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Effects of cobalt in nickel-base superalloys

The role of cobalt in a representative wrought nickel-base superalloy was determined. The results show cobalt affecting the solubility of elements in the gamma matrix, resulting in enhanced gamma' volume fraction, in the stabilization of MC-type carbides, and in the stabilization of sigma phase. In the particular alloy studied, these microstructural and microchemistry changes are insufficient in extent to impact on tensile strength, yield strength, and in the ductilities. Depending on the heat treatment, creep and stress rupture resistance can be cobalt sensitive. In the coarse grain, fully solutioned and aged condition, all of the alloy's 17% cobalt can be replaced by nickel without deleteriously affecting this resistance. In the fine grain, partially solutioned and aged condition, this resistance is deleteriously affected only when one-half or more of the initial cobalt content is removed. The structure and property results are discussed with respect to existing theories and with respect to other recent and earlier findings on the impact of cobalt, if any, on the performance of nickel-base superalloys.

Tien, J. K.

Effects of long-time elevated temperature exposures on hot-isostatically-pressed power-metallurgy Udimet 700 alloys with reduced cobalt contents

Because almost the entire U.S. consumption of cobalt depends on imports, this metal has been designated "strategic'. The role and effectiveness of cobalt is being evaluated in commercial nickel-base superalloys. Udiment 700 type alloys in which the cobalt content was reduced from the normal 17% down to 12.7%, 8.5%, 4.3%, and 0% were prepared by standard powder metallurgy techniques and hot isostatically pressed into billets. Mechanical testing and microstructural investigations were performed. The mechanical properties of alloys with reduced cobalt contents which were heat-treated identically were equal or better than those of the standard alloy, except that creep rates tended to increase as cobalt was reduced. The effects of long time exposures at 760 C on mechanical properties and at 760 C and 845 C on microstructures were determined. Decreased tensile properties and shorter rupture lives with increased creep rates were observed in alloy modifications. The exposures caused gamma prime particle coarsening and formation of sigma phase in the alloys with higher cobalt contents. Exposure at 845 C also reduced the amount of MC carbides.

Hart, F. H.

Cobalt ferrite based magnetostrictive materials for magnetic stress sensor and actuator applications

Magnetostrictive material based on cobalt ferrite is described. The cobalt ferrite is substituted with transition metals (such manganese (Mn), chromium (Cr), zinc (Zn) and copper (Cu) or mixtures thereof) by substituting the transition metals for iron or cobalt to form substituted cobalt ferrite that provides mechanical properties that make the substituted cobalt ferrite material effective for use as sensors and actuators. The substitution of transition metals lowers the Curie temperature of the material (as compared to cobalt ferrite) while maintaining a suitable magnetostriction for stress sensing applications.

Jiles, David C.

Open-Loop Flight Testing of COBALT GN&C Technologies for Precise Soft Landing

A terrestrial, open-loop (OL) flight test campaign of the NASA COBALT (CoOperative Blending of Autonomous Landing Technologies) platform was conducted onboard the Masten Xodiac suborbital rocket testbed, with support through the NASA Advanced Exploration Systems (AES), Game Changing Development (GCD), and Flight Opportunities (FO) Programs. The COBALT platform integrates NASA Guidance, Navigation and Control (GN&C) sensing technologies for autonomous, precise soft landing, including the Navigation Doppler Lidar (NDL) velocity and range sensor and the Lander Vision System (LVS) Terrain Relative Navigation (TRN) system. A specialized navigation filter running onboard COBALT fuzes the NDL and LVS data in real time to produce a precise navigation solution that is independent of the Global Positioning System (GPS) and suitable for future, autonomous planetary landing systems. The OL campaign tested COBALT as a passive payload, with COBALT data collection and filter execution, but with the Xodiac vehicle Guidance and Control (G&C) loops closed on a Masten GPS-based navigation solution. The OL test was performed as a risk reduction activity in preparation for an upcoming 2017 closed-loop (CL) flight campaign in which Xodiac G&C will act on the COBALT navigation solution and the GPS-based navigation will serve only as a backup monitor.

Carson, John M., III

Fischer-Tropsch Cobalt Catalyst Activation and Handling Through Wax Enclosure Methods

Fischer-Tropsch (F-T) synthesis is considered a gas to liquid process which converts syn-gas, a gaseous mixture of hydrogen and carbon monoxide, into liquids of various hydrocarbon chain length and product distributions. Cobalt based catalysts are used in F-T synthesis and are the focus of this paper. One key concern with handling cobalt based catalysts is that the active form of catalyst is in a reduced state, metallic cobalt, which oxidizes readily in air. In laboratory experiments, the precursor cobalt oxide catalyst is activated in a fixed bed at 350 C then transferred into a continuous stirred tank reactor (CSTR) with inert gas. NASA has developed a process which involves the enclosure of active cobalt catalyst in a wax mold to prevent oxidation during storage and handling. This improved method allows for precise catalyst loading and delivery into a CSTR. Preliminary results indicate similar activity levels in the F-T reaction in comparison to the direct injection method. The work in this paper was supported by the NASA Fundamental Aeronautics Subsonics Fixed Wing Project.

