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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 505 records · Page 28

Discovery of van Hove singularities: electronic fingerprints of 3Q magnetic order in a van der Waals quantum magnet

Magnetically intercalated transition metal dichalcogenides are emerging as a rich platform for exploring exotic quantum states in van der Waals magnets. Among them, Co x TaS 2 has attracted intense interest following the recent discovery of a distinctive 3Q magnetic ground state and a pronounced topological Hall effect below a critical doping of x ≈ 1/3, both intimately tied to cobalt concentration. To date, direct signatures of this enigmatic 3Q magnetic order in the electronic structure remain elusive. Here we report a comprehensive doping dependent angle resolved photoemission spectroscopy study that unveils these long-sought fingerprints. Our data reveal an unexpected inverse-Mexican-hat dispersion along the K-M-K' direction, accompanied by two van Hove singularities. These features are consistent with theoretical predictions for a 3Q magnetic order near three-quarters band filling on a cobalt triangular lattice. These results provide evidence of 3Q magnetic order in the electronic structure, establishing TMD van der Waals magnets as tunable materials to explore the interplay between magnetism and topology.

Luo, Hai-Lan [University of California, Berkeley, ↗

Method for Manufacturing Thin-film Lithium Microbatteries

A process for making thin-film batteries including the steps of cleaning a glass or silicon substrate having an amorphous oxide layer several microns thick; defining with a mask the layer shape when depositing cobalt as an adhesion layer and platinum as a current collector; using the same mask as the preceding step to sputter a layer of LiCoO2 on the structure while rocking it back and forth; heating the substrate to 300 C. for 30 minutes; sputtering with a new mask that defines the necessary electrolyte area; evaporating lithium metal anodes using an appropriate shadow mask; and, packaging the cell in a dry-room environment by applying a continuous bead of epoxy around the active cell areas and resting a glass slide over the top thereof.

Jay F Whitacre↗

Composition dependence of bulk properties in the Co-intercalated transition metal dichalcogenide $\mathrm{Co_{1/3}TaS_2}$

Spontaneous Hall conductivity has recently been reported in the triangular lattice antiferromagnet Co 1/3 TaS 2 under a zero magnetic field. This phenomenon originates from the distinctive noncoplanar triple-Q magnetic ground state, possessing uniform real-space Berry curvature characterized by scalar spin chirality. We investigated the physical properties of Co 1/3 TaS 2 by judiciously controlling the composition, revealing a drastic change in its bulk properties, even by slight variations in cobalt composition, despite the same crystal structure. For 0.299≤x≤0.325, Co x TaS 2 keeps all the characteristics of the ground state consistent with the previous studies—two antiferromagnetic phase transitions at T N1 and T N2 ( N1 ), a large spontaneous Hall conductivity [σ xy (H=0)], and a weak ferromagnetic moment along the c axis. However, samples with x≥0.330 exhibit distinct bulk properties, including the absence of both σ xy (H=0) and the weak ferromagnetic moment. Our neutron diffraction data reveal that Co x TaS 2 with x≥0.330 develops coplanar helical magnetic order with q m1 =(1/3, 0, 0). This is entirely different from what has been seen in x≤0.325, explaining the observed composition dependence.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High temperature reactions of ceramics and metals with chlorine and oxygen

The reactions of chlorine and oxygen with solids are complex and quite dependent on material and reaction conditions. However, there are four reaction schemes that describe many of these reactions. These are direct reaction of chlorine with the oxide layer, penetration of the oxide layer by chlorine, paralinear behavior where oxidation and chlorination are of comparable rates, and finally, gas phase reactions where the volatile chlorides react with oxygen. Examples of chlorine and oxygen reactions with cobalt, nickel, chromium, molybdenum, and silicon carbide illustrate each of these four reaction schemes.

