting samples all have a nonzero, sample-dependent linear term * and an upturn inC/T at very low temperature. We show that this anomalous behavior is at least partly due to the presence of a small amount (1%) of BaCuO_2+x impurity phase in the measured samples. This is evidenced by the correlation between * and the Curie component of the susceptibility, which is proportional to the amount of paramagnetic impurities.     

Bulk thermal expansion studies of BiCaSrCu2O x and Bi2CaSr2Cu2O x

The compounds BiCaSrCu₂O _x and Bi₂CaSr₂Cu₂O _x were prepared by ceramic techniques and characterized by X-ray powder diffractometry (XRD) and microthermogravimetry (TG) and their bulk thermal expansion measurements were carried out using dilatometry in the temperature range 298T1073 K in air. The results have been analyzed and are compared with those obtained earlier for YBa₂Cu₃O₇. The XRD analysis shows that both BiCaSrCu₂O _x and Bi₂CaSr₂Cu₂O _x are single phase in nature, having an orthorhombic symmetry. The TG analysis carried out in oxygen, air, and nitrogen shows negligible weight loss (R~0.1%) on heating to 1073 K, indicating that these two compounds, unlike YBa₂Cu₃O₇, are quite stable. The analysis of bulk thermal expansion data reveals that the average linear thermal expansion coefficient ( ₁) for both BiCaSrCu₂O _x and Bi₂CaSr₂Cu₂O _x is almost the same ( ₁ 10.5×10^–6 K^–1) and is found to be nearly half of that for YBa₂Cu₃O₇ ( ₁ 18×10^–6 K^–1), suggesting that the interatomic bonding in both BiCaSrCu₂O _x and Bi₂CaSr₂Cu₂O _x is stronger as compared to YBa₂Cu₃O₇.     

Energy Scales in the Local Magnetic Excitation Spectrum of YBa2Cu3O6+y

The wave-vector integrated dynamical spin susceptibility _2D() of YBa ₂ Cu ₃ O _6+y cuprates is considered. _2D is calculated in the superconducting state from a renormalized mean-field theory of the t–t–J-model, based on the slave-boson formulation. Besides the well-known 41 meV resonance a second, much broader peak ('hump') appears in Im _2D. It is caused by particle-hole excitations across the maximum gap ⁰ . In contrast to the resonance, which moves to lower energies when the hole filling is reduced from optimal doping, the position of this 'hump' at 2 ⁰ stays almost unchanged. The results are in reasonable agreement with inelastic neutronscattering experiments.     

Ionic conductivity and crystal structure relationships in Ti/Cu substituted Bi4V2O11

Crystal structure and oxide ion conductivity of a series of Ti and Ti-Cu double substituted Bi₄V₂O₁₁ compounds, Bi₂V_(1–x)Ti _x O_(11–x)/2 (0.085 x 0.15), and Bi₂V_0.9Cu_(0.1–x)TixO_5.35+x (0 x 0.1), were investigated using X-ray powder diffraction and ac impedance spectroscopy in the temperature and frequency range of 100–700°C and 10^–2–10⁷ Hz, respectively.Structural phase transitions, and , occur as a function of composition in Ti substituted compounds for which the is evidenced to be stable at room temperature when x exceeds 0.125. For all Ti-Cu double substituted compounds studied, the room temperature phase was identified to be phase.The required amount of Ti for phase stabilization at room temperature was significantly reduced and the conductivity improved when Cu substituted a part of Ti. Therefore, for the Bi₂V_0.9Cu_(0.1–x)Ti _x O_5.35+x (0 x 0.075) compounds the ionic conductivity increased and activation energy decreased with decreasing x. At low temperature, the highest ion conductivity was obtained for Bi₂V_0.9Cu_0.1O_5.35. At high temperature (T>500°C), a different behavior was observed. The total conductivity increased at first with decreasing x values down to x = 0.05 and then decreased. The maximum conductivity was obtained for Bi₂V_0.9Cu_0.05Ti_0.05O_5.4, and the activation energy decreased with decreasing x values, such as what happened at low temperature.     

Electron Paramagnetic Resonance of Tb3+ Ions in YBa2Cu3O6

The first observation of electron paramagnetic resonance (EPR) of Tb³⁺ doped into YBa₂Cu₃O₆ is reported. EPR is used to determine the local symmetry of the rare-earth ion and to study the effect of suppression of high-T _c superconductivity by doping. The distance between the lowest singlets of Tb³⁺ ion 7.1 GHz 0.24 cm^–1 and g-factor g 17.9 have been estimated from measurements. Both these parameters are in a good agreement with the corresponding calculated values. No evidence of Tb⁴⁺ ions was found.     