Fischer-Tropsch

Cold Spray Cobalt Magnetostrictive Electromagnetic Acoustic Transducers for High Temperature Structure Monitoring

The Department of Energy’s Advanced Sensors and Instrumentation program seeks to develop and qualify advanced sensors for the nuclear industry. Reliable high temperature and high radiation sensors for detection and characterization of structural flaws in pipes, vessels, and structurally critical components is a weakness for both conventional light water reactors with coolant T-hot approaching 350oC, and for advanced reactors with T-hot temperatures in excess of 500 to 800oC. Magnetostrictive Electromagnetic Acoustic Transducers using a cold spray cobalt coating have been proposed as a sensor design that can withstand these kinds of temperatures and radiation levels to serve as online sensors to detect flaws before cracks, pits, or erosion/corrosion flaws progress to through-wall failures. This report tests cold spray cobalt as part of a magnetostrictive EMAT for high temperature service. Cobalt is known to have strong magnetostrictive properties however the effect of cold spray application is not well studied. This program was surprised to discover that cold sprayed cobalt exhibited little or no magnetostrictive behavior until it was thermally annealed. Following annealing to 650oC however, cold spray cobalt did exhibit a magnetostrictive response. Work to date prior to this milestone report publication showed that magnetostrictive EMAT was successfully tested to 400oC with an alnico permanent magnet. The program plans to extend testing with an electromagnet to higher temperatures. This follow-on work will be reported under subsequent publications or as a revision to this report.

Glass, Samuel W.

Friction and wear of plasma-sprayed coatings containing cobalt alloys from 25 deg to 650 deg in air

Four different compositions of self-lubricating, plasma-sprayed, composite coatings with calcium fluoride dispersed throughout cobalt alloy-silver matrices were evaluated on a friction and wear apparatus. In addition, coatings of the cobalt alloys alone and one coating with a nickel alloy-silver matrix were evaluated for comparison. The wear specimens consisted of two, diametrically opposed, flat rub shoes sliding on the coated, cylindrical surface of a rotating disk. Two of the cobalt composite coatings gave a friction coefficient of about 0.25 and low wear at room temperature, 400 and 650 C. Wear rates were lower than those of the cobalt alloys alone or the nickel alloy composite coating. However, oxidation limited the maximum useful temperature of the cobalt composite coating to about 650 C compared to about 900 C for the nickel composite coating.

Sliney, H. E.

Friction and wear of plasma-sprayed coatings containing cobalt alloys from 25 deg to 650 deg in air

Four different compositions of self-lubricating, plasma-sprayed, composite coatings with calcium fluoride dispersed throughout cobalt alloy-silver matrices were evaluated on a friction and wear apparatus. In addition, coatings of the cobalt alloys alone and of one coating with a nickel alloy-silver matrix were evaluated for comparison. The wear specimens consisted of two, diametrically opposed, flat rub shoes sliding on the coated, cylindrical surface of a rotating disk. Two of the cobalt composite coatings gave a friction coefficient of about 0.25 and low wear at room temperature, 400 and 650 C. Wear rates were lower than those of the cobalt alloys alone or the nickel alloy composite coating. However, oxidation limited the maximum useful temperature of the cobalt composite coating to about 650 C compared to about 900 C for the nickel composite coating.

Sliney, H. E.

Effects of cobalt on the microstructure of Udimet 700

Cobalt, a critical and "strategic" alloying element in many superalloys, was systematically substituted by nickel in experimental alloys Udimet 700 containing 0.1, 4.3, 8.6, 12.8 and the standard 17.0 wt.% cobalt. Electrolytic and chemical extraction techniques, X-ray diffraction, scanning electron and optical microscopy were used for the microstructural studies. The total weight fraction of gamma' was not significantly affected by the cobalt content, although a difference in the size and quantities of the primary and secondary gamma' phases was apparent. The lattice parameters of the gamma' were found to increase with increasing cobalt content while the lattice mismatch between the gamma matrix and gamma' phases decreased. Other significant effects of cobalt on the weight fraction, distribution and formation of the carbide and boride phases as well as the relative stability of the experimental alloys during long-time aging are also discussed.

Engel, M. A.