Jacobson, N. S.↗

Performance of a Haynes 188 metallic standoff thermal protection system at Mach 7

A flight weight, metallic thermal protection system (TPS) model applicable to reentry and hypersonic vehicles was subjected to multiple cycles of both radiant and aerothermal heating to evaluate its aerothermal performance and structural integrity. The TPS was designed for a maximum operating temperature of 1255 K and featured a shingled, corrugation stiffened corrugated skin heat shield of Haynes 188, a cobalt base alloy. The model was subjected to 3 radiant preheat/aerothermal tests for a total of 67 seconds and to 15 radiant heating tests for a total of 85.9 minutes at 1255 K. The TPS limited the primary structure to temperatures below 430 K in all tests. No catastrophic failures occurred in the heat shields, supports, or insulation system. The TPS continued to function even after exposure to a differential temperature 4 times the design value produced thermal buckles in the outer skin. The shingled thermal expansion joint effectively allowed for thermal expansion of the heat shield without allowing any appreciable hot gas flow into the model cavity, even though the overlap gap between shields increased after several thermal cycles.

Avery, D. E.↗

Structural analyses of engine wall cooling concepts and materials

The severe thermal environments under which hypersonic aircraft such as the National Aerospace Plane (NASP) will operate require cooling of the engine walls, especially in the combustor. A preliminary assessment is made of some candidate materials based on structural analyses for a number of convective cooling configurations. Three materials were studied: graphite/copper and tungsten/copper composite alloys with 50 percent fiber volume fractions and a wrought cobalt-base superalloy, Haynes 188. Anisotropic mechanical and thermal properties for the composites were obtained from a computer code, ICAN, which determines the composite material properties from the individual properties of the fiber and matrix materials. The structural analyses were performed by using the MARC nonlinear finite element code. Heat transfer analyses were conducted to calculate the metal temperature distributions.

Kaufman, Albert↗

Structurally Regenerable High Entropy Aluminate Spinel Catalysts for Dry Reforming of Methane

The dry reforming of methane reaction is a promising means to convert two potent greenhouse gases, methane and carbon dioxide, into industrially valuable synthesis gas. However, the presence of reducing gases and high operating temperatures degrade conventional nickel catalysts via excessive coke formation and particle sintering. These catalysts are not readily regenerated because the oxidative heat treatments employed to remove coke further promote active particle sintering. In this work, we designed high entropy aluminate spinel oxides (MAl 2 O 4 where M = Co, Mg, Ni, and divalent site vacancies in nominal equimolar concentration) as selective and regenerable reforming catalysts. Under reaction conditions, reducible nickel and cobalt cations exsolved from the spinel lattice to form highly selective bimetallic particles on the oxide surface. Instead of sintering, these particles uniquely redissolved back into the aluminate lattice upon reoxidation and regained the original spinel structure. This phenomenon is ascribed to entropic stabilization, wherein an increase in configurational entropy creates a thermodynamic driving force for redispersing supported metal particles back into the multi‐cationic oxide structure. During the dry reforming reaction, nickel atoms similarly exsolved from a NiAl 2 O 4 sample and reduced to form metallic nickel particles. However, subsequent oxidation of this sample promoted sintering and oxidation of the nickel particles to an inactive state. High entropy materials thus provide a unique mechanism of regeneration, which is inaccessible in conventional catalysts.

coke deposition↗

Engineering surface segregation of perovskite oxide through wet exsolution for CO catalytic oxidation

