Fabrication of single-grain GdBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7−<Emphasis Type="Italic">x</Emphasis></Subscript> bulk superconductors with a new kind of liquid source by the top seeded infiltration and growth technique

Compared to the conventional melt growth (MG) method, the top seeded in- filtration and growth (TSIG) process is an effective way for preparing bulk REBa₂Cu₃O_7−x (RE-123) with finely dispersed RE₂BaCuO₅ (RE-211) particles. However, it is more complicated and time-consuming, because three kinds of precursor powders, namely, RE-211, RE-123 and BaCuO₂, have to be prepared for the conventional TSIG process. In this paper, a new liquid source (NLS) composed of RE-211 and Ba₃Cu₅O₈, was proposed for simplifying the TSIG process, which is different from the regular liquid source (RLS) composed of RE-123 and Ba₃Cu₅O₈. In this modified TSIG technique, we need to prepare only RE-211 and BaCuO₂ powders. Single-grain GdBa₂Cu₃O_7−x (GdBCO) bulk superconductors have been fabricated using the RLS and NLS separately. The morphology, microstructure and levitation force of the bulk GdBCO have also been investigated. The results indicate that the NLS can be used to simplify the process flow and improve the efficiency on the fabrication of single-grain GdBCO superconductors.     

High performance GdBa2Cu3O7−z film preparation by non-fluorine chemical solution deposition approach

Biaxially textured GdBa₂Cu₃O_7?z (GdBCO) films with T_c above 93 K have been prepared on (0 0 l) LaAlO₃ substrate by self-developed non-fluorine polymer-assisted chemical solution deposition (PA-CSD) approach. The GdBCO films show smooth and crack-free morphology. Many nanoscale particles with homogeneous distribution are observed in the GdBCO films, which have not been observed yet in the YBa₂Cu₃O_7?z (YBCO) films prepared by the same processing technique. Besides a high J_c (77 K, 0 T) of 2.28 MA/cm², the optimized GdBCO films show a better J_c–B behavior and an improved high-field J_c, compared to the YBCO films.     

Effects of Y2O3 additions on the oxygen diffusion in top-seeded melt growth processed YBa2Cu3O7−y superconductors

To understand the effect of Y₂BaCuO₅ (Y211)/YBa₂Cu₃O_7?y (Y123) interfaces on the oxygen diffusion in single grain YBa₂Cu₃O_7?y superconductors, single grain Y123 superconductors with 0.05 and 0.3 moles of Y₂O₃ additions were fabricated by a top-seeded melt growth (TSMG) process. Y123 compacts with Y₂O₃ additions were subjected to melt growth heating cycles with a cooling rate of 1 °C/h through a peritectic temperature (1015 °C) and then annealed at 450 °C for 200 h in flowing oxygen. The superconducting temperature (T_c) and critical current density (J_c) were estimated for the three different regions (top surface (s), intermediate (i) and center (c)) of samples. The amount of Y211/Y123 interface area in single grain Y123 superconductors was successfully controlled by Y₂O₃ additions. The T_c values of s regions were higher than those of i and c regions, which indicates the presence of more oxygen at the sample surfaces. In addition, the T_c values of i and c regions of the Y123 sample with 0.3 mole Y₂O₃ addition were higher than those of the same regions of the Y123 sample with 0.05 mole Y₂O₃ addition due to the promoted oxygen diffusion through Y211/Y123 interfaces and other related defects. In spite of the promoted oxygen diffusion by Y₂O₃ addition, the large T_c difference among the regions still existed, which suggests sluggish oxygen diffusion into single Y123 grains.     