Creep fatigue of low-cobalt superalloys: Waspalloy, PM U 700 and wrought U 700

The influence of cobalt content on the high temperature creep fatigue crack initiation resistance of three primary alloys was evaluated. These were Waspalloy, Powder U 700, and Cast U 700, with cobalt contents ranging from 0 up to 17 percent. Waspalloy was studied at 538 C whereas the U 700 was studied at 760 C. Constraints of the program required investigation at a single strain range using diametral strain control. The approach was phenomenological, using standard low cycle fatigue tests involving continuous cycling tension hold cycling, compression hold cycling, and symmetric hold cycling. Cycling in the absence of or between holds was done at 0.5 Hz, whereas holds when introduced lasted 1 minute. The plan was to allocate two specimens to the continuous cycling, and one specimen to each of the hold time conditions. Data was taken to document the nature of the cracking process, the deformation response, and the resistance to cyclic loading to the formation of small cracks and to specimen separation. The influence of cobalt content on creep fatigue resistance was not judged to be very significant based on the results generated. Specific conclusions were that the hold time history dependence of the resistance is as significant as the influence of cobalt content and increased cobalt content does not produce increased creep fatigue resistance on a one to one basis.

Leis, B. N.

The substitution of nickel for cobalt in hot isostatically pressed powder metallurgy UDIMET 700 alloys

Nickel was substituted in various proportions for cobalt in a series of five hot-isostatically-pressed powder metallurgy alloys based on the UDIMET 700 composition. These alloys were given 5-step heat treatments appropriate for use in turbine engine disks. The resultant microstructures displayed three distinct sizes of gamma-prime particles in a gamma matrix. The higher cobalt-content alloys contained larger amounts of the finest gamma-prime particles, and had the lowest gamma-gamma-prime lattice mismatch. While all alloys had approximately the same tensile properties at 25 and 650 gamma C, the rupture lives at 650 and 760 C peaked in the alloys with cobalt contents between 12.7 and 4.3 pct. Minimum creep rates increased as cobalt contents were lowered, suggesting their correlation with the gamma-prime particle size distribution and the gamma-gamma-prime mismatch. It was also found that, on overaging at temperatures higher than suitable for turbine disk use, the high cobalt-content alloys were prone to sigma phase formation.

Harf, F. H.

Porous cobalt spheres for high temperature gradient magnetically assisted fluidized beds

Porous metallic cobalt spheres have been prepared as high temperature capable media for employment in gradient magnetically assisted fluidization and filtration technologies. Cobalt impregnated alginate beads are first formed by extrusion of an aqueous suspension of Co3O4 into a Co(II) chloride solution. The organic polymer is thermally decomposed yielding cobalt oxide spheres, followed by reduction to the metallic state, and densification. Cobalt beads have been produced with porosities ranging between 10 and 50%, depending upon sintering conditions. The product media have been characterized by scanning electron microscopy (SEM), nitrogen adsorption porosimetry, and vibrating sample magnetometry. c2003 Elsevier Science Ltd. All rights reserved.

NASA Discipline Life Support Systems

Understanding the Origin of Negative Temperature Dependence and Activity of N-Coordinated Cobalt Sites During Ethylene Dimerization

The on-demand production of short-chain linear alpha olefins (LAOs; C4-C8) via C2H4 dimerization and oligomerization is industrially attractive, prompting extensive research on designing active, selective, and stable catalysts for industrial use. Cobalt supported on ammoniated carbon (Co(NH3)x/C) catalysts have shown remarkable activity and selectivity in this process. However, critical aspects such as the active phase, active site structure, the role of the catalyst support, cobalt loading effects, and the inverse correlation of the reaction rate with temperature remain inadequately understood. This study systematically explores these factors using a combination of steady-state differential catalytic tests, in situ molecular characterization including diffuse reflectance UV-Vis (DR-UV-Vis), Infrared, and Raman spectroscopies, and ex situ X-ray diffraction (XRD) and high annular aberration-corrected dark field transmission electron microscopy (HAADF-STEM). Various supports (SiO2, Al2O3, NH4-ZSM-5, g-C3N4, and C) and cobalt loadings (1.0-3.0 Co nm-2) were studied to determine the optimal catalyst composition and identify the active phase and sites. Carbon-supported catalysts uniquely produce C4-8 LAOs during C2H4 dimerization, with site-time-yield remaining constant (~10-3 s-1) for 1.0-4.0 Co nm-2 at prolonged reaction times (24-48?h time-on-stream). At higher loadings of 6.0 Co nm-2, the formation of crystalline CoO and Co3O4 phases reduces catalytic activity and LAO selectivity. Our findings show that active catalysts lack crystalline cobalt oxides and instead feature dispersed Co2+ sites, tetra-coordinated to a mix of N/NH3 and O/H2O ligands, which catalyze C2H4 dimerization via the Cossee-Arlman mechanism, exhibiting 1st order dependence on C2H4 concentration. The observed inverse rate-temperature correlation is attributed to compensation effects (i.e., presence of Cremer-Constable relationship) linked to changes in adsorption enthalpic and entropic factors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Decoupling the catalytic and degradation mechanisms of cobalt active sites during acidic water oxidation