Cation segregation occurring near the surface or interfaces of solid catalysts plays an important role in catalytic reactions. Unfortunately, the native surface of perovskite oxides is dominated by passivated A-site segregation, which severely hampers the catalytic activity and durability of the system. To address this issue, we present a wet exsolution method to reconstruct surface segregation in perovskite cobalt oxide. Here, under reduction etching treatment of glycol solution, inert surface Sr segregation was transformed into active Co 3 O 4 segregation. By varying the reaction time, we achieved differing coverage of the active Co 3 O 4 segregation on the La 0.5 Sr 0.5 CoO 3-δ (LSCO) perovskite oxide surface. This study reveals that CO oxidation activity exhibits a volcano-shaped dependence on the coverage of Co 3 O 4 segregation at the surface of a perovskite cobalt oxide. Furthermore, we find that a suitable coverage of Co 3 O 4 segregation can dramatically improve the catalytic activity of the perovskite catalyst by enhancing interface interactions. Co K-edge, Co L-edge, and O K-edge X-ray absorption spectra confirm that the synergistic effect optimizes the covalence of the metal-oxygen bond at the surface and interface. This work not only contributes to the design of perovskite-type catalysts, but also provides important insight into the relationship between surface segregation and catalytic activity.

36 MATERIALS SCIENCE↗

Structure of Thin-Film Lithium Microbatteries

A process for making thin-film batteries including the steps of cleaning a glass or silicon substrate having an amorphous oxide layer several microns thick; defining with a mask the layer shape when depositing cobalt as an adhesion layer and platinum as a current collector; using the same mask as the preceding step to sputter a layer of LiC(0)O2, on the structure while rocking it back and forth; heating the substrate to 300 C. for 30 minutes; sputtering with a new mask that defines the necessary electrolyte area; evaporating lithium metal anodes using an appropriate shadow mask; and, packaging the cell in a dry-room environment by applying a continuous bead of epoxy around the active cell areas and resting a glass slide over the top thereof. The batteries produced by the above process are disclosed.

Jay F Whitacre↗

In–Depth Analysis of the Degradation Mechanisms of High–Nickel, Low/No–Cobalt Layered Oxide Cathodes for Lithium–Ion Batteries

A rational compositional design of high-nickel, cobalt-free layered oxide materials for high-energy and low-cost lithium-ion batteries would be expected to further propel the widespread adoption of electric vehicles (EVs), yet a composition with satisfactory electrochemical properties has yet to emerge. The previous work has demonstrated a promising LiNi 0.883 Mn 0.056 Al 0.061 O 2 (NMA-89) composition that outperformed high-nickel, cobalt-containing analogs in cycling stability and maintained a comparable rate performance and thermal stability. Herein, the capacity fading mechanism of NMA-89 in a pouch full cell with a 4.2 V cutoff is compared to that of its cobalt-containing analogs. The results reveal that particle cracking in LiNi 0.89 Mn 0.055 Co 0.055 O 2 (NMC-89) and LiNi 0.883 Co 0.053 Al 0.064 O 2 (NCA-89) leads to a loss of active material and an increase in surface area, thereby exacerbating structural and surface instabilities, accelerating impedance and polarization growth, and ultimately reducing their capacity retentions. LiNi 0.89 Mn 0.044 Co 0.042 Al 0.013 Mg 0.011 O 2 (NMCAM-89) and NMA-89 experience subdued surface reactions and maintain spherical particle structures, both of which are conducive to their capacity retentions during long-term cycling. Furthermore, this investigation offers insights into how specific transition-metal ions dictate the electrochemical stability of high-Ni layered oxide cathode materials, highlights the benefit of Mn-Al combination in NMA-89, and presents potential strategies to further enhance the performance of this novel class of cathode materials.

degradation mechanisms↗

Work function determination of promising electrode materials for thermionic energy converters

The work function determinations of candidate materials for low temperature (1400 K) thermionics through vacuum emission tests are discussed. Two systems, a vacuum emission test vehicle and a thermionic emission microscope are used for emission measurements. Some nickel and cobalt based super alloys were preliminarily examined. High temperature physical properties and corrosion behavior of some super alloy candidates are presented. The corrosion behavior of sodium is of particular interest since topping cycles might use sodium heat transfer loops. A Marchuk tube was designed for plasma discharge studies with the carbide and possibly some super alloy samples. A series of metal carbides and other alloys were fabricated and tested in a special high temperature mass spectrometer. This information coupled with work function determinations was evaluated in an attempt to learn how electron bonding occurs in transition alloys.