Fluctuation induced magneto-conductivity studies in YBa2Cu3O7−δ + xBaZrO3 composite high-Tc superconductors

Fluctuations on the electrical conductivity of polycrystalline YBa₂Cu₃O_7?δ + xBaZrO₃ (x = 1.0, 2.5, 5.0 and 10.0 wt.%) superconductors were investigated from the resistivity vs. temperature data for zero field and 8 T (Tesla) external magnetic fields. Attempts have been made to identify the optimum inclusion of BaZrO₃ (BZO) in YBa₂Cu₃O_7?δ (YBCO) superconductors. The phase formation, texture and grain alignments were analyzed by XRD and SEM techniques. Then the effects of superconducting fluctuations on the electrical conductivity of granular composite superconductors were studied for zero field and 8 T external magnetic fields. Though inclusions of BZO sub-micron particles are not expected to influence superconducting order-parameter fluctuation (SCOPF) much, the transition from 2D to 3D of the order parameter in the mean-field region depends on the BZO content in the composites. It has been observed that BZO residing at the grain boundary of YBCO matrix influences the tailing region without having significant change in the mean-field critical temperature. In the present work, attention has been focused mostly in the experimental domain relatively above the T_c. It reveals that, 1 wt.% composite exhibits a better superconducting property in comparison with pure YBCO.     

Synthesis and electrochemical characterization of M2Mn3O8 (M = Ca,Cu) compounds and derivatives

M₂Mn₃O₈ (M = Ca²⁺, Cu²⁺) compounds were synthesized and characterized in lithium cells. The M²⁺ cations, which reside in the van der Waals gaps between adjacent sheets of Mn₃O₈⁴⁻, may be replaced chemically (by ion-exchange) or electrochemically with Li. More than 7 Li⁺/Cu₂Mn₃O₈ may be inserted electrochemically, with concomitant reduction of Cu²⁺ to Cu metal, but less Li can be inserted into Ca₂Mn₃O₈. In the case of Cu²⁺, this process is partially reversible when the cell is charged above 3.5 V vs. Li, but intercalation of Cu⁺ rather than Cu²⁺ and Li⁺/Cu⁺ exchange occurs during the subsequent discharge. If the cell potential is kept below 3.4 V, the Li in excess of 4 Li⁺/Cu₂Mn₃O₈ can be cycled reversibly. The unusual mobility of + 2 cations in a layered structure has important implications both for the design of cathodes for Li batteries and for new systems that could be based on M²⁺ intercalation compounds.     

Fabrication of Cu2O nanocrystalline thin films photosensor prepared by RF sputtering technique

Cuprous oxide (Cu₂O) nanocrystalline thin films were prepared on two types of substrates known as crystalline silicon and amorphous glass, by radio frequency reactive magnetron sputtering method. Scanning electron microscopy images confirmed that Cu₂O particles covered the entire surface of both substrates with smoothing distribution. The root mean square surface roughness for the prepared Cu₂O thin films on glass and Si (111) substrates is 4.16, and 3.36 nm, respectively. Meanwhile, X-ray diffraction results demonstrated that the two phases of Cu₂O and CuO were produced on Si (111) and glass substrates. The optical bandgap of Cu₂O thin films synthesised on glass substrate is 2.42 eV. Furthermore, the prepared Cu₂O nanocrystalline thin films have showed low reflectance value in the visible spectrum. Metal-Semiconductor-Metal photodetector based Cu₂O nanocrystalline thin films deposited onto Si (111) was fabricated using aluminium and platinum, with the current-voltage and photoresponse characteristic investigated under various applied bias voltages. The fabricated Metal-Semiconductor-Metal (M-S-M) photodetector had shown 126% sensitivity in the presence of 10 mW/cm² of 490 nm light with 1.0 V bias, displaying 90 and 100 ms response and recovery times, respectively. These findings have demonstrated the suitability of M-S-M Cu₂O photodetector as an affordable photosensor in the future.     

Behavior of silver substitution in single-grain TSMG YBCO bulk superconductor

Ag concentration in the single-grain TSMG Y₁Ba₂(Cu_1?xAg_x)₃O₇ bulk superconductor with nominal Ag concentration for x = 0.05 was measured by WDX microprobe. The partition coefficient of Ag between Y123 crystal and the melt, k_Ag, was estimated to be k_Ag = 0.1. It is also shown that the solubility of Ag in the Y₂BaCuO₅ phase is below the WDX detection limit. As the measured Ag concentration is about four times higher than the concentration of Ag for optimum chemical pinning, the clustering of Ag atoms is supposed and a mechanism of Ag clustering is proposed.     

