Determination of oxygen content in YBa2Cu3O6.5+x

A method for determining the oxygen content of the high-temperature superconductor YBa₂Cu₃O_6.5+x is described. The superconductor is dissolved in 4.4 M hydrobromic acid, forming bromine. The mixture is then diluted with hydrochloric acid to obtain a solution of bromine and Cu(II) in 0.44 M hydrobromic acid and 1.1 M hydrochloric acid. As(III) is added in slight excess of that required to react with the bromine and the unreacted As(III) is determined by titration with potassium bromate. Oxygen does not interfere. The results of this method are in agreement with those of other iodimetric procedures. The dissolution of the superconductor in 4.4 M hydrobromic acid is much faster than in hydrochloric acid, the medium used in one iodimetric technique. YBa₂Cu₃O_6.5+x sintered fibers and powder samples weighing from ca. 0.5 to 200 mg were analyzed for oxygen content.     

Determination of stoichiometry of Li1+yCoO2 materials by flame atomic absorption spectrometry and automated potentiometric titration

A rapid, accurate and precise analytical method to determine the stoichiometry of pure, excess lithium and magnesium-doped Li_1+yCoO₂ materials is described. The method is based on the determination of lithium, cobalt and magnesium by flame atomic absorption spectrometry after dissolution of samples in dilute hydrochloric acid. Five-point calibration curves using aqueous standard solutions have been constructed for all the analytes. Relative standard deviation (R.S.D.) of five repeated measurements are better than 0.3% for all metals when the absorbance signal of analytes is set near the middle of the regression lines.The total oxygen content is indirectly determined by potentiometric titration of average oxidation state of cobalt. The Co³⁺ present in the oxide powders is reduced to Co²⁺ at room temperature with a known excess of 0.1 M Fe²⁺ solution in 6 M sulphuric and phosphoric acid mixture. The samples completely dissolved in a few minutes developing a pink coloured and clear solution. The excess of Fe²⁺ ions is back titrated with potassium dichromate standard solution using automated potentiometric end-point detection. The difference between the total cobalt content (found by AAS) and Co³⁺ (found by potentiometric titration) gives the amount of Co²⁺ present in the materials. The S.D. of the determined Co³⁺ value has been estimated to be below 0.03 mg for samples of 10-20 mg. By the proposed method the LiCoO₂ is well characterised and can be applied as a standard reference material for use in lithium batteries technology.     

YBa2Cu3O7-x/Thermoplastic polymer composite thermistors

Conducting YBa₂Cu₃O_7-x was incorporated in to polyethylene matrices to produce composite materials with low room temperature resistivity and sizable positive temperature coefficient (PTC) resistance effects. The intensity of the PTC effect for these composites was found to be as large as 10 orders of magnitude. The location of the PTC phenomenon is determined by the choice of polymer matrix. The mechanism for the PTC effect in crystalline polymer composites is related to the percolation behaviour of the composites and the thermal expansion of the polymer matrix.     

Chemical activity in YBa2Cu3O7 − δ across the normal to superconducting phase transition

The Gibbs free enthalpy, chemical activity across the transition temperature to superconductivity, T_c in YBa₂Cu₃O_{7 − δ} is obtained from reciprocally enhanced X-Ray absorbance, XAS and diffraction, XRD data near the Ba L_3,2 edges' energy E_a, and orientations in the X-ray beam for preferred Miller indexed [HKL] planes' scattering, that are enhanced near T_c. The standard enthalpy and entropy for the formation of mixed normal metal/superconducting domains above T_c, determined individually across the two Ba L_3,2 edges, to better than a percent accuracy: ΔH^≠_≥ = − 220 meV, and ΔS^≠_≥ = − 2 meV/K when 121 ≥ T ≥ 92 K ≈ T_c1, indicate that energy is gained, with an increased order by forming a mixture with reduced entropy. Below T_c the standard enthalpy and entropy to form at least two mixed superconducting phases are halved to ΔH^≠_≤ = − 86 meV, ΔS^≠_≤ = − 1 meV/K when 92 K ≥ T ≥ T_c2 ≈ 72 K. Thus reciprocal XAS/XRD enhancement at orientations in the X-ray field, of preferred 2D planes, induced by the transition to superconductivity in the layer solid, indicates one, the importance of the 2D-plane electron density scattering near T_c, and two, identifies the 2D-plane chemical activity, by the electron density leading to symmetry allowed excitations, a role similar to that of the electron density in linear bonds for molecular activity.     

