Solubility and diffusion studies of ultra pure transition elements in ultra pure alkali metals fifth quarterly report, 28 jun. - 3 oct. 1964
Solubility and diffusion of ultrapure transitional elements and compounds in alkali metals
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Solubility and diffusion of ultrapure transitional elements and compounds in alkali metals
This report contains results of structural analyses performed in support of the NASA structural testing of an all-composite stitched/RFI (resin film infusion) wing stub box. McDonnell Douglas Aerospace Company designed and fabricated the wing stub box. The analyses used a global/local approach. The global model contains the entire test article. It includes the all-composite stub box, a metallic load-transition box and a metallic wing-tip extension box. The two metallic boxes are connected to the inboard and outboard ends of the composite wing stub box, respectively. The load-transition box was attached to a steel and concrete vertical reaction structure and a load was applied at the tip of the extension box to bend the wing stub box upward. The local model contains an upper cover region surrounding three stringer runouts. In that region, a large nonlinear deformation was identified by the global analyses. A more detailed mesh was used for the local model to obtain more accurate analysis results near stringer runouts. Numerous analysis results such as deformed shapes, displacements at selected locations, and strains at critical locations are included in this report.
Solubility and diffusion studies of ultrapure transition elements in ultrapure alkali metals
The paper considers the interface between two bulk metals and the effect of this interface on adhesive bonding, resistance to tangential displacements, friction and the interfacial transport from one surface to another. Using Auger emission spectroscopy, field ion microscopy, and low energy electron diffraction techniques, the influence of surface orientation, lattice registry, crystal lattice structure and defects, metal surface chemistry and alloying on the characteristics of the interface was studied for noble, platinum, transition, and Group 4B metals. With dissimilar metals in contact, epitaxial transfer of the cohesively weaker to the cohesively stronger metal has been observed. Surface chemical activity of the noble and platinum metals is shown to affect interfacial behavior as does a valence bonding in the transition metals, and the degree of metallic nature in the Group 4B elements. Alloying elements, e.g., Si and Fe, can alter interfacial behavior by segregation to the surface of metals or by altering bulk properties such as crystal transformation kinetics.
This paper describes experiments conducted with a purpose of fabricating superconducting composites from Pb, Bi, and Ba2YCu3O(x), together the results of SEM examinations and energy dispersive spectroscopy performed on products. Results showed a limited utility of Pb and Pb(1-x)Bi(x) as matrices for ceramic superconductors. It was found that cold pressing followed by sintering at 200 C resulted in a composite which excluded flux below 90 K but did not show zero electrical resistance until the metal superconducting transition. Processing at 400 or 950 C resulted in oxygen depleted perovskite and/or metal oxides; these materials displayed greatly degraded superconducting properties. Finally, processing at 800 C resulted in high Tc only for composites containing more than 90 wt pct ceramic.
Oxidation/corrosion of metals at high temperatures primary life-limiting mechanism of parts in rocket engines. Combination of metals greatly increases operating temperature and longevity of these parts. Consists of two transition-element metals - iridium and rhenium - that melt at extremely high temperatures. Maximum operating temperature increased to 2,200 degrees C from 1,400 degrees C. Increases operating lifetimes of small rocket engines by more than factor of 10. Possible to make hotter-operating, longer-lasting components for turbines and other heat engines.
Preliminary results on observations of chromospheric and transition layer emission of stars with different metal abundances are reported. Metal deficient stars generally show reduced emission in the Mg II resonance lines and also in the other chromospheric and transition layer emission lines. This is interpreted as showing that energy fluxes other than acoustic fluxes must at least be coresponsible for the coronal and transition layer heating.
Theoretical studies of selected diatomic and triatomic molecules containing copper and the simple metals Li, Na, K, Be, and Al are presented, with emphasis on elucidating the nature of the bonding in mixed transition metal-simple metal systems. Large Gaussian basis sets are used in the diatomic calculations, and are used to calibrate the triatomic calculations, in which somewhat smaller Gaussian basis sets are employed. Electron correlation is incorporated using both the single-reference singles plus doubles configuration interaction and coupled pair functional methods. It is found that alkali atoms form very polar sigma bonds with copper, and that the ionicity increases with the inclusion of higher excitations because they improve the electron affinity of copper, which in turn allows a larger negative charge on copper. Aluminum is found to form stronger bonds than beryllium, since it does not have to undergo sp hybridization. Some of the trimers bond by forming three-center three-electron bonds. These multicenter bonds are quite strong even when compared to the two-electron bonds in the dimers or to other bonding mechanisms in the trimers.
Disclosed is a process for oxidizing volatile organic compounds to carbon dioxide and water with the minimal addition of energy. A mixture of the volatile organic compound and an oxidizing agent (e.g. ambient air containing the volatile organic compound) is exposed to a catalyst which includes a noble metal dispersed on a metal oxide which possesses more than one oxidation state. Especially good results are obtained when the noble metal is platinum, and the metal oxide which possesses more than one oxidation state is tin oxide. A promoter (i.e., a small amount of an oxide of a transition series metal) may be used in association with the tin oxide to provide very beneficial results.