Inducing self-assembly of Y2BaCuO5 nanoparticles via Ca-doping for improved pinning in YBa2Cu3O7−x

Different mechanisms may exists as a means to provide additional or specialized enhancement of existing nanoparticulate pinning in YBa₂Cu₃O_7?x (YBCO) thin films. In the particular case of Y₂BaCuO₅ (Y211) nanoparticles, Ca-doping of these nanoparticles via addition to the Y211 target material provides an additional increase to the J_c(H). YBCO + Y211 samples were created by pulsed laser deposition with alternating targets of YBCO with Y211 and Y211 doped with Ca. Initial indications suggest that this improvement in pinning results from some scattered short-ranged self-assembly of the nanoparticles into short nanocolumns.     

Synthesis and characterization of (Bi,Cu)Sr2(RE,Ca)Cu2Oz (RE: Y or rare-earth element)

Samples with nominal compositions of x = 0–0.1 in (Bi_(1+3x)/3Cu_(2?3x)/3)Sr₂(RE_1?xCa_x)Cu₂O_z ((Bi,Cu)-“1-2-1-2”; RE: Y or rare-earth element) were synthesized by a solid-state reaction method and characterized by means of X-ray diffractometry (XRD). It is confirmed that the (Bi,Cu)-“1-2-1-2” forms only when RE = Y, Dy and Ho. Single- or nearly single-phase samples are obtained for x = 0–0.05 and the Ca-free composition of this compound is determined to be (Bi_1/3Cu_2/3)Sr₂RECu₂O_z. Since ionic radii of Y, Dy and Ho are very close to each other and this seems to be an essential factor for the stability of the (Bi,Cu)-“1-2-1-2”.     

Effects of calcium doping on the superconducting properties of top-seeded melt growth processed Y1.5Ba2−xCaxCu3Oy superconductors

The effect of calcium doping on the superconducting properties of top seeded melt growth (TSMG) processed Y_1.5Ba_2?xCa_xCu₃O_y superconductors was studied in terms of calcium content (X_ca). YBa_2?xCa_xCu₃O_7?δ (X_ca = 0, 0.005, 0.01, 0.02, 0.04, 0.1, 0.3) powders were synthesized by the powder calcination method. YBa_2?xCa_xCu₃O_7?δ powders were mixed with 0.25 mole Y₂O₃ powder and 1 wt.% CeO₂ as Y₂BaCuO₅ (Y211) refiner, and finally made into Y₁.₅Ba_2?xCa_xCu₃O_y (Y1.5) + 1 wt.% CeO₂ composition. The single Y123 growth on the top surface was observed up to X_ca = 0.1, while the multiple Y123 growth was observed at X_ca ? 0.1. The superconducting transition temperature (T_c) and critical current density (J_c) of TSMG processed Y1.5 samples were inversely proportional to X_ca. The Y211 size increased with increasing X_ca due to the enhancement of Y211 coarsening by calcium doping. No Y211 refining effect by CeO₂ was observed in the calcium doped samples. The T_c and J_c decrease by calcium doping are likely to be due to the calcium incorporation with the Y123 lattice and formation of coarse Y211 particles.     

用顶部籽晶熔渗生长工艺由新成分液相源制备单畴GdBCO超导块材

用R₂O₃(R分别为Gd,Y和Yb),BaCuO₂和CuO配制了三种新成分液相源.利用顶部籽晶熔渗生长工艺,分别用这三种新成分液相源制备了单畴Gd-Ba-Cu-O超导块材,并对所得样品的生长特性和微观结构进行了研究.结果表明,使用新液相源可以缩短实验周期,提高制备效率,并能获得织构度良好的单畴块材.此外,由Y₂O₃或Yb₂O_{3相似文献}   

