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At least 19 records

Effect of oxygen stoichiometry on T(sub c) of Bi-based superconductors

The role of oxygen stoichiometry on T(sub c) is relatively well established on La2CuO(4+x) and the YBa2Cu3O(7-x) (123) superconductors, as compared to the Bi-based superconductors. Results are presented of investigations on the effects of oxygen stoichiometry on the transition temperature T(sub c) of Bi2Sr2CaCu2O(8+x) (2212 phase), and Pb-doped Bi2Sr2Ca2Cu3O(10+X) (2223 phase). It is shown that the effects of oxygen stoichiometry on T(sub c) of these two phases are very different. These results may be helpful in understanding the mechanism of superconductivity in the Bi-based superconductors.

Zhao, J.↗

Effects of oxygen stoichiometry on the scaling behaviors of YBa2Cu3O(x) grain boundary weak-links

The effects of oxygen stoichiometry on the transport properties of the pulsed laser deposited YBa2Cu3O(x) bicrystalline grain boundary weak-link junctions were studied. It is found that not only the cross boundary resistive transition foot structure can be manipulated repeatedly with oxygen annealing processes but the junction behaviors are also altered in accordance. In the fully oxygenated state i.e with x = 7.0 in YBa2Cu3O(x) stoichiometry, the junction critical current exhibits a power of 2 scaling behavior with temperature. In contrast, when annealed in the conditions of oxygen-deficient state (e.g with x = 6.9 in YBa2Cu3O(x) stoichiometry) the junction critical current switches to a linear temperature dependence behavior. The results are tentatively attributed to the modification of the structure in the boundary area upon oxygen annealing, which, in turn, will affect the effective dimension of the geometrically constrained weak-link bridges. The detailed discussion on the responsible physical mechanisms as well as the implications of the present results on device applications will be given.

Wu, K. H.↗

Cryogenic Extension of NASA Species Polynomials Using Hydrogen and Oxygen at Stoichiometry

The Helmholtz free energy for a mixture has been used in many chemistry and combustion studies for mixtures. An approach is described where polynomial fits intended for a thermally perfect ideal gases can be modified and implemented into a Helmholtz free energy model, such as those used by NIST in their REFPROP program. However, the limitation of the polynomial fits must be respected and should only used in a valid temperature interval where the flow field can be treated as a thermally perfect ideal gas when these species are present. This approach can allow a CFD simulation to have cryogenic regions of a flow field where high fidelity cryogenic species models are needed and allows for the use of species in other areas at higher temperatures where combustion species do not have such a model available or is not needed. Presented in the paper are CFD 1D detonation wave and species mass fraction simulation results which have cryogenic upstream conditions of Hydrogen and Oxygen at stoichiometry.

Combustion↗

Cryogenic Extension of NASA Species Polynomials Using Hydrogen and Oxygen at Stoichiometry

NASA has been conducting research in Rotating Detonation Rocket Engines (RDREs) for several years. A recent test at the Marshall Spaceflight Center has successfully shown operation of a RDRE that ran for 251 seconds which had combustion chamber cryogenic inlet conditions [1]. However, an overall pressure gain was not observed in the performance of the engine. Such an indication could mean an optimal chamber design is yet to be discovered. Such a design could significantly reduce parasitic pressure loses and improve overall engine efficiency beyond that of conventional rockets. To investigate different chamber configurations, new CFD capability is needed to accurately capture cryogenic thermophysical and transport property data. Such an effort is currently part of NASA’s Early Career Initiative (ECI) program. This paper focuses on the thermophysical property mixture model approach that makes use of NASA’s polynomial fits of species and another cryogenic model chosen from NIST’s Refprop program. Presented in this paper are results of a 1D denotation CFD simulation of stoichiometric Hydrogen and Oxygen mixture at a cryogenic upstream condition.