Advancement of iridium-free catalysts for the low-pH oxygen evolution reaction (OER) is required to enable multi-gigawatt-scale proton-exchange water electrolysis. Cobalt-based materials might address this requirement, but little is known about the mechanism of operation of these OER catalysts at low pH. Here we investigate the nature and evolution of the active cobalt sites along with charge- and mass-transfer processes that support their catalytic function within a cobalt–iron–lead oxide material using in situ spectroscopic, gravimetric and electrochemical techniques. We demonstrate that corrosion of the cobalt sites and their reformation through electrooxidation of dissolved Co 2+ do not affect the catalytic mechanism and are decoupled from the OER. The OER-coupled charge transfer is supported by Co (3+δ)+ -oxo-species, which are structurally different from those reported for alkaline/near-neutral conditions and are formed on a relatively slow timescale of minutes. These mechanistic insights might assist in developing genuinely practical catalysts for this vital technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Influence of silicon on friction and wear of iron-cobalt alloys

Sliding friction and wear experiments were conducted with ternary ordered alloys of iron and cobalt containing various amounts of silicon to 5 weight percent. The friction and wear of these alloys were compared to those for binary iron-cobalt alloys in the ordered and disordered states and to those for the conventionally used bearing material, 440-C. Environments in which experiments were conducted included air, argon, and 0.25percent stearic acid in hexadecane. Results indicate that a ternary iron - cobalt - 5-percent-silicon alloy exhibits lower friction and wear than the simple binary iron-cobalt alloy. It exhibits lower wear than 440-C in all three environments. Friction was lower for the alloy in argon than in air. Auger analysis of the surface of the ternary alloy indicated segregation of silicon at the surface as a result of sliding.

Buckley, D. H.

Preliminary study of a solar selective coating system using black cobalt oxide for high temperature solar collectors

Black cobalt oxide coatings (high solar absorptance layer) were deposited on thin layers of silver or gold (low emittance layer) which had been previously deposited on oxidized (diffusion barrier layer) stainless steel substrates. The reflectance properties of these coatings were measured at various thicknesses of cobalt for integrated values of the solar and infrared spectrum. The values of absorptance and emittance were calculated from the measured reflectance values, before and after exposure in air at 650 C for approximately 1000 hours. Absorptance and emittance were interdependent functions of the weight of cobalt oxide. Also, these cobalt oxide/noble metal/oxide diffusion barrier coatings have absorptances greater than 0.90 and emittances of approximately 0.20 even after about 1000 hours at 650 C.

Mcdonald, G.

Reaction of cobalt in SO2 atmospheric at elevated temperatures

The reaction rate of cobalt in SO2 argon environments was measured at 650 C, 700 C, 750 C and 800 C. Product scales consist primarily of an interconnected sulfide phase in an oxide matrix. At 700 C to 800 C a thin sulfide layer adjacent to the metal is also observed. At all temperatures, the rapid diffusion of cobalt outward through the interconnected sulfide appears to be important. At 650 C, the reaction rate slows dramatically after five minutes due to a change in the distribution of these sulfides. At 700 C and 750 C the reaction is primarily diffusion controlled values of diffusivity of cobalt (CoS) calculated from this work show favorable agreement with values of diffusivity of cobalt (CoS) calculated from previous sulfidation work. At 800 C, a surface step becomes rate limiting.

Jacobson, N. S.

Effects of cobalt in nickel-base superalloys

A study has been carried out to assess the role of cobalt in Udimet 700, a representative nickel-base superalloy containing 17 percent or more cobalt. The study spans the spectrum of microstructural, microchemical, and mechanical behavior aspects which together form a basis for superalloy performance in jet engines. The results suggest that cobalt affects the solubility of elements in the gamma matrix, which leads to enhanced gamma-prime volume fraction and to the stabilization of MC-type carbides and sigma phase. However, these microstructural and microchemical changes are too slight to significantly affect the strength and ductile properties. Depending on the heat treatment, the creep and stress rupture resistance can be cobalt-sensitive. In the coarse-grained, fully solutioned and aged condition, all of the alloy's 17 percent Co can be replaced by nickel without decreasing the creep and stress rupture resistance. These findings are discussed with reference to existing theories and experimental data obtained by other workers.

Tien, J. K.