30 mm wide process of GdBCO PLD/clad-type textured metal substrates

Gd₁Ba₂Cu₃O_x (GdBCO) coated conductors using bi-axially textured clad-type substrates have been developed for high temperatures superconducting (HTS) power cables. In this project, large amount of coated conductors (CCs) are necessary for the several tests of basic properties of HTS power cables and the fabrication of a 15 m long 3-in-one HTS model cable. In order to ensure an adequate amount and properties of coated conductors, the stable manufacturing technology and the high production rate at each process are required.In this report, we have newly installed a high power laser of 300 W for the PLD system, resulting in improvement of the manufacturing stability and the deposition rate for GdBCO film. In addition, we have optimized target–substrate distance in PLD process, and the uniformity of I_c distribution across 30 mm wide tapes were remarkably improved. Furthermore, the surface morphology of buffer layers were enhanced by optimizing the deposition condition using electron beam (EB) evaporation method, and the maximum I_c value for a short sample has achieved 497 A/cm at 77 K in the self-field. Based on these progresses, we are currently developing the stable manufacturing process for long CCs with over 400 A/cm.     

Synthesis under ambient pressure and tri-axial magnetic orientation in REBa2Cu4O8 (RE = Y,Sm, Eu,Gd, Dy,Ho, Er)

We report the rare-earth (RE)-dependent magnetization axes of REBa₂Cu₄O₈, which was synthesized by a flux method under ambient pressure, using powder samples tri-axially oriented in a modulated rotating magnetic field of 10 T. By optimizing the growth temperature and cooling rate, RE124 crystals were successfully grown for RE = Y, Sm, Eu, Gd, Dy, Ho, and Er. From the X-ray diffraction measurement, the magnetically oriented directions were largely dependent on the type of RE ions of RE124. However, the tri-axial magnetic anisotropies of RE124 could be qualitatively understood in terms of the magnitude relation between the single-ion magnetic anisotropy of RE³⁺ ions and the magnetic anisotropy generated by the CuO₂ plane and Cu–O chain. For the practical use of this magneto-scientific process, the control of magnetization axes and tri-axial magnetic anisotropies through crystallochemical control is indispensable.     

Domain structure and Y2BaCuO5distribution in single- and multiple-domain melt-textured YBaCuO

Microstructural features such as subgrains, Y₂BaCuO₅particles, and high-angle boundaries were studied in single- and multiple-domain melt-textured YBaCuO levitators. Subgrains elongated in the c- or a-direction and rectangular in cross section were formed during solidification by cellular growth. Formation of subgrains by combination of a- and c-growth was also observed. Their boundaries were predominantly low angle, and were not cracked or wetted by second phases. Macrosegregation of Y₂BaCuO₅particles developed mainly in the regions formed by c-axis growth. The segregation is related to a Y₂BaCuO₅particle pushing by the YBa₂Cu₃O_7 - xgrowth front, in combination with coarsening by Ostwald ripening and agglomeration. The structure of 90° high-angle grain boundaries appeared to be similar to that of the low-angle grain boundaries.     

On the rate constants of OH + HO2 and HO2 + HO2: A comprehensive study of H2O2 thermal decomposition using multi-species laser absorption

Hydrogen peroxide (H₂O₂) and hydroperoxy (HO₂) reactions present in the H₂O₂ thermal decomposition system are important in combustion kinetics. H₂O₂ thermal decomposition has been studied behind reflected shock waves using H₂O and OH diagnostics in previous studies (Hong et al. (2009) [9] and Hong et al. (2010) [6,8]) to determine the rate constants of two major reactions: H₂O₂ + M → 2OH + M (k₁) and OH + H₂O₂ → H₂O + HO₂ (k₂). With the addition of a third diagnostic for HO₂ at 227 nm, the H₂O₂ thermal decomposition system can be comprehensively characterized for the first time. Specifically, the rate constants of two remaining major reactions in the system, OH + HO₂ → H₂O + O₂ (k₃) and HO₂ + HO₂ → H₂O₂ + O₂ (k₄) can be determined with high-fidelity.No strong temperature dependency was found between 1072 and 1283 K for the rate constant of OH + HO₂ → H₂O + O₂, which can be expressed by the combination of two Arrhenius forms: k₃ = 7.0 × 10¹² exp(550/T) + 4.5 × 10¹⁴ exp(?5500/T) [cm³ mol^?1 s^?1]. The rate constants of reaction HO₂ + HO₂ → H₂O₂ + O₂ determined agree very well with those reported by Kappel et al. (2002) [5]; the recommendation therefore remains unchanged: k₄ = 1.0 × 10¹⁴ exp(?5556/T) + 1.9 × 10¹¹⁺exp(709/T) [cm³ mol^?1 s^?1]. All the tests were performed near 1.7 atm.     

