Effect of Oxygen Loss on Densification When Hot Isostatic Pressing YBa2Cu3O7−δ

Hot isostatic pressing of the high-T_c superconductor YBa₂Cu₃O_7−δ can lead to loss of oxygen and transformation of the material from the high-T_c orthorhombic phase to the nonsuperconducting tetragonal phase. It is shown that glass encapsulation helps retain the orthorhombic structure, whereas steel encapsulation resulted in formation of the tetragonal phase. Reasons for this phenomenon are discussed. The equilibrium oxygen gas pressure for the oxygen decomposition reaction in YBa₂Cu₃O₇, however, prevents full densification of this material in glass when employing hot isostatic pressing conditions of 200 MPa and 845°C.     

Transmission Electron Microscopy Study on the Annealing of YBa2Cu3O7-δ

Annealing in oxygen-rich atmosphere at temperatures between 400° and 600°C is an important step in the manufacture of superconducting YBa₂Cu₃O_7-δ. The symmetry of the orthorhombic phase requires that if more than one type of twin plane is present within a grain, a distorted region should exist inside the multiple twinned grain. This distorted region hinders the tetragonal-to-orthorhombic transformation and may account for some retained tetragonal phase inside an otherwise orthorhombic grain. A physical model is presented describing the formation of such regions and their eventual transformation into low-angle grain boundaries after long annealing. Extended annealing at intermediate temperatures apparently leads to the formation of planar faults in off-stoichiometric samples. Transmission electron microscope image contrast and energy dispersive X-ray analyses of highly defective regions suggest these defects are CuO _x ( x = 1, 2) extra layers. These extra layers tend to form near grain boundaries or free surfaces, where oxygen is readily available.     

Novel Solution-Soaking Method for Adding Dopants to YBa2Cu3O7−x to Achieve Higher Sintered Densities

YBa₂Cu₃O_7−x was doped with various metal ions by a new technique in which a pellet (after binder burnout) was soaked in a solution containing the appropriate ions and then dried. The sintered density of the treated pellets depended on the dopant in the solution, and in many cases it was much higher than that obtained for pure YBa₂Cu₃O_7−x (93% to 96% as compared with 85% to 90%). A study of the microstructure revealed that, in those cases where higher sintered densities were obtained, the grain size was much smaller. The grain morphology, however, did not change. It is likely that the high concentration of dopant adsorbed on the grain surface during solution soaking enhanced the rate of sintering.     

Superplastic Deformation in Fine-Grained YBa2Cu3O7−x

The superplastic behavior of YBa₂Cu₃O_{7− x} ceramic superconductors was studied. Large compressive deformation over 100% strain was measured in the temperature range of 775°–875°C, with a strain rate of 1 × 10⁻⁵ to 1 × 10⁻³/s, and a grain size of 0.5–1.4 μm. The nature of the deformation was investigated in terms of three deformation parameters: the stress exponent ( n ), the grain size exponent ( p ), and the activation energy ( Q ). The measured values of these parameters were n = 2 ± 0.3, p = 2.7 ± 0.7, and Q = 745 ± 100 kJ/mol. With the aid of the deformation map, the deformation mechanism was identified as grain boundary sliding accommodated by grain boundary diffusion. The conclusion is consistent with the microstructural observations made by SEM and TEM: the invariance of equiaxed grain shape, the absence of significant dislocation activity, no grain boundary second phases, and no significant texture development.     

Experimental and Thermodynamic Study of Nonstoichiometry in 〈YBa2Cu3O7-x〉

The dependence of the nonstoichiometry of 〈YBa₂Cu₃O_7−x〉 (solid) has been studied over 5 orders of magnitude in oxygen pressure and from 573 to 1173 K. Hydrogen-reduction methods for determining the absolute oxygen to-metal ratio were developed. The resulting data were used to derive a chemical thermodynamic representation of the experimental variables. The data were used to derive a chemical thermodynamic representaltion of the experimental variables. The data were also compared with several other investigations to indentify the selfconsistent sets of data. The present data and thermodynamic data from the literature were correlated on an Ellingham diagram.     

Defect Equilibria and Transport in YBa2Cu3O7-x at Elevated Temperatures: II, Nonstoichiometry

Aspects of nonstoichiometry for the Y-Ba-Cu (1: 2: 3) system are considered. The general formula YBa₂Cu₃O_7-x has been assumed for considerations of nonstoichiometry in 1: 2:3 oxide cuprates. Assuming that copper ions may occupy different lattice positions (independently of their valency), the equilibrium constants for oxygen intercalation were determined:     

Simultaneous Thermogravimetry and Evolved-Gas Analysis of YBa2Cu3O7 and LaBa2Cu3O7 Superconductors

Concurrent thermogravimetry (TG) and evolved-gas analysis (EGA) were done for YBa₂Cu₃O_7-z and LaBa₂Cu₃-O_7-z superconductors. The sample weights were monitored by thermobalance and the evolved O₂ and CO₂ species were monitored by quadruple mass spectrometer (QMS). No diffraction peak for the impurity phase containing a carbonate group was observed in the X-ray diffraction patterns for these samples, but the release of CO₂ was detected by EGA. CO₂ gas began to evolve from YBa₂Cu₃O_7-z at 543°C and from LaBa₂Cu₃O_7-z at 692°C. Preparation of high-quality YBa₂Cu₃O_7-z and LaBa₂Cu₃O_7-z superconductors is discussed on the basis of results of these thermal analyses.     