Determination of Cu(III) and Cu(II) + Cu(III) in superconducting copper ceramics

Summary Copper(III) and total copper in superconducting Y-Ba-Cu oxide and related compounds can be determinated by two successive iodimetric titrations after the sample has been dissolved under Ar in HCl/KI medium. First, the iodine equivalent to copper(III) ist titrated with Na₂S₂O₃ solution at pH 4.8, copper(II) being masked with EDTA. The total copper is then determined in the same solution by demasking with acid and iodide, followed by iodimetric titration. The method is both accurate and reproducible. The relative standard deviations for 1.074% copper(III) and 23.37% total copper are 0.8% and 0.3%, respectively.     

Metal-organic deposition of YBa2Cu3Ox and Bi2Sr2Ca1Cu2Ox films on various substrates starting from different fluorine-free metallorganic compounds

YBa₂Cu₃O_x (Y-123) and Bi₂Sr₂Ca₁Cu₂O_x (Bi-2212) films on various substrates have been prepared by Metal-Organic Deposition starting from different metallorganic fluorine-free compounds and using a very simple instrumentation. The processing conditions include a rapid pyrolysis step in air and an annealing step in oxygen for Y-123 and in air for Bi-2212. The films obtained have been characterized by X-ray diffraction (XRD) and the formation of a superconducting phase of Y-123 or Bi-2212 was confirmed measuring the critical temperature (T _c) with Ac-susceptibility and resistive measurements. Microstructure and final cationic ratios have been studied by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS).     

Neutron and X-ray investigations on the oxygen bonding in YBa2Cu3O7-x combined with physico-chemical methods

The occupancy of the oxygen lattice positions at different annealing conditions in YBa₂Cu₃O_(7–x) were determined by Rietveld refinements using neutron and X-ray diffraction data. The occupation density for the oxygen positions O1 to O4 were ascertained. The values of the oxygen content of the samples from this method were compared with those measured by thermoanalysis. The O1 and O4 oxygen atoms are exchangeable by thermal treatment. The oxygen in the planes is fixed and can not be removed by thermal treatment up to 935°C. The binding strength of O1 in the lattice is stronger than that of O4 atoms; this is demonstrated by a higher temperature of dissociation of the O1 atoms. The amount of the oxygen taken up is not exactly equal to the oxygen actually in the lattice positions. In the temperature region below 400°C adsorption and chemisorption processes are become dominant.     

Thermal analysis and thermal expansion studies on high density YBa2−xLaxCu3O7−δ, 0x0.2

The compositions in the YBa_2−xLa_xCu₃O_7−δ (0x0.2) system were prepared by the solid state reaction, employing a novel high-temperature oxygen sintering route. The modified sintering route yields dense slab like microstructures with large grains. The decomposition (incongruent melting) temperature of the YBa₂Cu₃O_7−δ (Y-123) phase was found to shift to higher temperatures with increasing oxygen partial pressure and lanthanum content. Structure remained orthorhombic up to x=0.2 with a decrease in the orthorhombic strain ((b−a)/b). Iodometric titration indicated a systematic increase in the oxygen content with increasing lanthanum content. Thermo-gravimetric studies in various oxygen partial pressures revealed that the oxygen diffusion in to the YBa₂Cu₃O_7−δ (δ>0.5) lattice is an exothermic event and takes place at temperatures not less than 573 K. High-temperature thermal-expansion measurements in air indicated that the nonlinearity in thermal expansion behaviour was reduced by the substitution of lanthanum.     

Interface analysis of the system Si/YBa2Cu3O7?x

Summary The influence of different preparation conditions and substrate surface orientations on the superconducting properties of thin YBa₂Cu₃O_7–x (YBCO) films on silicon was studied. Comparative electrical and surface spectroscopic measurements were performed. SAM and SIMS depth profile analysis show an enrichment of barium at the interface between the superconductor and silicon for samples with T_c<76 K. Comparison with XPS data obtained for thin silicon films on YBCO indicates the formation of barium and yttrium silicates at the interface under these conditions.     

Textural and catalytic properties of the FexOy/Fe-KClO4 system

Selected properties of commercial iron powders, standardised in the atmosphere of hydrogen, have been studied. The reactivity of iron oxides in the thermal decomposition of KClO₄ in the solid-state mechanical mixture of Fe and KClO₄ containing 9, 13, 17, 21 and 25 wt.% of KClO₄, respectively, has been tested by the differential thermal analysis (DTA) and thermogravimetric analysis (TG). It has been established that the Fe₃O₄ phase on the surface of the iron powder act as an effective catalysts in the thermal decomposition of KClO₄.     

