Ba2Ca2Cu3Ox Precursor Effects on Synthesis of (Hg,Pb)Ba2Ca2Cu3O8+δ Superconductor

The influence of Ba₂Ca₂Cu₃O_x precursor on the synthesis and properties of (Hg,Pb)Ba₂Ca₂Cu₃O_8+δ has been examined. Fine homogeneous Hg-free precursor powder of Ba₂Ca₂Cu₃O_x of desirable phase composition was prepared by sol-gel method using EDTA acid as a complexing agent. A reproducible superconducting sample of Hg_0.8Pb_0.2Ba₂Ca₂Cu₃O_8+δ with fine-grained, dense microstructure, composed predominantly of (Hg,Pb)-1223 phase and with advantageous magnetic properties, was synthesized by high pressure crystallization in mercury environment of well-calcined Ba₂Ca₂Cu₃O_x precursor. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structural Investigation of the Effect of Praseodymium in Eu1-xPrxBa2Cu3O7-δ and EuBa2-xPrxCu3O7-δ Perovskites by 151Eu and 141Pr Mössbauer Spectroscopy

¹⁵¹Eu and ¹⁴¹Pr Mössbauer spectroscopy was applied to study the effects of Pr substitution for Eu or Ba atoms in Eu_1-x Pr _x Ba₂Cu₃O_7- and EuBa_2-x Pr _x Cu₃O_7-, respectively. It was found that there exists a correlation between the ¹⁵¹Eu isomer shift and the onset temperature of the superconducting transition, independent of the location of Pr. This shows that the extra electrons provided by the Pr increase the electronic density in the copper oxide planes and in the 4f orbitals of Eu³¹, simultaneously. The polycrystalline compound EuBa_1.3Pr_0.7Cu₃O_7- has been investigated by ¹⁴¹Pr Mössbauer spectroscopy. The observed ¹⁴¹Pr isomer shift, (4.2 K) = 0.10(15) mm/s relative to PrF₃, reflects a valence state of 3+ for the Pr located at the Ba site in EuBa_1.3Pr_0.7Cu₃O_7-, being in contrast to the valence state of 3.4+ found earlier for Pr which was situated at the rare earth site. This means that the valence state of Pr substituted for Eu is different from that of Pr substituted for Ba. These results suggest that the suppression of superconductivity by Pr substituted for the rare earth atoms is a consequence of the hole filling effect.     

Thermoanalytical Studies of Ga-substituted MBa2Cu3O7–δ Superconducting Compounds Formation (M=Yb,Eu)

A thermoanalytical study in non-isothermal conditions was realized on Ga-substituted MBa₂Cu₃O_7-δ superconducting compounds formation (M=Yb, Eu). The presence of different oxides in the reaction mixtures leads to different reactivity of the system. The type of lanthanoide ion present in the studied compositions determines the reactivity of the system. In the system containing Eu the solid state reactions start at lower temperature than in the system containing Yb. Ga-substitution does not change evidently the thermal behavior of the unsubstituted samples. Different reactivities of the studied reaction mixtures led, after similar thermal treatment in isothermal conditions, to samples with different structure and superconducting properties. This revised version was published online in August 2006 with corrections to the Cover Date.     

Properties and consolidation of nanocrystalline 3Cu–Al2O3 composite by rapid sintering

Nanopowders of Cu and Al₂O₃ were synthesized from 3CuO and 2Al powders by high-energy ball milling. Nanocrystalline Al₂O₃ reinforced composite was consolidated by pulsed-current activated sintering method within 2 min from mechanically synthesized powders of Al₂O₃ and Cu. The relative density of the composite was 96%. The average hardness and fracture toughness values obtained were 540 kg/mm² and 6.3 MPa m^1/2, respectively.

     

Neutron Diffraction Study on Structure of α－LiIO_3 Single Crystal under DC Voltage

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Stereoselective hydrogenation of 2-hexyne on Cu/γ-Al2O3 catalysts

The stereoselective hydrogenation of 2-hexyne in ethanol on Cu/-Al₂O₃ catalysts (1–40 % Cu) at 4–10 atm and 80–120 °C has been studied. The reaction affordscis-2-hexene as the only reaction product in 100 % yield at [Cu] 30 %. For samples with 20 % Cu, hydrogenation proceeds in parallel with absorption of H₂ by the catalyst.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1314–1315, July, 1993.     

