Stability of Bi2Sr2Ca1Cu2O8 ±δ Thick Films at Elevated Oxygen Pressures and Temperatures

Bi₂Sr₂Ca₂Cu₂O_8±δ-type compound thick films were exposed to oxygen-argon-gas mixtures (1% to 20% oxygen gas) at elevated pressures (up to 207 MPa) and temperatures (500° to 940°C) for times ranging from 5 to 96 h. At a sufficiently high oxygen fugacity and temperature, Bi₂Sr₂Ca₁Cu₂O_8±δ decomposed via a solid-state reaction. Room-temperature X-ray diffractometry and electron probe microanalysis of decomposed films revealed the presence of Bi₂(Sr,Ca)₂-Cu₁O_6±θ ro-type compound, Bi₂Sr₂,Ca₁O_8±δ-type compound, and CuO. Bi₂Sr₂Ca₁Cu₂O_8±δ decomposition was accompanied by a modest weight gain, which was consistent with an oxidation reaction. The solid-state decomposition reaction could be reversed by heat treatment of decomposed films at 860°C in pure, flowing oxygen at ambient pressure.     

Quantitative Electron Microscopy of (Bi,Pb)2Sr2Ca2Cu3O10+δ/Ag Multifilament Tapes During Initial Stages of Annealing

The microstructural and compositional evolution during initial annealing of a superconducting (Bi,Pb)₂Sr₂Ca₂Cu₃O_10+δ/Ag tape is studied using quantitative transmission electron microscopy. Special attention is devoted to the occurrence of Pb-rich liquids, which are crucial for the Bi₂Sr₂CaCu₂O_8+δ to (Bi,Pb)₂Sr₂Ca₂Cu₃O_10+δ transformation. Ca and/or Pb-rich (Bi,Pb)₂Sr₂CaCu₂O_8+δ grains dissolve into a liquid, which reacts with Ca-rich phases to increase the liquid's Ca-content. This leads to (Bi,Pb)₂Sr₂Ca₂Cu₃O_10+δ formation. Apparently, a Ca/Sr ratio of around 1 is sufficient to keep (Bi,Pb)₂Sr₂Ca₂Cu₃O_10+δ nucleation going. It is confirmed that Ag particles are transported from the Ag-sheath into the oxide core by the liquid and not by mechanical treatment of the tape.     

Superconducting Properties of Barium-Doped (Bi,Pb)2Sr2Ca2Cu3Ox Glass-Ceramics

The Ba-doped superconducting (Bi,Pb)₂Sr_{2- x} Ba _x Ca₂Cu₃O _y and (Bi,Pb)₂Sr₂Ca_{2- x} Ba _x Cu₃O _y (0 ≦ x ≦ 1.0) were prepared by using a melt-quenching method, and the effect of Ba additions on the glass-forming ability and the crystalline phase was examined. The glass-forming ability was not improved by substitution of Ba for Sr or Ca, and particularly BaPbO₃ as well as CaO was observed in the melt-quenched sample of (Bi,Pb)₂SrBaCa₂Cu₃O _y . BaPbO₃ crystals were precipitated in all glass-ceramics with Ba substituted for Sr or Ca. The partial substitution of Ba substituted for Sr was effective for the formation of the high- T _c phase, and (Bi,Pb)₂Sr_1.4Ba_0.6Ca₂Cu₃O _y glass-ceramics obtained by annealing at 830°C for 100 h exhibited superconductivity with a T _c of 103 K, although BaPbO₃ and the low- T _c phase were still largely present.     

Retrograde Densification of Calcined and Glass Precursors of Approximate (Bi,Pb)2Sr2Ca2Cu3O10 Stoichiometry

Retrograde densification of pelletized calcines and glasses having an approximate (Bi,Pb)₂Sr₂Ca₂Cu₃O₁₀ starting stoichiometry and sintered at ∼850°C can be described by first-order rate equations. Retrograde densification in the calcine precursors was largely due to the development of open pores, and was approximately proportional to the concentration of the (Bi,Pb)₂Sr₂CaCu₃O₁₀ phase. In the glasses, retrograde densification is mainly caused by porosity accompanying the growth of a needlelike Sr─Ca─Cu─O phase, together with (Bi,Pb)₂Sr₂Ca₂Cu₃O₁₀ and (Bi,Pb)₂Sr₂CaCu₂O₈.     