Characterization of Cu1.4Mn1.6O4/PPy composite electrodes

In this work, we have studied the multilayered polypyrrole(PPy)/oxide composite electrode on glassy carbon (GC) having the structure GC/PPy/PPy(Cu_1.4Mn_1.6O₄)/PPy using X-ray Photoelectron Spectroscopy and Mn K-edge and Cu K-edge XANES and EXAFS. The mixed oxide particles have been incorporated into the PPy matrix simultaneously to the electropolymerization of Py from a solution containing 0.1 M Py + 0.15 M KCl + Cu_1.4Mn_1.6O₄. The XPS data have shown that, prior to the incorporation of the oxide into the PPy matrix, it contains Cu⁺, Cu²⁺, Mn³⁺ and Mn⁴⁺. The XPS, XANES and EXAFS results have shown that when the oxide is incorporated into the PPy matrix, the Cu⁺ present in the original oxide suffers dismutation to give Cu²⁺ and metallic Cu. The metallic Cu is segregated out of the spinel structure. The Mn K-edge XANES and EXAFS data show that, after the incorporation into the PPy matrix, Mn is present as Mn³⁺ and Mn⁴⁺ occupying octahedral sites in a spinel-related structure while the Cu K-edge XANES and EXAFS data indicate that copper occupies tetrahedral sites predominantly in that structure but having a large degree of disorder in the second and higher coordination shells.     

Equilibrium of 1:2:3 CLBLCO superconductors with oxygen: reaction equation,thermodynamics and improvement of homogeneity

Equilibrium of 1:2:3 superconductors (Ca_xLa_1−x)(Ba_1.75−xLa_0.25+x)Cu₃O_y (this compound has in the past variously denoted as CLBLCO, CLBCO or CaLaBaCuO) with oxygen was studied for x=0.1 and x=0.4 in the temperature range of 150–950 °C under 1 atm. O₂. The main process is the reversible reaction −Cu₃²⁺O_6.625+0.25O₂=−Cu₂²⁺Cu³⁺O_7.125 which is completed with the formation of one Cu³⁺. The enthalpy (in kJ/mol CLBLCO) and entropy (in J(mol CLBLCO)⁻¹K⁻¹) of this reaction were calculated from the temperature dependence of the equilibrium constant. The values are ΔH=−33.1 and ΔS=−29.9 for x=0.1 and ΔH=−49.4 and ΔS=−42.7 for x=0.4.It was found that the equilibrium of ceramic pellet of CLBLCO with oxygen cannot be practically achieved below 300 °C while the equilibrium for powder is achieved even at 200 °C. Low rate of reaction of CLBLCO with oxygen causes the problem in low temperature equilibration. In contrast, diffusion of oxygen ions in the ceramics is observed even at 200 °C. This diffusion proceeds without the change of the oxygen content and may be applied in order to improve the homogeneity of the distribution of oxygen ions.     

Intensification of depolymerization of polyacrylic acid solution using different approaches based on ultrasound and solar irradiation with intensification studies