Effects of Single Vacancy on Electronic and Optical Properties for γ-Si3N4

The energetics, electronic structures, and optical properties of several neutral vacancies for γ-Si₃N₄ are studied based on density function theory within the generalized gradient approximation. The binding and formation energies of nitrogen vacancy are smaller than that of silicon vacancies, implying that nitrogen vacancy can be easily formed in γ-Si₃N₄.Corresponding density of states of different point vacancies is analyzed. We concluded that the neutral silicon vacancies introduce the p-type carriers into the system, whereas single nitrogen vacancy leads to an n-type semiconductor. The results show indirect semiconductor of nitrogen vacancy for γ-Si₃N₄. The effects of optical properties are discussed on single vacancies for γ-Si₃N₄. For silicon vacancies, the materials have much higher static dielectric constants than these of nitrogen vacancy and perfect γ-Si₃N₄. The single nitrogen vacancy for γ-Si₃N₄ has no effects on absorption and reflection in visible and infrared light. For silicon vacancy, it is significantly increased.     

电流注入对La0.8Te0.2MnO3/YBa2Cu3O7-δ双层结构中YBa2Cu3O7-δ超导电性的影响

用电泳法在厚度为5 mm×10 mm×0.5 mm的YBa2Cu3O7-δ上沉积厚约70 μm的 La0.8Te0.2MnO3 形成La0.8Te0.2MnO3/YBa2Cu3O7-δ (F/S)双层结构. 通过扫描电子显微镜观察双层结构剖面的形貌, 采用标准的四引线法测量YBa2Cu3O7-δ层的电阻特性. 在F/S双层结构中通入1 mA的注入电流, 无论电流从S层流入F层( Iinj), 或者电流从F层流入S层(-Iinj), 正常电阻均比未加注入电流时的电阻低; 超导转变温度均比未加注入电流的转变温度高.     

Effect of substrate materials on the superconducting properties of electrophoretically deposited YBa2Cu3O7−x coatings

Coatings of the high-temperature superconductor YBa₂Cu₃O_7–x (x = 0.1–0.2) (YBCO), were deposited on commercial Ni,Ti and stainless steel substrates, by an electrophoretic deposition technique. Sintering and annealing procedures were followed in order to get strongly adherent superconducting films. The suitability of the used substrates was tested by measuring the stoichiometry and the superconducting properties of the deposited coatings by X-ray diffraction analysis (XRD), Raman spectroscopy and magnetization measurements with a superconducting quantum interference device (SQUID).     

Enhancement of electrochemical performance and thermal compatibility of GdBaCo2/3Fe2/3Cu2/3O5+δ cathode on Ce1.9Gd0.1O1.95 electrolyte for IT-SOFCs

Transition-metal doped double-perovskite structure oxides GdBaCo_2/3Fe_2/3Ni_2/3O_5+δ (FN-GBCO), GdBaCo_2/3Fe_2/3Cu_2/3O_5+δ (FC-GBCO), GdBaCoCuO_5+δ (C-GBCO) and pristine GdBaCo₂O_5+δ (GBCO) were synthesized via a citrate combustion method. The thermal-expansion coefficient (TEC) and electrochemical performance of the oxides were investigated as potential cathodes for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The TEC exhibited by the FC-GBCO cathode up to 900 °C is 14.6 × 10^?6 °C^?1, which is lower than the value of GBCO (19.9 × 10^?6 °C^?1). Area specific resistances (ASR) of 0.165 Ω cm² at 700 °C and 0.048 Ω cm² at 750 °C were achieved for the FC-GBCO cathode on a Ce_0.9Gd_0.1O_1.95 (CGO) electrolyte. An electrolyte supported (300 μm thick) single-cell configuration of FC-GBCO/CGO/Ni-CGO attained a maximum power density of 435 mW cm^?2 at 700 °C. The unique composition of GBCO co-doped with Fe and Cu ions in the Co sites exhibited reduced TEC and enhancement of electrochemical performance and good chemical compatibility with CGO, and this composition is proving to be a potential cathode for IT-SOFCs.     

Dependence of the Structure and Properties of (M,Cu)Sr2(Ln,Ca)Cu2O8−δ (1212) and (M,Cu)Sr2(Ln,Ce4+)2Cu2O10−δ (1222) Phases on the Cation M

The composition and structure of (M,Cu)(Sr,Ln)₂(Ln,Ca,Sr)Cu₂O_8– phases, where M = B, Al, Cr, Pb, Bi, Ru, or Mo (1212 type), and (M,Cu)(Sr,Ln(₂(Ln,Ce⁴⁺)₂Cu₂O_10– phases, where M = V, Cr, Mn, Ru, or Mo (1222 type), have been determined. The role of the M cation in the formation of the crystal structures and the superconductivity phenomenon was analyzed. The relationship between the type of M cation and structural parameters was discovered.     

Analysis of the energetic heterogenity of HgBa2Ca2Cu3O8+δ surfaces: Q-TG and Q-DTG data

Energetic heterogeneity of adsorbents is conditioned by the differences in topology of adsorption centres, dispersion of pore sizes and other factors. This paper describes theoretical and experimental studies that demonstrate a method for estimation of the energetic heterogeneity of adsorbents by making use of the results from single thermogravimetry Q-TG and Q-DTG curves, recorded under quasi-equilibrium conditions, for preadsorbed liquid on a porous solid surface.This revised version was published online in November 2005 with corrections to the Cover Date.     