Photoinduced Changes of the Electrical Anisotropy in Oxygen-Depleted YBa2Cu3O x

Long-term photoexcitation experiments were performed on Y Ba ₂ Cu ₃ O _x (x6.6) thin films, prepared by pulsed-laser deposition on tilted SrTiO₃ substrates. From the anisotropic resistance of the samples, the in-plane and the out-of-plane resistivities were calculated. Photoexcitation was carried out with a He-Ne laser at various temperatures from 70 K to 305 K. We observed that the electrical anisotropy _c/_ab increased at low temperatures, but decreased at high temperatures. This unusual behavior resembles that of the in-plane Hall mobility in a previous study. Possible interpretations according to the models for the photodoping effect in YBa ₂ Cu ₃ O _x are discussed.     

Synthesis and Luminescent Properties of ZnGa2S4:Eu,F and ZnGa2O4:Eu,F

ZnGa₂S₄:Eu,F and ZnGa₂O₄:Eu,F were synthesized and characterized by x-ray diffraction and photoluminescence (PL) measurements. ZnGa₂S₄:Eu,F has a tetragonal structure (sp. gr. ) with a= 5.272 Å and c= 10.451 Å, and ZnGa₂O₄:Eu,F has a cubic structure (sp. gr. Fd3m) with a= 8.32 Å. The PL spectrum of ZnGa₂S₄:Eu,F consists of a broad band (FWHM = 1.11 eV) at 565 nm due to the Eu²⁺ 5D ¹ 7F ² transition, and the spectrum of ZnGa₂O₄:Eu,F shows four emissions due to the Eu^{3+ 5} D ₀ ⁷ F ₄ (_max = 682 nm), ⁵ D ₀ ⁷ F ₂ (_max = 615 nm), ⁵ D ₀ ⁷ F ₁ (_max = 595 nm), and ⁵ D ₀ ⁷ F ₀ (_max = 584 nm) transitions.     

Changes in valency state of ions in CuMn2O4 at high temperatures

Thin films of copper manganite with three different molar ratios of CuMn viz 11, 12 and 13 have been deposited on quartz plates. The electrical conductivity of these thin films has been studied as a function of temperature. The energy of activation for electrical conduction in these compounds is found to increase from 0.20 eV to about 0.62 eV above 600° K. Differential thermal analysis of bulk sample of copper manganite also shows a small endothermic change at 600° K, while thermogravimetric analysis does not show any change in weight. It has been concluded from these results that the stable form of the ionic configuration of copper manganite at low temperatures, i.e. Cu¹⁺[Mn³⁺Mn⁴⁺]O₄ changes at high temperatures to Cu²⁺[Mn₂ ³⁺]O₄     

Microstructural development and mechanical properties of pressureless-sintered SiC with plate-like grains using Al2O3-Y2O3 additives

Dense SiC ceramics with plate-like grains were obtained by pressureless sintering using -SiC powder with the addition of 6 wt% Al₂O₃ and 4 wt% Y₂O₃. The relationships between sintering conditions, microstructural development, and mechanical properties for the obtained ceramics were established. During sintering of the -SiC powder compact the equiaxed grain structure gradually changed into the plate-like grain structure that is closely entangled and linked together through the grain growth associated with the phase transformation. With increasing holding time, the fraction of phase transformation, the grain size, and the aspect ratio of grains, increased. Fracture toughness increased from 4.5 MPa m^1/2 to 8.3 MPa m^1/2 with increasing size and aspect ratio of the grains. Crack deflection and crack bridging were considered to be the main operative mechanisms that led to improved fracture toughness.     

Mechanical relaxation of 4 wt% Y2O3-ZrO2 tetragonal single crystals

The mechanical relaxation was examined by a resonance piezoelectric method for a 3.5 wt % Y₂O₃-ZrO₂ polycrystal and 4 wt% Y₂O₃-ZrO₂ tetragonal single crystals with orientations in the 100 and 111 directions. The relaxation was observed for the 111-oriented crystal, but not for the 100-crystal. The results indicated that the relaxation was active only for the elastic compliance, S₄₄, and inactive for (s ₁₁–s ₁₂). The amplitude of the anelastic relaxation measured for the polycrystalline and the 111-crystal body was 4.2 × 10^–12 m²N^–1 and 6.7×10^–12 m² N^–1, respectively. An observed broad relaxation peak suggested that complex processes exist even in single crystals.     

Superconducting properties of the lithium-substituted YBa2Cu4O8 prepared by the sol-gel method

The effects of the lithium substitution for copper on the properties of the superconducting YBa₂Cu₄O₈ were studied. Single-phase YBa₂Cu_4–x LixO₈ was successfully prepared by the sol-gel method under ambient pressure over a composition range of 0x 0.08, while impurity phases appeared at x=0.10 and 0.20. The lattice constants of YBa₂Cu_4–x Li _x O₈ were almost invariant with increasing lithium content x. The superconducting transition temperature decreased monotonically with increasing x in the range, 0x0.08. The suppression of superconductivity was discussed in terms of the impurity effect in the CuO₂ planes.     