Depolymerization of polyacrylic acid (PAA) as sodium salt has been investigated using ultrasonic and solar irradiations with process intensification studies based on combination with hydrogen peroxide (H₂O₂) and ozone (O₃). Effect of solar intensity, ozone flow and ultrasonic power dissipation on the extent of viscosity reduction has been investigated for individual treatment approaches. The combined approaches such as US + solar, solar + O₃, solar + H₂O₂, US + H₂O₂ and US + O₃ have been subsequently investigated under optimum conditions and established to be more efficient as compared to individual approaches. Approach based on US (60 W) + solar + H₂O₂ (0.01%) resulted in the maximum extent of viscosity reduction as 98.97% in 35 min whereas operation of solar + H₂O₂ (0.01%), US (60 W), H₂O₂ (0.3%) and solar irradiation resulted in about 98.08%, 90.13%, 8.91% and 90.77% intrinsic viscosity reduction in 60 min respectively. Approach of US (60 W) + solar + ozone (400 mg/h flow rate) resulted in extent of viscosity reduction as 99.47% in 35 min whereas only ozone (400 mg/h flow rate), ozone (400 mg/h flow rate) + US (60 W) and ozone (400 mg/h flow rate) + solar resulted in 69.04%, 98.97% and 98.51% reduction in 60 min, 55 min and 55 min respectively. The chemical identity of the treated polymer using combined approaches was also characterized using FTIR (Fourier transform infrared) spectra and it was established that no significant structural changes were obtained during the treatment. Overall, it can be said that the combination technique based on US and solar irradiations in the presence of hydrogen peroxide is the best approach for the depolymerization of PAA solution.     

Performance of perovskite-related oxide cathodes in contact with lanthanum silicate electrolyte

The cathodic performance of selected mixed-conducting electrodes, including perovskite-type SrMn_0.6Nb_0.4O_3 ? δ, Sr_0.7Ce_0.3Mn_0.9Cr_0.1O_3 ? δ and Gd_0.6Ca_0.4Mn_0.9Ni_0.1O_3 ? δ, and Ruddlesden–Popper La₂Ni_0.5Cu_0.5O_4 + δ, LaSr₂Mn_1.6Ni_0.4O_7 ? δ, La₄Ni_3 ? xCu_xO_10 ? δ (x = 0–0.1) and La_3.95Sr_0.05Ni₂CoO_10 ? δ, was evaluated in contact with apatite-type La₁₀Si₅AlO_26.5 solid electrolyte at 873–1073 K and atmospheric oxygen pressure. The electrochemical activity of porous nickelate-based layers was found to correlate with the concentration of mobile ionic charge carriers and bulk oxygen transport, thus lowering in the series La₄Ni_2.9Cu_0.1O_10 ? δ > La₄Ni₃O_10 ? δ > La_3.95Sr_0.05Ni₂CoO_10 ? δ and decreasing on copper doping in K₂NiF₄-type La₂Ni_1 ? xCu_xO_4 ? δ. The relatively high overpotentials of nickelate-based cathodes, varying in the range ? 240 to ? 370 mV at 1073 K and current density of ? 200 mA/cm², are primarily associated with surface diffusion of silica from La₁₀Si₅AlO_26.5, which partially blocks the electrochemical reaction zone. As compared to the intergrowth nickelate materials, the manganite-based electrodes exhibit substantially worse electrochemical properties, in correlation with the level of oxygen-ionic and electronic conduction in Mn-containing phases. The effects of cation interdiffusion between the cell components as a performance-deteriorating factor are briefly discussed.     

Strongly enhanced flux pining of GdBCO coated conductors with BaSnO3 nanorods by pulsed laser deposition

We report the effects of BSO addition on the crystallinity, texture, and the field dependency of critical current density (J_c) of GdBCO coated conductors (CCs) prepared by pulsed laser deposition (PLD). Undoped and BSO-doped GdBCO films showed only c-axis oriented growth, and the incorporated BSO nanorods exhibited epitaxial relationship with the GdBCO matrix. In comparison with undoped film, BSO-doped GdBCO film exhibited greatly enhanced J_c and higher pinning force densities in the entire field region of 0–5 T (H//c) at 77 and 65 K. The BSO-doped GdBCO film showed the maximum pinning force densities (F_p) of 6.5 GN/m³ (77 K, H//c) and 32.5 GN/m³ (65 K, H//c), ～2.8 times higher than those of the undoped sample. Cross-sectional TEM analyses exhibited nano-structured BSO nanorods roughly aligned along the c-axis of the GdBCO film, which are believed effective flux pinning centers responsible for strongly improved critical current densities in magnetic fields.