Fundamental Material Aspects Underlying the Preparation of High-Temperature Superconducting (Bi,Pb)2+xSr2Ca2Cu3O10+d Ceramics

Phase equilibria of the quasi-quinary system Bi₃O₃-PbO-SrO-CaO-CuO were studied between 650° and 900°C in air with emphasis on the high-temperature superconducting phase (Bi,Pb)_{2+ x} Sr₂Ca₂Cu₃O_{10+ d} (2223). The 2223 phase lies in equilibrium with a number of nonsuperconducting phases and also with the superconducting phase (Bi,Pb)₂Sr₂CaCu₂O_{8+ d} (2212). The single-phase region was found to be very limited. The Pb solubility of the 2223 phase is strongly temperature dependent. The phase relations are very sensitive to variations of the cation concentration and temperature. This effect significantly influences the preparation of 2223 ceramics.     

Preparation of Superconducting Bi(Pb)-Sr-Ca-Cu-O Thick Films on Magnesia Substrate

Superconducting Bi(Pb)-Sr-Ca-Cu-O powders were prepared by the emulsion-drying method The powders consisting of the low- T _c phase (Bi(Pb)₂Sr₂Ca₁Cu₂O_y) and small amount of Ca₂PbO₄ were prepared by calcining under low oxygen partial pressure at 750°, 800°C. These calcined powders were used to prepare thick films on single-crystal MgO(100) substrates using a screen-printing technique to study the effect of the calcinations temperature and annealing procedure on the high-T_c phase (Bi(Pb)₂Sr₂Ca₂Cu₃O_y)formation. The formation of high-T_c phase was observed to be dependent on the calcinations conditions. The high- T_c phase formed very quickly (sintering at 840°C for 4 h), and the best films showed a sharp superconducting transition at about 105 K.     

Phase Equilibria near (Bi,Pb)-2223, As a Function of Oxygen Partial Pressure

The phase equilibria near (Bi,Pb)₂Sr₂Ca₂Cu₃O_10+delta ((Bi,Pb)-2223) was studied in the temperature range of 750°-820°C in air and in reducing atmospheres. In air, (Bi,Pb)-2223 was in equilibrium with one or more of the following phases: (Bi,Pb)₂Sr₂CaCu₂O_8+delta ((Bi,Pb)-2212), (Sr,Ca)₁₄Cu₂₄O₄₁ (14:24), (Ca,Sr)₂CuO₃, (Bi,Pb)₄(Sr,Ca)₅-CuO _x (451), Ca₂PbO₄, and CuO. Ca₂PbO₄ and the 451 phase were not in equilibrium with (Bi,Pb)-2223 at an oxygen partial pressure ( p _O2) of 10^-3 atm, which is indicative of higher lead solubility in (Bi,Pb)-2223 under more-reducing conditions. In a second set of experiments, the lead content in both (Bi,Pb)-2212 single crystals and (Bi,Pb)-2223 powders was investigated as a function of p _O2 at a constant temperature of 750°C. Lead solubility in (Bi,Pb)-2212 and (Bi,Pb)-2223 increased as p _O2 decreased.     

Effect of Lead Loss and Sheath Structure on Phase Formation and Alignment in (Bi,Pb)2Sr2Ca2Cu3O10+δ/Ag Composite Conductors

The effects of metallic constituent evaporation and sheath structure on grain growth and alignment in silver-sheathed (Bi,Pb)₂Sr₂Ca₂Cu₃O_10+δ (Bi-2223)/Ag composites have been investigated by inductively coupled plasma/atomic emission spectroscopy (ICP/AES), X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectroscopy. Specimens of Bi-2223/Ag composites fabricated by the oxide-powder-in-tube technique were peeled (opened) lengthwise to expose the ceramic powder core, and then heat-treated in 0.075 atm of oxygen for selected temperatures and times. The results were compared with those for as-processed samples with closed silver sheaths treated under identical conditions. ICP/AES analysis indicated that lead was the only metallic element to undergo substantial evaporation during annealing of opened samples. The lead-release process in parallel with the Bi-2223 formation reaction had an activation energy of ∼25 kJ/mol. Lead loss from the opened samples resulted in incomplete conversion to Bi-2223. The combined results show that the silver sheath effectively prevents evaporative lead loss, preserves and promotes densification, and induces texturing of the layered phases.     