Combustion↗

Magnetism and superconductivity of some Tl-Cu oxides

Many copper oxide based Thallium compounds have now been discovered. In comparison to the Bi-compounds, the Tl-system shows a richer diversity; viz., High Temperature Superconductors (HTSC) can be obtained with either one or two Tl-0 layers (m = 1,2); also, the triple-digit phases are easier to synthesize. The value of d, oxygen stoichiometry, is critical to achieving superconductivity. The Tl system is robust to oxygen loss; Tl may be lost or incorporated by diffusion. A diffusion coefficient equal to 10 ms at 900 C was determined. Both ortho-rhombic and tetragonal structures are evidenced, but HTSC behavior is indifferent to the crystal symmetry. This system has the highest T(sub c) confirmed. T(sub c) generally increases with p, the number of CuO layers, but tends to saturate at p = 3. Zero resistance as high as 125K has been observed. Most of these HTSC's are hole type, but the Ce-doped specimens may be electronic. The magnetic aspects were studied; because in addition to defining the perfectly diamagnetic ground state as in the conventional superconductors, magnetism of the copper oxides show a surprising variety. This is true of both the normal and the superconducting states. Also, due to the large phonon contribution to the specific heat at the high T(sub c) accurate thermal measurement of important parameters such as the sp. heat jump, electronic density of states, D(Ef) and coherence length are uncertain, and thus, are estimated from the magnetic results. Results from the Tl-system CuO, LaBaCuO, 120 and the Bi-CuO compounds are discussed. The emphasis is on the role of magnetism in the TlCuO HTSC, but technological aspects are also pointed out.

Datta, Timir↗

Magnetism and superconductivity of some Tl-Cu oxides

Many copper oxide based Thallium compounds are now known. In comparison to the Bi-compounds, the Tl-system shows a richer diversity; i.e., High Temperature Superconductors (HTSC) can be obtained with either one or two Tl-0 layers (m = 1,2); also, the triple-digit phases are easier to synthesize. The value of d, oxygen stoichiometry, is critical to achieving superconductivity. The Tl system is robust to oxygen loss; Tl may be lost or incorporated by diffusion. A diffusion coefficient equal to 10 ms at 900 C was determined. Both ortho-rhombic and tetragonal structures are found, but HTSC behavior is indifferent to the crystal symmetry. This system has the highest T(sub c) confirmed. T(sub c) generally increases with p, the number of CuO layers, but tends to saturate at p = 3. Zero resistance was observed at temperatures as great as 125 K. Most of these HTSC's are hole type, but the Ce-doped specimens may be electronic. The magnetic aspects were studied; because in addition to defining the perfectly diamagnetic ground state as in conventional superconductors, magnetism of the copper oxides show a surprising variety. This is true of both the normal and the superconducting states. Also, due to the large phonon contribution to the specific heat at the high T(sub c) jump, electronic density of states, D(Ef), and coherence length are uncertain, and thus, are estimated from the magnetic results. Results from the Tl-system CuO, LaBaCuO,120 and the Bi-CuO compounds are discussed. The emphasis is on the role of magnetism in the Tl-CuO HTSC, but technological aspects are also pointed out.

Datta, Timir↗

Structural chemistry of Au(III)-substituted Ba2YCu3O(7-delta)

A series of gold-substituted perovskite superconductors Ba2Y(Cu/1-x/Aux)3O(7-delta)(x = 0-0.1) was synthesized. For x = 0.1, there was no change in the a and b lattice parameters (a = 3.826 A and b = 3.889 A), but a 0.06 A c-axis expansion to 11.75 A was observed. Substituted gold was found to be trivalent by X-ray photoelectron spectroscopy. Replacing Cu(1) in the copper oxide chain with a slight reordering of oxygen is consistent with c-axis expansion. The formal charge of the site remains trivalent, while remaining Cu in the chains is reduced to Cu(I), resulting in an oxygen stoichiometry of less than 7. Finally, no large effect on Tc is observed (Tc = 89 K for x = 0.10), in contrast to the effect of a number of other metal ion dopants. These results are discussed relative to the chemistry of Au(III) and to the use of the metal in structures containing gold and ceramic superconductors.

Hepp, A. F.↗

Study of local structure and magnetism in high-T(sub c) copper oxide superconductors

The muon spin rotation (MUSR) study of local magnetism of Sr-doped La2CuO4 is reviewed. Emphasis is placed on magnetic order as detected by local and bulk probes with local atomic environments studied by x ray absorption fine structure (XAFS). Correlations between the MUSR study of local magnetic ordering and the bulk magnetization study are presented along with a discussion of the dependence upon oxygen stoichiometry. Results are presented for both superconducting phases and magnetic phases. Recent data which reveals the existence of local magnetic ordering in the hydrogen-doped YBa2Cu3O7 system are also discussed.