Disclosed is a process for oxidizing formaldehyde to carbon dioxide and water without the addition of energy. A mixture of formaldehyde and an oxidizing agent (e.g., ambient air containing formaldehyde) is exposed to a catalyst which includes a noble metal dispersed on a metal oxide which possesses more than one oxidation state. Especially good results are obtained when the noble metal is platinum, and the metal oxide which possesses more than one oxidation state is tin oxide. A promoter (i.e., a small amount of an oxide of a transition series metal) may be used in association with the tin oxide to provide very beneficial results.
The temperature of the interface and/or a superficial layer of a substrate during ion plating was investigated using a metallic glass of the composition Fe67Co18B14Si1 as the substrate and as the temperature sensor. Transmission electron microscopy and diffraction studies determined the microstructure of the ion-plated gold film and the substrate. Results indicate that crystallization occurs not only in the film, but also in the substrate. The grain size of crystals formed during ion plating was 6 to 60 nm in the gold film and 8 to 100 nm in the substrate at a depth of 10 to 15 micrometers from the ion-plated interface. The temperature rise of the substrate during ion plating was approximately 500 C. Discontinuous changes in metallurgical microstructure, and physical, chemical, and mechanical properties during the amorphous to crystalline transition in metallic glasses make metallic glasses extremely useful materials for temperature sensor applications in coating processes.
The temperature of the interface and/or a superficial layer of a substrate during ion plating was investigated using a metallic glass of the composition Fe67Co18B14Si1 as the substrate and as the temperature sensor. Transmission electron microscopy and diffraction studies determined the microstructure of the ion-plated gold film and the substrate. Results indicate that crystallization occurs not only in the film, but also in the substrate. The grain size of crystals formed during ion plating was 6 to 60 nm in the gold film and 8 to 100 nm in the substrate at a depth of 10 to 15 micrometers from the ion-plated interface. The temperature rise of the substrate during ion plating was approximately 500 C. Discontinuous changes in metallurgical microstructure, and physical, chemical, and mechanical properties during the amorphous to crystalline transition in metallic glasses make metallic glasses extremely useful materials for temperature sensor applications in coating processes.
Historically, the theoretical treatment of the liquid phases has always been more difficult and complicated than that for solid and gas phases. A liquid has no lattice structure as crystalline solids and the atoms/molecules in the liquid can migrate through it relatively rapidly. On the other hand, it is also interacting with many other atoms/molecules so that the simplifications of the kinetic theory of gases cannot be employed. For more complicated liquids, such as the liquids of high ionicity and those containing hydrogen bonds and electric dipoles, the understanding is far from complete. At the same time, accurate information on the physics and chemistry of semiconductor melts is needed for the quantitative descriptions of the process of crystal growth from melt. The pre-crystallization phenomena in the liquid phase are critical because the properties of the grown crystals depend on the state and structure of the melt as well as the thermal history of the melt during solidification process. However, the data on the liquid phase, such as thermophysical properties of semiconductor melts are scarce, especially for the HgTe-based II-VI ternary compound semiconductors because of their high vapor pressure and extreme toxicity. Analysis of the thermophysical properties of the melt can provide information about structural transitions of the melt during the solidification process. From a broader point of view, the structure of liquids is much more complicated than the crystalline solids, especially the relaxation behavior through different thermal histories. The theory of hetero-phase fluctuations of liquids is applicable to any many-body systems including condensed-matter physics, field theory, physics of nuclear-matter, cosmology, biology and even sociology. This book summarizes the physics and chemistry from the experimental measurements and theoretical analyses of phase diagram, thermodynamic properties, density, thermal conductivity, viscosity, and electrical conductivity on the binary, pseudo-binary and ternary melts of the most advanced IR-detector material systems of HgCdTe and HgZnTe as well as the analyses of these results. The main objectives of this study are: (1) to provide the phase diagrams and thermodynamic properties of Hg-Cd-Te and Hg-Zn-Te systems through quantitatively fitting the experimental data by assuming an associated solution model for the liquid phase, (2) to experimentally measure the thermophysical properties of the Hg-Cd-Te and Hg-Zn-Te melts, including density, viscosity, electrical conductivity and thermal conductivity as functions of temperature and composition and (3) to enhance the fundamental knowledge of hetero-phase fluctuations and relaxation phenomena in the melts and extend our understanding of the solidification process in order to interpret the experimental results of crystal growth so as to improve the melt growth processes of the compound semiconductor. The physics and chemistry of Te and HgTe-based ternary melts were explored through the studies of the structural transformation during melting, the supercooling during solidification, the relaxation phenomena after rapid cooling of the melts and the metal-semiconductor transition in the melts through the analyses of electrical conductivity and Lorenz number. An in-depth study on the thermophysical properties and their time-dependent structural dynamic processes taking place in the vicinity of the solid-liquid phase transition of the narrow homogeneity range HgTe-based ternary semiconductors as well as the analysis of the homogenization process in the melt will also be presented.