30 kbar Phase Equilibria of the La2O3–SrO–CuO System at 950°C

Phase equilibria of the La₂O₃–SrO–CuO system have been determined at 950°C at 30 kbar (3 GPa). Stable phases at the apexes of the ternary phase diagram are CuO, La₂O₃, and SrO. Stable intermediate phases are La₂, CuO₄ and La₂Cu₂O₅ in the LaO_1.5–CuO binary and Sr₂CuO₃, SrCuO₂, and Sr₁₄Cu₂₄O₄₁ in the CuO–SrO binary. The La_{2– x} Sr _x -CuO_4–δ solid solution is stable for 0.00 is ≤ x ≤ 1.29, the La_{2– x} Sr_{1+ x} Cu₂O_6+δ solid solution is stable for 0.03 ≤ x ≤0.20, the La_{2– x} Sr _x Cu₂O_5–δ solid solution is stable for 0.00 ≤ x ≤1.08, and the La _x Sr_{14– x} Cu₂₄O₄₁ solid solution is stable for 0.00 ≤ x ≤ 6.15. The 30 kbar phase diagram differs from the 1 atm (0.1 MPa) and 10 kbar (1 GPa) results principally in the absence of La_{1– x} Sr_{2+ x} Cu₂O_5.5+δ as a stable phase and the extended range of the La_{2– x} Sr _x Cu₂O_5–δ solid solution at 30 kbar.     

Ag2O-Doped Bi2Sr2Ca1Cu2Ox Superconductors Prepared via Melt-Quenching

Ag₂O-doped superconducting Bi₂Sr₂Ca₁Cu₂O _x ceramics were prepared by a melt-quenching–reheating method. It is found that the Ag₂O-doped, as-cast specimens exhibit superconductivity ( T _c= around 80 K) by heat treatment at temperatures around 800°C even in an evacuated and sealed silica glass tube, while the undoped specimens do not and vaporize by the corresponding heat treatment. Conversion of the Ag₂O-doped, as-cast specimens into superconducting ceramics when heated in an evacuated vessel is explained in terms of the oxygen donor of Ag₂O in the specimen. This finding enables us to fabricate a desired shape of superconducting Bi₂Sr₂Ca₁Cu₂O _x ceramics sealed in metals or glasses. The addition of Ag₂O to Bi₂Sr₂Ca₁Cu₂O _x melt, however, had deleterious influences on the superconducting properties ( T _c and J _c) of the resultant ceramics when obtained by heat treatment in air.     

Phase Regions and Kinetics of Formation of (Bi,Pb)2Sr2Ca2Cu3Ox in Ag-Sheathed Tape

Ag-sheathed (Bi,Pb)₂Sr₂Ca₂Cu₃O, (2223) tapes were made by the oxide-powder-in-tube method. Tapes were heat-treated isothermally at several different temperatures in 7.5% O₂/Ar, then quenched into oil to retain the phase assemblages at the reaction temperatures. 2223 formed between ∼810° and ∼837°C. The Avrami equation was applied to describe the kinetics of 2223 formation from a mixture of Bi₂Sr₂CaCu₂O _x and nonsuperconducting phases, mainly Ca₂PbO₄ and CuO. The calculated Avrami exponent, n ∼ 1, indicated that the kinetics in this system could be described as a diffusion-controlled, two-dimensional nucleation and growth process. The apparent activation energy for forming 2223 was ∼2900 kJ/mol from ∼817° to ∼825°C and ∼890 kj/mol from ∼825° to ∼837°C. A temperature-time-transformation diagram was constructed based on the kinetic data; it describes the transformational behavior of this particular system.     