Budnick, J. I.↗

Synthesis and structural chemistry of Au(III)-substituted Ba2YCu3O(7-delta)

Gold-substituted superconductors, Ba2Y(Au(x)Cu(1-x))3O(7-delta) (x = 0-0.1) were synthesized. For x = 0.1, there was no change in the a and b lattice parameters (a = 3.826 A and b = 3.889 A) but a 0.06 A c axis expansion to 11.75 A was observed. Substituted gold is found to be trivalent by XPS. Replacing Cu(1) in the copper oxide chain with a slight reordering of oxygen is consistent with c axis expansion. The formal charge of the site remains trivalent; remaining Cu in the chains may be reduced resulting in an oxygen stoichiometry is less than or equal to 7. A small effect on T(sub c)(89 K for x = 0.10) is observed upon gold substitution.

Hepp, A. F.↗

Studies of local magnetism and local structure in La(2-x)Sr(x)CuO4

The muon spin rotation (MUSR) study of local magnetism of Sr-doped La2CrO4 is reviewed. Emphasis is placed on magnetic order as detected by local and bulk probes with local atomic environments studies by x ray absorption fine structure (XAFS). Correlations between the MUSR study of local magnetic ordering and the bulk magnetization study are presented along with a discussion of the dependence upon oxygen stoichiometry. Results are presented for both superconducting phases and magnetic phases. Recent data which reveals the existence of local magnetic ordering in the hydrogen-doped YBa2Cu3O7 system are also discussed.

Budnick, J. I.↗

Air oxidation of hydrazine. 1. Reaction kinetics on natural kaolinites, halloysites, and model substituent layers with varying iron and titanium oxide and O- center contents

Air oxidation of hydrazine was studied by using a group of kaolinites, halloysites, and substituent oxides as models for the tetrahedral and octahedral sheets. The rate was found to be linear with oxygen. The stoichiometry showed that oxygen was the primary oxidant and that dinitrogen was the only important nitrogen-containing product. The rates on kaolinites were strongly inhibited by water. Those on three-dimensional silica and gibbsite appeared not to be. That on a supposedly layered silica formed from a natural kaolinite by acid leaching showed transitional behavior--slowed relative to that expected from a second-order reaction relative to that on the gibbsite and silica but faster than those on the kaolinites. The most striking result of the reaction was the marked increase in the rate of reaction of a constant amount of hydrazine as the amount of clay was increased. The increase was apparent (in spite of the water inhibition at high conversions) over a 2 order of magnitude variation of the clay weight. The weight dependence was taken to indicate that the role of the clay is very important, that the number of reactive centers is very small, or that they may be deactivated over the course of the reaction. In contrast to the strong dependence on overall amount of clay, the variation of amounts of putative oxidizing centers, such as structural Fe(III), admixed TiO2 or Fe2O3, or O- centers, did not result in alteration of the rate commensurate with the degree of variation of the entity in question. Surface iron does play some role, however, as samples that were pretreated with a reducing agent were less active as catalysts than the parent material. These results were taken to indicate either that the various centers interact to such a degree that they cannot be considered independently or that the reaction might proceed by way of surface complexation, rather than single electron transfers.

NASA Discipline Number 52-20↗

Effect of off-design operation of MHD generators on NO/x/ chemical kinetics

The purpose of this study is to provide a capability for determining the chemical kinetic behavior of one family of pollutants, the nitrogen oxides, in the flow of a coal-fired MHD generator facility. The method used in the study allows the prediction of the nonequilibrium concentration of the minor NO(x) species in a flow otherwise assumed in equilibrium. Consideration is given to the effect of preheat, stoichiometry, and oxygen enrichment of the NO(x) concentration. The effect of preheat and stoichiometry is found to have a significant influence on the NO(x) concentration at the exit of the radiant boiler.

Simmons, G. A.↗

Loss of oxygen from Venus

Ionization of thermal and nonthermal oxygen atoms above the plasmapause on Venus supplies an escape flux for O averaging 6 x 10 to the 6th atoms/sq cm-sec. Hydrogen and oxygen atoms escape with stoichiometry characteristic of water. It is argued that escape of H is controlled by the oxidation state of the atmosphere, regulated by escape of O.