EPR and magnetic susceptibility studies of xCr2O3-(1-x) 3B2O3-PbO glasses

By using X-ray diffraction analysis, EPR and magnetic measurements, the chromium-ion distribution in xCr₂O₃-(1–x) [3B₂O₃-PbO] glasses with 0x35 mol% Cr₂O₃ was studied. EPR investigation evidenced the presence of both Cr³⁺ and Cr⁵⁺ ions, the latter being in small proportion, in agreement with the atomic magnetic moment values. For concentrations x20 mol% Cr₂O₃ the isolated Cr³⁺ ions coexist with those coupled by super-exchange magnetic interactions, the isolated ones prevailing only for x<3 mol% Cr₂O₃. For x>20 mol % Cr₂O₃ microcrystalline precipitates were detected, giving rise to an antiferromagnetic transition with Néel temperature, N _N310 K and paramagnetic Curie temperature, _p=–480 K.     

Incommensurate Dynamical Properties of Optimally Doped YBa2Cu3O6.9

The resonance and incommensurate peaks in optimally doped high-T _c superconductor YBa₂Cu₃O_6.9 are observed by means of TOF neutron scattering technique. Obtained overall dynamical properties in a wide Q-E space show distinct incommensurate structure around antiferromagnetic (AF) zone center (, ). The incommensurability of =0.1 at 36 meV corresponds to the previous triple-axis neutron measurement. Variation of temperature dependence suggests the spectral weight of antiferromagnetic fluctuation observed around 25 meV at (, ) shifts to resonance peak position below T _c. Moreover obtained results with E _i=80 meV neutron energy indicate new feature of dynamical incommensurate structure at higher frequency region up to 53 meV.     

X-ray Diffraction and Thermodynamic Studies of GdLiCr2O5

GdLiCr₂O₅ is synthesized from Gd₂O₃, Cr₂O₃, and Li₂CO₃ by solid-state reaction. This compound has an orthorhombically distorted perovskite structure with lattice parametersa= 10.78 Å, b= 10.63 Å, and c= 11.04 Å (V = 1263.9 ų, V _subcell = 158.0 ų, _x = 3.66 g/cm³, _meas = 3.57 ± 0.09 g/cm³). The heat capacity of GdLiCr₂O₅ is measured between 298.15 and 673 K by dynamic calorimetry. At 423 K, C _p ⁰ exhibits a lambda-type anomaly due to a second-order phase transition. The best fit equations for C _p ⁰(T) are derived, and the thermodynamic functions S ⁰(T), H ⁰() – H ⁰(298.15 K), and "(T) are calculated.     

Microstructure, electrochemical surface and electrocatalytic properties of IrO2+Ta2O5 oxide electrodes

X-ray diffraction (XRD) and scanning electron microscopy (SEM) have been used to characterize physical structure of IrO₂+Ta₂O₅ films over the whole composition range by thermodecomposition of chloride solutions heated at 450°C. Solid solubilization between Ta component and IrO₂ rutile in the mixed films was measured, and three typical surface morphologies of the oxide coatings were observed. The surface electrochemical properties of Ti/IrO₂-Ta₂O₅ electrodes were studied by cyclic voltammetry at varying potential scan rate, and a double-layer electrochemical structure containing the inner and outer layers has been distinguished. The voltammetric charge appears to decline with the decrease of grain size of oxide coatings as a result of the effect of surface tension. However, the coatings of 70% IrO₂+30% Ta₂O₅ with the finest grains still exhibit the highest apparent activity for oxygen evolution evaluated by the anodic current at a constant potential. This result is interpreted by the measurements of open-circuit potential (E _oc) and double-layer capacitance (C _dl) using electrochemical impedance spectroscopy (EIS). Thereby, the reliability of voltammetric charge obtained in double-layer potential region in determining the real electrocatalytic activity for O₂ evolution has been discussed.     

1 : 2 Long-range ordering and defect mechanism of WO3-doped perovskite Ba(Mg1/3Ta2/3)O3

The nature of the B-site cation ordering and the associated defect process necessary to stabilize the ordered domains were investigated using the WO₃-doped BaMg_1/3Ta_2/3O₃ BMT system as a typical example of BaB_1/3B_2/3O₃-type complex perovskites. It was shown that only the 1 : 2 long-range ordering of the B-site cation existed in both undoped and WO₃-doped BMT perovskites. The atomic defect mechanism associated with the stoichiometric 1 : 2 long-range ordering was systematically investigated. It is concluded that the substitution of W⁶⁺ for Ta⁵⁺ in the WO₃-doped BMT enhances the degree of the 1 : 2 long-range ordering and produces the positively charged W _Ta sites with a concomitant generation of tantalum vacancies V_Ta and mobile oxygen vacancies V _O for the ionic charge compensation.     

EPR study of Cu2+ in Na2O-NaF-B2O3-Bi2O3 glasses

Electron paramagnetic resonance (EPR) studies have been performed on the glass system (30–x) NaF-xNa₂O-50B₂O₃-20Bi₂O₃ doped with CuO as a paramagnetic probe. The calculated g values indicate that Cu²⁺ is in a tetragonally elongated octahedral co-ordination, and the Jahn-Teller character gives rise to anisotropic hyperfine structure. The spin-Hamiltonian parameters and -bonding parameter, ², are calculated. Varying the fluoride ion concentration and its effect on these parameters is also discussed.