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New experimental spinel/melt partition coefficients for Ni and Co have been measured in basalt samples with natural levels of Ni and Co, are lower than previous high doping experiments, and are applied to several planetary basalt suites. Additional information is contained in the original extended abstract.
It has become increasingly clear over the past decade that high temperature processes played important roles in the Primitive Solar Nebula. Unfortunately, basic data, such as the vapor pressures of Fe, Ni, Co or SiO have not been measured over the appropriate temperature range (near T approx. 2000K), but must be extrapolated from lower temperature measurements often made more than 50 years ago. The extrapolation of the available data to higher temperatures can be quite complex (e.g., see [1] for SiO vapor pressures) and can depend on other factors such as the oxygen fugacity or the presence of hydrogen gas not accounted for in the original measurements. Moreover, modern technology has made possible more accurate measurements of such quantities over a wider temperature range. We have acquired a commercial Thermo-Cahn Thermogravimetric system capable of vacuum operation to 1700C and measurement of a 10g change in sample mass using up to a 100g sample, with microgram accuracy. With this new system we have initiated a series of basic vapor pressure measurements on simple metals such as Fe[2] and Ni[3] with the intention to extend such measurements to more complex systems once we gain sufficient experience.
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During the reporting period June 23, 2011 to August 31, 2013, CAER researchers carried out research in two areas of fundamental importance to the topic of cobalt-based Fischer-Tropsch Synthesis (FTS): promoters and stability. The first area was research into possible substitute promoters that might be used to replace the expensive promoters (e.g., Pt, Re, and Ru) that are commonly used. To that end, three separate investigations were carried out. Due to the strong support interaction of γ-Al2O3 with cobalt, metal promoters are commonly added to commercial FTS catalysts to facilitate the reduction of cobalt oxides and thereby boost active surface cobalt metal sites. To date, the metal promoters examined have been those up to and including Group 11. Because two Group 11 promoters (i.e., Ag and Au) were identified to exhibit positive impacts on conversion, selectivity, or both, research was undertaken to explore metals in Groups 12 - 14. The three metals selected for this purpose were Cd, In, and Sn. At a higher loading of 25%Co on alumina, 1% addition of Cd, In, or Sn was found to-on average-facilitate reduction by promoting a heterogeneous distribution of cobalt consisting of larger lesser interacting cobalt clusters and smaller strongly interacting cobalt species. The lesser interacting species were identified in TPR profiles, where a sharp low temperature peak occurred for the reduction of larger, weakly interacting, CoO species. In XANES, the Cd, In, and Sn promoters were found to exist as oxides, whereas typical promoters (e.g., Re, Ru, Pt) were previously determined to exist in an metallic state in atomic coordination with cobalt. The larger cobalt clusters significantly decreased the active site density relative to the unpromoted 25%Co/Al2O3 catalyst. Decreasing the cobalt loading to 15%Co eliminated the large non-interacting species. The TPR peak for reduction of strongly interacting CoO in the Cd promoted catalyst occurred at a measurably lower temperature than in the unpromoted catalyst. Nevertheless, the Co clusters remained slightly larger, on average, in comparison with the unpromoted 15%Co/Al2O3 reference catalyst. None of the promoted catalysts (i.e., with Cd, In, or Sn) exhibited surface Co0 site densities higher than that of the unpromoted catalyst. In activity testing, the activities were even much lower than what was expected from the H2-TPD results. Two possible explanations were proposed: (1) the promoters may be located on the surfaces of cobalt particles, blocking surface Co0 but being able to desorb hydrogen or (2) the promoters may facilitate Co oxidation during FTS, as previously observed by Huffman and coworkers when K was added to cobalt catalysts.
A method of manufacturing nickel electrodes distinctive for its use of a composite material for the electrode made up of nickel compound, electrode material, cobalt in metal form or cobalt in compound form is investigated. The composite is over-discharged (same as reverse charging) in an alkaline solution. After dealkalization, synthetic resin adhesive is added and the electrode is formed. Selection of the cobalt compound is made from a group consisting of cobalt oxide, cobalt hydroxide, cobalt carbonate and cobalt sulfate. The method upgrades plate characteristics by using an active material in a non-sintered type nickel electrode, which is activated by electro-chemical effect.
A nickel electrode having improved charging efficiency, an increased coefficient of discharging utilization, and large capacity is disclosed. Nickel hydroxide or nickel oxide is retained in a porous nickel substrate which is immersed in an aqueous solution of cobalt acetate with a pH 4.0 to 6.8. The electrode thus obtained is then immersed in an alkaline solution or heated to change cobalt acetate into cobalt hydroxide or cobalt oxide whereby the surface of nickel active material is covered with cobalt crystals and alloying of cobalt and nickel is promoted at the same time.