Mcelroy, M. B.↗

Partical Melting of bulk Bi-2212

Dense and textured Bi-2212 bulk samples have been produced by the partial melting process. The appropriate amount of liquid phase necessary for complete densification has been adjusted by controlling the maximum processing temperature. The maximum temperature itself has to be adapted to several parameters as powder stoichiometry, silver addition and oxygen partial pressure. Prolonged annealing at 850 and 820 C and cooling in N2 atmosphere led to nearly single phase material with T(sub c) = 92 K. Critical current densities j(sub c) of 2'200 A/sq cm at 77 K/0 T have been achieved in samples of more than 1 mm thickness. Reducing the thickness below 0.4 mm enhances j(sub c) considerably to values is greater than 4'000 A/sq cm. The addition of 2 wt% Ag decreases the solidus temperature of the Bi-2212 powder by 21 C. Therefore, the maximum heat treatment temperature of Ag containing samples can be markedly lowered leading to a reduction of the amount of secondary phases. In addition, Ag enhances slightly the texture over the entire cross section and as a result j(sub c) at 77 K/0 T.

Heeb, B.↗

Ensemble Diffraction Measurements of Spray Combustion in a Novel Vitiated Coflow Turbulent Jet Flame Burner

An experimental investigation is presented of a novel vitiated coflow spray flame burner. The vitiated coflow emulates the recirculation region of most combustors, such as gas turbines or furnaces; additionally, since the vitiated gases are coflowing, the burner allows exploration of the chemistry of recirculation without the corresponding fluid mechanics of recirculation. As such, this burner allows for chemical kinetic model development without obscurations caused by fluid mechanics. The burner consists of a central fuel jet (droplet or gaseous) surrounded by the oxygen rich combustion products of a lean premixed flame that is stabilized on a perforated, brass plate. The design presented allows for the reacting coflow to span a large range of temperatures and oxygen concentrations. Several experiments measuring the relationships between mixture stoichiometry and flame temperature are used to map out the operating ranges of the coflow burner. These include temperatures as low 300 C to stoichiometric and oxygen concentrations from 18 percent to zero. This is achieved by stabilizing hydrogen-air premixed flames on a perforated plate. Furthermore, all of the CO2 generated is from the jet combustion. Thus, a probe sample of NO(sub X) and CO2 yields uniquely an emission index, as is commonly done in gas turbine engine exhaust research. The ability to adjust the oxygen content of the coflow allows us to steadily increase the coflow temperature surrounding the jet. At some temperature, the jet ignites far downstream from the injector tube. Further increases in the coflow temperature results in autoignition occurring closer to the nozzle. Examples are given of methane jetting into a coflow that is lean, stoichiometric, and even rich. Furthermore, an air jet with a rich coflow produced a normal looking flame that is actually 'inverted' (air on the inside, surrounded by fuel). In the special case of spray injection, we demonstrate the efficacy of this novel burner with a methanol spray in a vitiated coflow. As a proof of concept, an ensemble light diffraction (ELD) optical instrument was used to conduct preliminary measurements of droplet size distribution and liquid volume fraction.

Cabra, R.↗

Temperature dependence of electrical conductivity and lunar temperatures

Metallic conduction mechanicsms are probably not important in lunar materials because of the small amounts of free metal and metallic oxides present. This is confirmed by the extremely low conductivities measured to date and the fact that the conductivity increases with temperature. The major conduction mechanicsm appears to be ionic. This conduction mechanism is very strongly controlled by temperature, by deviations from stoichiometry, by electric field strengths, and by oxygen fugacity.

Olhoeft, G. R.↗

Isotopic study of oxygen diffusion in oxide coatings

Diffusion of oxygen in thin films of silicon dioxide was studied using oxygen isotopically enriched in oxygen of atomic mass 18 (O-18). This subject is of interest because thin films of dielectrics such as SiO2 are proposed for use as a protective coatings for solar mirrors in low Earth orbit, which is a strongly oxidizing environment. Films of this material were prepared with a direct current magnetron using reactive sputtering techniques. To produce (O-18)- enriched SiO2, a standard 3.5-in.-diameter silicon wafer was reactively sputtered using (O-18)-enriched (95 percent) oxygen as the plasma feed gas. The films were characterized using Rutherford backscattering and Secondary Ion Mass Spectrometer (SIMS) to establish stoichiometry and purity. Subsequently, the films were exposed to an air-derived oxygen plasma in a standard laboratory plasma reactor for durations of up to 10 hr. The concentration ratio of O-16 as a function of depth was determined using SIMS profiling and compared to a baseline, nonplasma exposed sample. A value for the diffusivity of oxygen near the surface of these films was obtained and found to be about 10(-15)sq cm/sec.

Gulino, Daniel A.↗