Preparation and Structural Investigation of Bi16(Sr,Ca)14O38

Single-crystal X-ray diffraction was used to investigate the structure of the ternary oxide of approximate formula Bi₁₄(Sr,Ca)₁₂O₃₃. The crystal examined was found to have a composition Bi₂Sr_0.68Ca_1.07O_4.75 or Bi₁₆Sr_5.44Ca_8.56O₃₈ as a result of refinement. It crystallizes in the monoclinic space group (C2/m), with cell parameters a = 21.764 (4) A, b = 4.3850 (13)° A, c = 12.905 (3) A, β= 102.72 (2)°, and V 1201.2 (5) A³. Strontium and calcium ions were found to substitute for each other. The structure consists of a network of alkaline-earth oxide polyhedra with broad channels parallel to the b axis, in which the bismuth ions reside. Two out of four crystallographically distinct Bi ions form infinite Bi—O zigzag ribbons of edge-linked Bi—O units, while each of the other two form oxygen corner-shared Bi—O chains along b . The lone pair electrons of the Bi ions point toward each other in the channels.     

Solid-Solution Ranges of the n= 2 and n= 3 Superconducting Phases in Bi2(SrxCa1 −x)n+1CunOy and the Effect on Tc

The cation solubility limits of the n = 2 and n = 3 superconducting phases in the Bi₂(Sr _x Ca_{1 − x} ) _{n +1}Cu _n O _y system were established along tie lines with compatible phases via electron probe microanalysis on bi- (or poly-) phasic samples prepared at 860°C. Pb additions (15 mol% of the Bi content) were used to facilitate formation of the n = 3 phase. In each case football-shaped volumes in composition space were established as the solubility limits which bordered on the nominal compositions 2212 or 2223 (Bi:Sr:Ca:Cu) with the long axis parallel to the Sr-Ca side of the quaternary (i.e., Sr-to-Ca intersolubility) but also extending toward Bi and Cu. This means that, for the most part, the superconducting phases are alkaline-earth deficient relative to the ideal 2212 and 2223 compositions. The Pb content in the 2223 phase is typically 10% of the Bi content. T _c variations could be correlated with variations in Sr or (Sr + Bi) content and the length of the c -axis parameter.     

Effect of Extrusion on the Critical Current Density of Bi1.4Pb0.6Sr2Ca2Cu3Ox Superconducting Wires

The effect of extrusion on improving the critical current density ( J _c) of Bi_1.4Pb_0.6Sr₂Ca₂Cu₃O _x superconducting wires is investigated. Calcined powders (Bi_1.4Pb_0.6Sr₂Ca₂Cu₃O _x ) are first mixed with a forming aid—a thermoplastic polymer (polyethylene)—for workability, and then extruded, using a capillary rheometer, to form wires 2 mm in diameter. The J _c value, measured by the four-probe method in liquid nitrogen at 77 K, is improved substantially by the following process: (1) the superconducting precursors are extruded at high viscosity with a forming aid, to align the platelike particles unidirectionally; (2) the forming aid alone is carefully burned out, without destroying the extruded configuration; and (3) the extruded wires are annealed at 850°C in air for more than 96 h.     

Effects of Temperature and Oxygen Partial Pressure on Nonstoichiometry of YBa2Cu3O6+δ

The oxygen content (6 +δ) in YBa₂Cu₃O_6+δ varies with temperature and oxygen partial pressure. An equation for the content as a function of temperature and oxygen partial pressure has been obtained based on the two-sublattice model of YBa₂Cu₃O₆( V ₀, O)₁. The results calculated using the equation are in very good agreement with published measured data.     

Influence of Ca2PbO4 on Phase Formation and Electrical Properties of (Bi,Pb)2Sr2Ca2Cu3O10/Ag Superconducting Composites