Formation of Grain-Boundary Carbon-Containing Phase During Annealing of YBa2Cu3O6+x

In situ annealing studies of YBa₂Cu₃O_6+x performed in an optical hot stage revealed that, at temperatures ∧450°, localized melting occurred. On subsequent cooling, a discrete second phase was observed at the YBa₂Cu₃O_6+x grain boundaries. Quantitative chemical analysis using X-ray wavelength dispersive spectroscopy indicated that the second phase was composed of a barium oxycarbonate. The source of the carbon in the second phase was identified to be CO₂ in the atmosphere.     

Defect Equilibria and Transport in YBa2Cu3O7-x at Elevated Temperatures: III, Defect Model and Conductivity Mechanism

Based on the measurements of electrical conductivity and thermopower (Seebeck coefficient) as a function of oxygen partial pressure, the defect structure and corresponding conduction mechanisms at elevated temperatures are considered for the Y-Ba-Cu-O (1:2:3) system. It has been postulated that the simple hopping model is not applicable to YBa₂Cu₃O_7-x. A modified conduction hopping mechanism has been proposed and equations describing the mobility of charge carriers in the studied system are derived. The most important advantage of the present model, in comparison to previous models, involves considering interactions between both electrons and electron holes and the resulting effect on their mobility terms. The observed departure of experimental data from the Heikes formula is explained by a very high concentration of defects and resulting substantial interactions between the defects which must be taken into account. The proposed transport model exhibits good agreement with experimental data of nonstoichiometry and the presently determined electrical conductivity and thermopower. It has been argued that the charge transfer mechanism depends substantially on the oxygen partial pressure and resulting oxygen content in the oxide lattice.     

Influence of Post Hot Isostatic Pressing on the Microstructural Development and Critical Current Density of YBa2Cu3O7-x

Samples of nearly theoretical density are produced by post hot isostatic pressing (post-HIP) of presintered YBa₂Cu₃O_7-x using argon as the pressure medium. The hot isostatically pressed samples show improved values for critical current density at 77 K. Experimental aspects of post-HIP are described, and microstructural development of YBa₂Cu₃O_7-x during sintering and post-HIP is discussed.     

Type II Magnetic Levitation on Sinter-Forged YBa2Cu3Ox Superconductor

Submicrometer powder of singlephase YBa₂Cu₃O_x (YBC), prepared from nitrate salts, were free-sintered and sinter-forged at 1223 K. The levitation force on magnets exerted by the superconductor was found to depend on the thickness of the superconductor, the shear strain imposed during sinter-forging, and the time and temperature of the high-pressure oxygen anneal after sinter-forging. The first result is direct proof of the type II nature of the YBC superconductor. In the second experiment a shear strain of 300% increased the levitation force by a factor of 3. The third result confirmed that YBC transforms to the tetragonal structure at 1223 K, which must be restored to the orthorhombic structure by annealing at lower temperature. Optimum results were obtained when the specimens were annealed in pressurized oxygen (3 MPa) for 50 h at 673 K.     

Vapor Pressure of Barium and Copper Components in YBa2Cu3O7−x Superconductor Ceramics

Purified air is passed over a specimen of YBa₂Cu₃O_{7– x} at 890°C; the vaporized substances are condensed in a pure alumina tube, then subjected to inductively controlled plasma analysis. Vapor pressure values of 2.5 × 10⁻⁵ Pa for BaO( g ), 1.2 × 10⁻⁴ Pa for Cu( g ), and 2.2 × 10⁻⁵ Pa for CuO( g ) are obtained under 2.1 × 10⁴ Pa (0.21 bar) of oxygen pressure. No Y vapor is detected at this temperature.     

Effects of Temperature and Strain Rate on the Plastic Deformation of Fully Dense Polycrystalline Y1Ba2Cu3O7−x Superconductor

The knowledge of the steady-state stress for plastic deformation as a function of temperature and strain rate is essential for hot-forming superconducting material into commercially useful shapes. In this paper, results are presented on the experimental determination of the rheology of fully dense polycrystalline Y₁Ba₂Cu₃O_7−x superconducting material at temperatures ranging from 750° to 950°C and strain rates of 10⁻⁴, 10⁻⁵, and 10⁻⁶ s⁻¹. The data are best fitted by a power law: ε(s⁻¹)=8.9 × 10⁻¹⁷. (s⁻¹) σ^2.5 (Pa) exp [−2.01 × 10⁵(J·mol⁻¹)|RT]. X-ray analysis shows that the superconducting material retains its phase composition after nearly 70% total strain of the sample. A strong anisotropy in the resistivity of the deformed samples is observed because of the development of a preferred orientation of the a or b axis of Y₁Ba₂Cu₃O_7−x orthorhombic perovskite single crystals perpendicular to the principal maximum compressive stress.     