As the oil supply declines, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to non-petroleum sources as a feedstock for aviation (and other transportation) fuels. The Fischer-Tropsch process uses a gas mixture of carbon monoxide and hydrogen which is converted into various liquid hydrocarbons; this versatile gas-to-liquid technology produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fischer-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur and aromatic compounds. It is most commonly catalyzed by cobalt supported on alumina, silica, or titania or unsupported alloyed iron powders. Cobalt is typically used more often than iron, in that cobalt is a longer-active catalyst, has lower water-gas shift activity, and lower yield of modified products. Promoters are valuable in improving Fischer-Tropsch catalyst as they can increase cobalt oxide dispersion, enhance the reduction of cobalt oxide to the active metal phase, stabilize a high metal surface area, and improve mechanical properties. Our goal is to build up the specificity of the Fischer-Tropsch catalyst while adding less-costly transition metals as promoters; the more common promoters used in Fischer-Tropsch synthesis are rhenium, platinum, and ruthenium. In this report we will describe our preliminary efforts to design and produce catalyst materials to achieve our goal of preferentially producing C8 to C18 paraffin compounds in the NASA Glenn Research Center Gas-To-Liquid processing plant. Efforts at NASA Glenn Research Center for producing green fuels using non-petroleum feedstocks support both the Sub-sonic Fixed Wing program of Fundamental Aeronautics and the In Situ Resource Utilization program of the Exploration Technology Development and Demonstration program.
As the oil supply declines, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to nonpetroleum sources as a feedstock for aviation (and other transportation) fuels. The Fischer-Tropsch process uses a gas mixture of carbon monoxide and hydrogen which is converted into various liquid hydrocarbons; this versatile gas-to-liquid technology produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fischer-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur and aromatic compounds. It is most commonly catalyzed by cobalt supported on alumina, silica, or titania or unsupported alloyed iron powders. Cobalt is typically used more often than iron, in that cobalt is a longer-active catalyst, has lower water-gas shift activity, and lower yield of modified products. Promoters are valuable in improving Fischer-Tropsch catalyst as they can increase cobalt oxide dispersion, enhance the reduction of cobalt oxide to the active metal phase, stabilize a high metal surface area, and improve mechanical properties. Our goal is to build up the specificity of the Fischer-Tropsch catalyst while adding less-costly transition metals as promoters; the more common promoters used in Fischer-Tropsch synthesis are rhenium, platinum, and ruthenium. In this report we will describe our preliminary efforts to design and produce catalyst materials to achieve our goal of preferentially producing C8 to C18 paraffin compounds in the NASA Glenn Research Center Gas-To-Liquid processing plant. Efforts at NASA Glenn Research Center for producing green fuels using non-petroleum feedstocks support both the Sub-sonic Fixed Wing program of Fundamental Aeronautics and the In Situ Resource Utilization program of the Exploration Technology Development and Demonstration program.
A new approach to the isolation of RNA from bacterial lysates employs selective precipitation by compaction agents, such as hexammine cobalt and spermidine. Using 3.5 mM hexammine cobalt, total RNA can be selectively precipitated from a cell lysate. At a concentration of 2 mM hexammine cobalt, rRNA can be fractionated from low molecular weight RNA. The resulting RNA mixture is readily resolved to pure 5S and mixed 16S/23S rRNA by nondenaturing anion-exchange chromatography. Using a second stage of precipitation at 8 mM hexammine cobalt, the low molecular weight RNA fraction can be isolated by precipitation. Compaction precipitation was also applied to the purification of an artificial stable RNA derived from Escherichia coli 5S rRNA and to the isolation of an Escherichia coli-expressed ribozyme. Copyright 2001 Academic Press.
Electrodeposition was studied at one-hundreth g and compared with bench studies at 1 g. The low gravity was achieved during KC-135 aircraft parobolic flights. Flow in a simple cobalt cell (1 M CoSO4) operating under typical commercial conditions (10 to 20 mA/sq cm and 1 V) was monitored with a Schlieren optical system. Natural convection was absent at one-hundreth g. Quantitative comparisons on a cobalt cell with shielded electrodes using interferometry were carried out. Fringe shift differences indicate greater semi-infinite linear diffusion at 1 g than at one-hundreth g for cobalt. Since a shielded electrode operates under diffusion controlled conditions, no differences between 1 g and one-hundreth g would be expected. Similar comparisons on a shielded electrode copper cell were inconclusive. Bench codeposition experiments using polystyrene neutral buoyancy particles coupled with a shielded electrode cobalt cell were begun. Tracking of 12 micron particles showed no measurable difference between thermal/Brownian motion when the cell was operational or nonoperational. Initial experiments on codeposition quality showed a strong dependence upon cathode surface preparation in a shielded electrode configuration.