Jacobson, D.↗

An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron

The goal was to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. Although hydrogen degradation of metallic materials is believed to result from dissolved protonic hydrogen, the heterogeneous hydrogen interface transport processes often dominate the kinetics of the degradation process. The initial step in the interface transport process is the dissociative chemisorption of the molecular species at the metal surface followed by hydrogen absorption into and transport through the bulk. Modern advanced aerospace applications often require the use of structural materials in high pressure hydrogen environments at temperatures which range from low cryogenic temperatures to very high temperatures (1300 K and greater). Materials proposed for these applications, such as the titanium aluminides, beta-titanium alloys, nickel- and cobalt-based superalloys, molybdenum-rhenium alloys, beryllium, and various beryllides, need to possess a high degree of immunity from hydrogen induced degradation of mechanical properties. In the present program, the interaction of hydrogen with the surfaces of alpha-2 (Ti3Al) titanium aluminide, gamma (TiAl) titanium aluminide, and beryllium were studied. The interaction of low pressure hydrogen with gamma titanium aluminide and beryllium was found to be relatively weak, in the sense that adsorption leads to a low surface concentration of dissociated hydrogen, i.e., the chemisorption process is reversible at room temperature (300 K) for gamma titanium aluminide and the sticking coefficient for chemisorption is extremely small for beryllium. Hydrogen was found to interact readily with alpha-2 titanium aluminide to form a stable surface hydride at 300 K. These results correlate well with other recent studies which show that the mechanical properties for alpha-2 titanium aluminide are readily degraded in hydrogen while gamma titanium aluminide exhibits less degradation and beryllium essentially no degradation. The interaction of oxygen with the surface of these materials has been studied, also, in the present program.

Shanabarger, Mickey R.↗

Lead tolerance and bioremoval by four strains of green algae from Nigerian fish ponds

Heavy metals from industry pose threats to human and environmental health. Microalgae are prime candidates to remove heavy metals from water and soil due to their metal-binding affinities, high growth rates, and contamination tolerance. Strain selection and composition of resulting contaminated biomass must be considered for downstream processing. In this study, we assessed the ability of four microalgae strains (Chlorophyceae) that were isolated from contaminated Nigerian fish ponds to take up dissolved lead at environmentally relevant concentrations (<0.05 mg L -1 – WHO standard). In a microplate assay, all strains grew in the presence of lead, tolerating concentrations up to 60 ppm, though the addition of dissolved lead affected the growth of the four strains. In a photobioreactor assay, all strains demonstrated the ability to take up dissolved lead, with removal efficiencies ranging from 86 to 93%. The concentrations of lead in contaminated biomass, removal efficiencies, and bioconcentration factors were greatest in one of the isolates Chlorella sp. MOW 12. Our results reinforce the fact that live microalgae have a greater biosorption capacity. Lead recovery from freeze-dried biomass using five different reagents showed that a 0.1 M hydrochloric acid solution was the most effective, with 83.4% recovery. We also showed that presence of lead in the culture medium resulted in an increase in the quantity of protein in the biomass. Elemental analysis of lead-bound biomass showed an increase in elements including boron and copper and a decrease in cobalt and sodium. Synergystic and antagonystic effect in uptake of other elements was strain specific, suggesting the possibility of tailored wastewater treatments depending on specific requirements.

59 BASIC BIOLOGICAL SCIENCES↗

X-Ray Absorption Spectroscopy in High Temperature Oxidation of Metals and Alloys

An experimental technique is described that allows for the joint study of the kinetics and of the oxide structure during the high temperature oxidation of metal surfaces. Oxygen is supplied at the metal through an electrochemical oxygen pump and the oxygen pressure, at the metal surface, is measured during oxidation by a YSZ (yttria stabilized zirconia) oxygen sensor. XAS (x-ray absorption spectroscopy) is performed in fluorescence mode at the cation K edge and after each oxidation step. An appropriate analysis of the XAS spectra could provide information on both the oxidation kinetics and oxide structure. Experimental data on the high temperature oxidation of nickel, cobalt, and Fe(64%)Ni(36%) alloy, at low oxygen pressure, are reported and analyzed according to the proposed data reduction. These results indicate the presented technique to be particularly suitable for studying the hot corrosion of oxide film too thick for common surface spectroscopy (AUGER, ESCA) and too thin for conventional thermogravimetric technique.