Thermopower of YBa2Cu3O7-δ–Ag Composites

The percolation behavior of normal-state thermopower, resistivity, and superconductivity have been studied in YBa₂Cu₃O_7-δ─Ag (YBCO─Ag) composite systems. The normal-state resistivity and thermopower show a percolation threshold at a Ag volume fraction ( V _Ag) of 20% to 30%, whereas the superconducting network shows a threshold at a V _Ag of ≅70% to 80%. The results obtained from this study show that the YBCO─Ag composite obtained from Ag₂O and YBCO powders is uniformly distributed with Ag and YBCO remaining as separate phases without changing their characteristics. The measurements of thermopower indicate that the normal-state thermopower and phonon-drag thermopower are affected by the Ag addition. The stability of YBCO is increased when it is in composite form.     

Defect Equilibria and Transport in YBa2Cu3O7-x at Elevated Temperatures: I, Thermopower, Electrical Conductivity, and Galvanic Cell Studies

Studies of the Y-Ba-Cu-O system at elevated temperatures (300 to 1173 K) and under controlled oxygen activity (10² to 10⁵ Pa) were performed by using electrical methods such as thermopower, electrical methods such as thermopower, electrical conductivity, and emf of solid-state galvanic cell measurements. The discontinuities of measured electrical parameters demarcate regions of different properties and phenomena: (a) the transition between the range when the oxide sample is quenched on one side and the equilibrium range on the other side and (b) the transition between the quasi-metallic and semiconducting (m/s) regimes. The temperature of the m/s transition increases from 950 K at p o₂= 10² Pa to 1150 K at 10⁴ Pa. These data have served to derive a T-p o₂ diagram for YBa₂Cu₃O_7-x. NO discontinuity of the measured electrical parameters has been observed under conditions accompanying the phase transition between the tetragonal and orthorhombic structures. A p-n type transition has been observed within the semiconducting regime. Electrochemical oxygen titration has led to the determination of the relationship between the lattice oxygen content and the oxygen activity in the ambient gas atmosphere.     

Hot Isostatic Pressing of YBa2Cu3O7-δ and YBa2Cu3O7–δ/Ag Composites

Hot isostatic pressing (HIP) can be used to produce fully dense shapes of high-temperature ceramic superconductors. Densification modeling of monolithic YBa₂Cu₃O_7-δ and the composite YBa₂Cu₃O_7-δ/Ag systems allows an understanding of the HIP process and has led to the development of successful protocols for HIP of these materials. Ag metal is the best encapsulation material found for both systems. HIP of monolithic YBa₂Cu₃O_7-δ requires a slow ramp of pressure in order to prevent decomposition into more basic oxides such as Y₂BaCuO₅ and CuO. HIP of composite YBa₂Cu₃O_7-δ/Ag requires careful powder processing to obtain dense material with a fine dispersion of Ag.     

Melt Processing of YBa2Cu3O7-x

Sintering YBa₂Cu₃O_{7- x} bulk forms at 1050°C followed by annealing at 980°C causes the development of a thick oriented surface layer (Lotgering factor = 0.7). The thickness of the layer depends on the thermal treatment, which is a two-step sintering process. Firing at 1050°C for 2.5 h followed by 30 h at 980°C leads to the development of a 0.1-mm-thick surface layer, with clear indication that longer annealing would result in a thicker film. Some orientation develops during un-axial compaction of the powders. Lotgering orientation factor calculation from X-ray diffraction analysis. SEM, and TEM were used to characterize the microstructure of these samples. T _c was similar to that of conventionally processed high-density samples, between 83 and 87 K. Some thermal treatments resulted in samples that displayed high resistivity above T _c , possibly caused by segregation of Cu to the grain boundaries.     

Hot Deformation of YBa2Cu3O7-δ and Composite YBa2Cu3O7-δ/Ag

The response of ceramic superconductors and ceramic composites to compressive stresses at high temperatures has been examined. Monolithic YBa₂Cu₃O_7-δ and composite YBa₂Cu₃O₇-δ₆/Ag were tested at constant true strain rates from 10^-6 to 10^-3 s^-1 at temperatures from 800° to 950°C. Fine-grained monolithic YBa₂Cu₃O_7-δ appears to have a regime of superplastic deformation between temperatures of 850° and 950°C at strain rates from 10^-6 to 10^-4 S^-1. The addition of 20 vol% Ag to a coarser-grained material enhances the ductility of the ceramic and lowers the flow stress by a factor of 3 to 10. However, there is no evidence of superplasticity in the composite material in the range of temperature and strain rate where it was tested.