The properties of modified NIMONIC 115 and UDIMET 720 with reduced levels of cobalt were evaluated. Vacuum induction melted and vacuum arc remelted ingots were hot rolled to 3/4 inch diameter bar. Hot workability was evaluated in terms of the ingot rolling behavior and the hot ductility of the as-rolled bar. Variations in workability and bar ductility were correlated to variations in incipient melting temperature and gamma prime solvus, both of which varied with cobalt content. Heat treatments were defined to yield, as far as possible, similar structures from alloy to alloy. At the lowest cobalt levels N-115 workability was severely limited and the alloys could not be worked to bar. It is suggested that incipient melting in combination with heavy grain boundary carbide precipitation reduced ingot workability. Final heat treatment of modified alloys was difficult in the situation where the gamma prime solvus temperature was close to the incipient melting point, indicating that it may not be feasible to fully solution low cobalt alloys to obtain the large grain size required for optimum creep resistance.
The heater head tubes of current prototype automotive Stirling engines are fabricated from alloy N-155, an alloy which contains 20 percent cobalt. Because the United States imports over 90 percent of the cobalt used in this country and resource supplies could not meet the demand imposed by automotive applications of cobalt in the heater head (tubes plus cylinders and regenerator housings), it is imperative that substitute alloys free of cobalt be identified. The research described herein focused on the heater head tubes. Sixteen alloys (15 potential substitutes plus the 20 percent Co N-155 alloy) were evaluated in the form of thin wall tubing in the NASA Lewis Research Center Stirling simulator materials diesel fuel fired test rigs. Tubes filled with either hydrogen doped with 1 percent CO2 or with helium at a gas pressure of 15 MPa and a temperature of 820 C were cyclic endurance tested for times up to 3500 hr. Results showed that two iron-nickel base superalloys, CG-27 and Pyromet 901 survived the 3500 hr endurance test. The remaining alloys failed by creep-rupture at times less than 3000 hr, however, several other alloys had superior lives to N-155. Results further showed that doping the hydrogen working fluid with 1 vol % CO2 is an effective means of reducing hydrogen permeability through all the alloy tubes investigated.
A large capacity nickel electrode is provided in which the charging efficiency and discharge utilization coefficient are improved in comparison to nickel electrodes which are produced by the conventional method. Nickel electrodes retaining nickel active material or nickel active material and cobalt compounds on a porous nickel substrate are immersed in a cobalt sulfate aqueous solution whose pH is adjusted in the range of 3.5 to 6.0, followed by crystallization of the hydroxide or oxide by pyrolysis or immersion in alkali, thereby coating the surface of the nickel active material with cobalt crystals and simultaneously promoting alloying of the nickel-cobalt.
A cobalt-free nickel-base superalloy composed of in weight % 15 Cr-5 Mo-3.5 Ti-4 Al-0.07 (max) C-remainder Ni is given a modified heat treatment. With this heat treatment the cobalt-free alloy achieves certain of the mechanical properties of the corresponding cobalt-containing nickel-base superalloy at 1200 F (650 C). Thus, strategic cobalt can be replaced by nickel in the alloy.
The sintering behavior of a mixture of hafnium carbide and 10 weight percent cobalt powders is presented. Compacts were heated in a vacuum at elevates temperatures for densification and removal of the cobalt. Densities of 99 percent of theoretical for the hafnium carbide were achieved with a maximum sintering temperature of 2200' C. Retained cobalt, grain size, microhardness, and weight loss were determined.
Metallic transfer between polycrystalline metals in sliding contact was examined. Hemispherical riders of iron, nickel, and cobalt were slid on tungsten, tantalum, niobium, and molybdenum disks in ultrahigh vacuum. Auger emission spectroscopy was used to monitor the elemental composition of the disk surfaces. Iron, nickel, and cobalt transferred to tungsten, whereas only cobalt transferred to tantalum, niobium, and molybdenum. The results of this investigation are discussed in terms of the cohesive energy and strain hardening characteristics of the specimen materials.