化学计量比和放氢背压对LiBH4+xMg2NiH4体系放氢性能的影响

研究了不同化学计量比(x=0.25, 0.5, 0.75, 1.0, 1.25)和放氢背压(1×10-4和0.4 MPa)对LiBH4+xMg2NiH4复合体系吸放氢性能的影响. 结果表明, 随着化学计量比(x)的增加, 复合体系的放氢温度逐渐降低, 放氢动力学性能得到提高, 但放氢容量逐渐降低; 其中, 在1×10-4和0.4 MPa初始放氢背压下, LiBH4+0.75Mg2NiH4体系具有最佳放氢动力学性能和较高的储氢容量. 结果表明, 放氢背压和化学计量比均会对高温下液相LiBH4 与固态Mg2NiH4 的润湿性产生影响, 进而影响复合体系的放氢路径和放氢动力学性能.     

Synthesis, crystal structure, infrared and Raman spectra of Sr4Cu3(AsO4)2(AsO3OH)4·3H2O and Ba2Cu4(AsO4)2(AsO3OH)3

The two new compounds, Sr₄Cu₃(AsO₄)₂(AsO₃OH)₄·3H₂O (1) and Ba₂Cu₄(AsO₄)₂(AsO₃OH)₃(2), were synthesized under hydrothermal conditions. They represent previously unknown structure types and are the first compounds synthesized in the systems SrO/BaO-CuO-As₂O₅-H₂O. Their crystal structures were determined by single-crystal X-ray diffraction [space group C2/c, a=18.536(4) Å, b=5.179(1) Å, c=24.898(5) Å, β=93.67(3)°, V=2344.0(8) Å³, Z=4 for 1; space group P4₂/n, a=7.775(1) Å, c=13.698(3) Å, V=828.1(2) Å³, Z=2 for 2]. The crystal structure of 1 is related to a group of compounds formed by Cu²⁺-(XO₄)³⁻ layers (X=P⁵⁺, As⁵⁺) linked by M cations (M=alkali, alkaline earth, Pb²⁺, or Ag⁺) and partly by hydrogen bonds. In 1, worth mentioning is the very short hydrogen bond length, D···A=2.477(3) Å. It is one of the examples of extremely short hydrogen bonds, where the donor and acceptor are crystallographically different. Compound 2 represents a layered structure consisting of Cu₂O₈ centrosymmetric dimers crosslinked by As1φ₄ tetrahedra, where φ is O or OH, which are interconnected by Ba, As2 and hydrogen bonds to form a three-dimensional network. The layers are formed by Cu₂O₈ centrosymmetric dimers of CuO₅ edge-sharing polyhedra, crosslinked by As1O₄ tetrahedra. Vibrational spectra (FTIR and Raman) of both compounds are described. The spectroscopic manifestation of the very short hydrogen bond in 1, and ABC-like spectra in 2 were discussed.     

YBa2Cu3O7 electro-magnetic optic effects in Ba L2,3 X-ray absorption near Tc

The onset of electro-magnetic optic effects, observed at the Ba L_2,3 edges synchrotron X-ray absorption by a YBa₂Cu₃O₇ single crystal, 20 K above the transition temperature to superconductivity, T_c ∼ 92 K is used to identify the role played by the Ba donor layer in the transition to superconductivity in the CuO₂ layers. Negative permeability leads to Faraday rotation of the transmitted beam below T = 112 to 56 K for the 22 μm thick single crystal (c-axis orientation of 8π/18 relative to ε_X-rays) and sharp changes in the density of empty final states lead to zero transmitted radiation in an interval ΔE at the given orientation. The temperature dependence: ΔE(L₂) = 1.4, 3.5 and 3.9 eV, while ΔE(L₃) = 5.3, 6 and 7 eV at T = 92, 74 and 63 K, respectively, indicates that the width of the empty final states bands increases as T decreases. ΔE(L₃)/ΔE(L₂) = 3.8 at 92 K to 1.8 at 63 K also indicates that the d_5/2 symmetry bands fill faster than those of d_3/2 symmetry below T_c, providing the first experimental evidence of unpaired spin-orbit states in the Ba donor layer of a superconductor. These effects, characteristic of ferromagnetic and anti-ferromagnetic materials near a resonance absorption, signal the onset of a Mott transition. The interaction between the layer states is described using 1D conjugate molecular orbitals.     

Magnetic investigation of Cu(NH3)4(NO3)2

The magnetic properties of Cu(NH₃)₄(NO₃)₂ have been measured at low temperatures. Broad maxima in both the susceptibility and specific heat are observed and are consistent with linear chain behavior of a Heisenberg antiferromagnet, with J/k = 3.9 ± 0.1 K. Long-range order sets in at T_c = 0.15 ± 0.01 K, and the ratio kT_c/|J| = 0.038 is the lowest observed as yet for a one-dimensional, S = 1/2 antiferromagnet.     