A transition from metallic to ceramic turbine components that can operate at higher turbine engine temperatures will push component surface temperatures from below 1200 °C into a 1300 to 1500 °C temperature range that is much more challenging for phosphor thermometry measurements. To address this challenge, Y 2 SiO 5 :Er was selected for its high temperature sensing performance by both luminescence lifetime and luminescence intensity ratio (LIR) methods as well as its thermochemical compatibility with the current generation of rare earth silicate environmental barrier coatings (EBCs) that are required to protect SiC/SiC ceramic composite components. Lifetime measurements that monitor the Er3+ 4S3/2→4I15/2 emission decay at 542 nm exhibited a slow decrease in decay time with temperature up to 1300° C, above which the decay decreased steeply to provide good temperature sensitivity in the 1300 to 1500 °C range (Fig. 1). LIR images were obtained where each pixel represented the ratio I488/I561 (I488 and I561 are the detected 488 nm 4F7/2→4I15/2 and the 561 nm 4S3/2→4I15/2 emission band intensities, respectively). Good temperature sensitivity (Fig. 2) and signal-to-background ratios were observed to above 1500 °C. Contrary to conventional guidance on selecting phosphors for high temperature sensing, the detected emission band intensities and decay times exhibited remarkably slow decreases with temperature up into the 1300 to 1500 °C range despite high phonon energies (>900 cm-1) that allow the energy gap between the 4S3/2 emitting reservoir level and the 4F9/2 level below it to be bridged by as few as three phonons. The benefits of utilizing a thermographic phosphor at very high temperatures that exhibits strong nonradiative multiphonon relaxation even at room temperature is explained by a competition between spontaneous and stimulated multiphonon emission, and the more temperature-sensitive decay time above 1300 °C is explained by a transition from high to low effective phonon energies.
Ni and Co variations in primary martian magmas exhibit anomalous incompatible behavior, which has remained an unexplained conundrum. Because martian magmas are S-rich, and some trace metals are reported to have enhanced solubility in S-bearing magmas, we have carried out a series of experiments to evaluate the effect of high-S melts on the olivine/melt partitioning of Ni, Co, Mn, V, and Cr. Near-liquidus experiments on a synthetic primary martian mantle melt (Yamato-980459 [Y98]) were completed in a piston-cylinder apparatus at 0.75 GPa. Previous studies in S-free systems illustrate that the partition coefficients for these elements are dependent chiefly on D(Mg(Ol/melt)) (the partition coefficient defined as wt% Mg in olivine/wt% Mg in melt, a proxy for temperature), and were used to calibrate a predictive expression that includes the effects of temperature [i.e., D(Mg(Ol/melt))], melt composition, and oxygen fugacity. These predictive expressions are then used to isolate any effect in DM olivine/melt due to dissolved sulfur. The results show that S might have a small effect for Co, but not enough to change Co partitioning from compatible to incompatible in our experiments. The addition of a sulfur term to the D(Co) predictive expressions shows that nearly 8000 ppm of sulfur would be required in the melt (at liquidus temperature of Y98) for D(Co) to become <1. These S contents are two times higher than those of a sulfide-saturated melt at the P-T conditions of a martian mantle source region. Therefore, the anomalous incompatible behavior observed in these primary magma suites must be due to another mechanism. High temperature, oxygen fugacity, and diffusion are not viable mechanisms, but magma mixing, assimilation, or kinetic crystallization effects remain possibilities.
Process is accomplished by reducing tungsten hexafluoride with hydrogen. Metallic tungsten of essentially 100 percent purity and density is produced and built up as dense deposit on heated mandrel assembly. Process variations are building up, sealing or bonding refractory metals at temperatures below transition temperatures of base metal substrates.
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The electrical, magnetic, and optical properties of charge-transfer salts containing tetrathiafulvalene (TTF) and the pseudohalides, thiocyanate (SCN) and selenocyanate (SeCN), have been investigated. These salts are quasi-one-dimensional compounds containing cation radicals only, in contrast to a cation-radical-anion-radical system, such as tetrathiafulvalene tetracyanoquinodimethane (TTF) (TCNQ). Measurements of electrical conductivity, thermoelectric power, and optical reflectivity of single crystals of the nonstoichiometric salts (TTF)12(SCN)7 and (TTF)12(SeCN)7 show metal-like characteristics above 200 K (high-temperature region). The conductivities at room temperature are approximately 750 mho/cm comparable to those found in (TTF) (TCNQ), and increase with decreasing temperature down to approximately 200 K. The thermoelectric power at room temperature is small and positive (approximately 9 microvolts/deg K), and decreases linearly with decreasing temperature in this region (as expected for metal-like hole conduction along the TTF chains). The ESR intensity, however, decreases with decreasing temperature above 200 K. At 170 K a metal-nonmetal transition occurs, and the transport and magnetic properties below this temperature are characteristic of a semiconducting state.