YBa2Cu3O7-x涂层导体的研究进展

以YBa2Cu3O7-2（YBCO）超导涂层为导体的第二代高温超导带材由于其优异的本征性能，吸引着科学家不断探索和研究其实用成材技术。近年来，百米级长带的研制成功，使其成为当前国际上超导研究的热点。综述了近年来二代超导带材的发展状况，并对在镍和镍合金基带上制备涂层导体的工艺技术以及其基本结构特征做了较为系统的介绍，包括基带的制备技术、隔离层的生长、化学法和物理气相沉积法生长YBCO等。     

Peritektische Zersetzung von YBa2Cu3O7−x

During the heating of YBCO a peritectic reaction takes place at 1020C, which can be described by: 2YBa₂Cu₃O_7–xY₂BaCuO₅+L+(1-2x)/2O₂ (1) whereL = 3BaCuO₂ +2CuO is a fluid with limited amount of yttrium.It has been reported, that many parameters can influence the reaction. From one side not only the starting size of grains but also the heating rate have an influence on the resulting Y₂BaCuO₅-phase. From the other side, there is a change of the peritectical temperature caused by changing of the partial pressure of O₂ and the presence of parasitic phase.From general kinetic consideration one can draw the conclusion, that different mechanisms (nucleation, phase-boundary reaction and diffusion) can control the reaction.Using DTA/TG measurements, the peritectic reaction has been examined. Classical kinetic methods (Kissinger and Friedman) has been used. The Friedman method has given the dependence of the activation energy from reaction degree. This suggests many steps reactions. The dependence of the DTA-peaks from the heat rate suggest a parallel steps of reaction. This assumption can be motivated by evaluation of free O₂, one solid and liquid phase formation. Amount of this phases depends on the heating rate. Additionally X-ray and microscopic methods has been used. In this way was shown, that the perovskit structure is stable up to peritectical temperature and than is dramatically destroyed. From microscopic observations has been got information about shape and size of solid phase and it's creation as a function of temperature, time and starting grain size.

Die Arbeit wurde BMBF gefördert und durch Land NRW unterschtützt.     

X-ray photoelectron spectroscopy of the YBa2Cu3O7−x superconductor system

X-ray photoelectron spectroscopy (XPS) or electron spectroscopy for chemical analysis (ESCA) has been employed to investigate the chemical nature and the electronic structure of the YBa₂Cu₃O_7−x system at different stages of preparation. The binding energy measurements showed that O 1s, Ba 3d and Y 3d core levels undergo appreciable changes during the firing and subsequent heat treatment. The chemical shift in O 1s is believed to be due to a higher concentration of holes in the superconductor phase. No indication for the existence of a monovalent Cu(I) species was found at any stage of preparation.     

Thermoanalytical investigations on the sol-gel synthesis of YBa2Cu3O72212;δ

The high temperature superconducting compound YBa₂Cu₃O_72212; (Y-123) is synthesised by sol-gel process using various precursors viz., acetate, acetate-citrate, nitrate-citrate and acrylamide. The phase purity of the final product depends on the homogeneity of the gels which intern depends on the bonding of the metal ions in the gels. The samples prepared by acrylamide and nitrate-citrate gel routes yielded phase pure Y-123 compound with better superconducting properties. The mechanism of formation of Y-123 in all these four gel routes is established by characterising the gels and intermediate phases using TG, DTA and XRD techniques. Kinetic analysis is carried out on the mass loss data using the method proposed by Phadni's and Deshpande. Avrami-Erofeev nuclei growth in case of acrylamide, diffusion controlled process in nitrate-citrate and phase boundary reaction mechanisms in case of acetate-citrate gels are found to be responsible for the formation of Y-123 phase.The authors are grateful to Dr. Baldev Raj, Director, Metals and Materials Group, for his constant encouragement and support. We thank Prof. G. V. Subba Rao, Director, Central Electrochemical Research Institute, Karaikudi for his keen interest in this work. Thanks are also due to Dr. Sundaram, CECRI, Karaikudi for his help in thermal analysis experiments.     

TG Study of the Dispersion Threshold of Mn2O3 on γ-Al2O3

Mn₂O₃/-Al₂O₃ catalysts were prepared by the impregnation method, and the maximum monolayer dispersion capacity or dispersion threshold value of Mn₂O₃ on the surface of -Al₂O₃ was determined to be 13.08% from the decomposition mass loss of supported Mn(NO₃)₂ in the monolayer state. This was compared with the values estimated from a close-packed monolayer model and an interaction model. It was confirmed that the high activities and selectivities of the catalysts for benzoic acid hydrogenation to benzaldehyde are due to the monolayer dispersion of the Mn₂O₃ on the surface of -Al₂O₃.This revised version was published online in November 2005 with corrections to the Cover Date.