Structural order and disorder in Co-based layered cuprates CoSr2(Y,Ce)sCu2O5+2s (s=1-3)

Crystal structures of a homologous series of Co-based layered cuprates, CoSr₂(Y,Ce)_sCu₂O_5+2s (s=1-3), have been investigated by high-resolution electron microscopy (HREM) and electron diffraction (ED) techniques. For all the three phases ED patterns showed double periodicity along a direction parallel to the CoO layers, indicating a regular alternation of two types of CoO₄-tetrahedra chains within the layers. Also seen was ordering of the chains along the layer-stacking direction for the s=1 phase (Co-1212); ED patterns simulated based on the proposed superstructure model well reproduced the observed patterns. For the s=2 (Co-1222) and s=3 (Co-1232) phases in which an additional fluorite-type layer-block is inserted between two CuO₂ planes, HREM and ED analysis revealed complete disorder of the CoO₄ chains along the layer-stacking direction. This implies that the interlayer ordering is mainly controlled by the distance between the neighboring CoO layers.     

Polarized crystal spectra of the mixed metal salt [(CH3)3NH]MnxCu1−xCl3·2H2O

The electronic absorption spectra in two polarizations are reported for crystals of the dichroic salt, TMAMn_xCu_1?xCl₃·2H₂O where TMA represents the trimethylammonium cation, (CH₃)₃NH⁺. Although TMACuCl₃·2H₂O is monoclinic, the mixed metal salts in which x ≥ 0.20 adopt the orthorhombic structure of TMAMnCl₃·2H₂O. The bands observed in the near ir region are adequately explained as d-d transitions of the Cu(II) ion in D_2h symmetry. Other polarized bands which occur in the visible region and are neither Mn(II) nor Cu(II) d-d transitions are discussed.     

A 13C endor study on Copper(II)/Zinc(II) bis-(diethyl-dithiocarbamate) Cu/Zn(et2dtc)2

¹³C ENDOR spectra of Cu(et₂dtc)₂ substituted into a single crystals of Zn(et₂dtc)₂ are reported. The symmetry of the incorporated guest molecule appears to be considerably influenced by the Zn(et₂dtc)₂ host lattice. The unexpectedly large isotropic ¹³C hfs coupling can be understood assuming a “transannular overlap” mechanism.     

13C and 14N ENDOR study on Copper(II)/Nickel(II) bis-(diethyl-dithiocarbamate) Cu/Ni(et2dtc)2

The ¹³C and ¹⁴N ENDOR spectra of Cu(et₂dtc)₂ substituted into single crystals of Ni(et₂dtc)₂ are reported. The centrosymmetric, planar structure of the host molecule has been retained by the guest. Comparison between the ¹³C ENDOR data obtained for Cu/Ni(et₂dtc)₂ and Cu/Zn(et₂dtc)₂ has been made considering the different structures of the et₂dtc complexes of Cu, Ni and Zn.     

[As(V)As(III)O6]: An uncommon anion group in the crystal structure of K2Cu3(As2O6)2

The crystal structure of K₂Cu₃(As₂O₆)₂ was determined from single-crystal X-ray data by a direct method strategy and Fourier summations [a = 10.359(4) Å, B = 5.388(2)Å, C = 11.234(4) Å, β = 110.48(2)°; space group C2/m; Z = 2; R_w = 0.025 for 1199 reflections up to sin /λ = 0.81 Å⁻¹]. In detail, the structure consists of As(V)O₄ tetrahedra and As(III)O₃ pyramids linked by a common O corner atom to [As(V)As(III)O₆]⁴⁻ groups with symmetry m. The bridging bonds As(V)---O [1.749(3) Å] and As(III)---O [1.838(2) Å] are definitely longer than the other As(V)---O bonds [mean 1.669 Å] and As(III)---O bonds [1.764(2) Å, 2×]. The angle As(V)---O---As(III) is 123.0(1)°. The Cu atoms are [4 + 2]- and [4 + 1]-, and the K atom is [9]-coordinated to oxygen atoms. The As₂O₆ groups and the Cu coordination polyhedra are linked to sheets parallel to (001). These sheets are connected by the K atoms. Single crystals of K₂Cu₃(As₂O₆)₂ suitable for X-ray work were synthesized under hydrothermal conditions.     

Cu-superconductors in organic catalysis I. Isomerization and hydrogenation of allyl alcohol on YBa2Cu3O7?x

On the superconductor YBa₂Cu₃O_7–x between 150 and 300°C, allyl alcohol is isomerized to propionaldehyde (70%) and hydrogenated to 1-propanol (30%) in hydrogen.