(Bi,Pb)₂Sr₂Ca₂Cu₃O₁₀ (Bi2223) precursor powders with large and small amounts of Ca₂PbO₄ phase were prepared and used to make superconductor/silver composite tapes. The melting behavior of the powders and tapes was examined by differential thermal analysis (DTA). The influence of Ca₂PbO₄ on the formation and microstructure of Bi2223, and electrical properties of the tapes, was investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and critical current measurements. It was found that the melting onset temperature ( T _m,onset) of precursor powders and composite tapes was strongly dependent on the amount of Ca₂PbO₄. Tapes with a small amount of Ca₂PbO₄ had a higher T _m,onset and a higher optimum sintering temperature compared with tapes with a large amount of Ca₂PbO₄. Also because of the higher sintering temperature, the total sintering time required for the former tapes was drastically shortened compared with the latter ones (250 vs 110 h). Furthermore, the microstructure and the current-carrying capacity of the tapes were significantly improved by reducing the Ca₂PbO₄ content of the precursor powders. These results are of practical significance for the commercialization of Bi-based high-temperature superconductors.     

Subsolidus Relations in the La2O3─CuO─CaO Phase Diagram and the La2O3─CuO Binary Join

The phase diagram for the CuO-rich part of the La₂O₃─CuO join was redetermined. La₂Cu₂O₅ was found to have a lower limit of stability at 1002°± 5°C and an incongruent melting temperature of ∼1035°C. LagCu₇O₁₉ had both a lower (1012°± 5°C) and an upper (1027°± 5°C) limit of stability. Subsolidus phase relations were studied in the La₂O₃─CuO─CaO system at 1000°, 1020°, and 1050°C in air. Two ternary phases, La_1.9Ca_1.1Cu₂O_5.9 and LaCa₂Cu₃O_8.6, were stable at these temperatures, with three binary phases, Ca₂CuO₃, CaCu₂O₃, and La₂CuO₄. La₂Cu₂O₅ and La₈Cu₇O₁₉ were stable only at 1020°C, and did not support solid-solution formation.     

Phase Separation and Crystallization of BiSrCaCu2Al0.5Ox Glass

Al₂O₃ addition to the melt of a BiSrCaCu₂O _x composition was found by TEM observation to cause the liquid-liquid phase separation of the melt-quenched glass, and to result in preferential precipitation of superconducting Bi₂Sr₂Ca₁Cu₂O _x crystals from the melt during the cooling process.     

Phase Equilibria of the La2O3-SrO-CuO System at 950°C and 10 kbar

Phase equilibria of the La₂O₃-SrO-CuO system have been determined at 950°C and 10 kbar (1 GPa). Stable phases at the apices of the ternary phase diagram are CuO, La₂O₃, and SrO. Stable intermediate phases are La₂CuO₄ in the LaO_1.5-CuO binary and Sr₂CuO₃, SrCuO₂, and Sr₁₄Cu₂₄O₄₁ in the CuO-SrO binary. The La_2-xSr _x CuO_4-δ solid solution is stable where 0.0 ≤ x ≤ 1.3, the La_2-xSr_1+xCu₂O_6+δ solid solution is stable where 0.0 ≤ x ≤ 0.2, the La_8-xSr _x Cu₈O_20-δ solid solution is stable where 1.3 ≤ x ≤ 2.7, the La _x Sr_14-x-Cu₂₄O₄₁ solid solution is stable where 0 ≤ x ≤ 6, and the La_1+xSr_2-xCu₂O_5.5+δ phase is stable where 0.04 ≤ x ≤ 0.16. The La₂O₃-SrO-CuO phase diagram at 950°C and 10 kbar is almost identical to that determined by other authors at 950°C and 1 atm, in terms of phase stability and solid-solution ranges.     

La(Sr)FeO3 SOFC Cathodes with Marginal Copper Doping

(La_0.8Sr_0.2)_0.98Fe_0.98Cu_0.02O_3−δ can be sintered directly onto YSZ (without the need for a protective ceria interlayer). Though subject to an extended "burn-in" period (∼200 h), anode-supported YSZ cells using the Cu-doped LSF achieve power densities ranging from 1.3 to 1.7 W/cm² at 750°C and 0.7 V. These cells have also demonstrated 500 h of stable performance. The results are somewhat surprising given that XRD indicates an interaction between (La_0.8Sr_0.2)_0.98Fe_0.98-Cu_0.02O_3−δ and YSZ resulting in the formation of strontium zirconate and/or monoclinic zirconia. The amount and type of reaction product was found to be dependent on cathode and electrolyte powder precalcination temperatures.