Daniele Gozzi↗

Thermal Deformation of Very Slender Triangular Rollable and Collapsible Booms

Metallic triangular rollable and collapsible (TRAC) booms have deployed two Cubesat-based solar sails in low Earth orbit, making TRAC booms the most popular solar sail deployment method in practice. This paper presents some concerns and solutions surrounding the behavior of these booms in the space thermal environment. A 3.5-cm-tall, 4-meter-long TRAC boom of Elgiloy cobalt alloy, when exposed to direct sunlight in a 1 AU deep space environment, has a predicted tip motion of as much as 0.5 meters. Such large thermal deflections could generate unacceptable distortions in the shape of a supported solar sail, making attitude control of the solar sail spacecraft difficult or impossible. As a possible means of mitigating this issue, the thermal distortion behaviors of three alternative material TRAC booms are investigated and compared with the uncoated Elgiloy baseline boom. A tenfold decrease in induced curvature is shown to be possible relative to the baseline boom. Potential thermal distortions of the LightSail-A solar sail TRAC booms are also examined and compared, although inconclusively, with available on-orbit camera imagery.

Stohlman, Olive R.↗

Cobalt and nickel concentrations in the 'komatiite component' of Apollo 16 polymict samples

Some estimates for the concentrations of Co and Ni in the primitive mafic component of Apollo 16 breccias and soils are large, comparable to concentrations in terrestrial komatiites. These estimates may be erroneously high because the contribution from meteoritic contamination of the samples has been underestimated. However, even if the correction for meteoritic Co and Ni is valid and the calculated residual Ni is not of meteoritic origin, the Ni is presently carried by Fe-Ni metal while the Fe and Mg are carried by mafic silicates. If any large-scale separation of metal and silicate phases has occurred, the concentration ratio of Ni to Fe + Mg in the mafic silicates of the ancient crust in the vicinity of the Apollo 16 site has not been preserved by Apollo 16 rocks. Apollo 16 polymict breccias and soils contain much higher concentrations of siderophile elements and Fe-Ni metal than other nonmare samples from the Moon. Thus, it is likely that the Ni/(Mg + Fe) ratio estimated for the komatiite component from Apollo 16 samples is high compared to the actual ratio for the lunar crust.

Korotev, Randy L.↗

Superior Ballistic Impact Resistance Achieved by the Co-Base Alloy Haynes 25

The fan case in a jet engine is required to contain a fan blade in the rare event of a blade loss during operation. Because of its function, the fan case is the largest structural component in high-bypass-ratio turbofan engines used in commercial aircraft. Therefore, the use of lighter and stronger materials would be advantageous in most engines and is practically a necessity in the latest generation of high-bypass engines. Small panels, 7 in. wide by 7 in. long, of a number of metallic alloys were impact tested at room temperature with a 0.50-caliber blunt-nose titanium alloy projectile at the NASA Glenn Research Center (ref. 1). These metallic systems included several high-strength aluminum (Al) alloys, Al-based laminates, aluminum metal matrix composites (Al-MMCs), nickel-base superalloys (Inconel 718 and 625), several titanium (Ti) alloys in different heat treated conditions, 304L stainless steel, a stainless-steel-based laminate, and a high strength steel (Nitronic 60). It was determined that a simple Co-base alloy (Haynes 25) had the best impact resistance on an areal weight basis. Haynes 25 was at least 10 percent better than IMI 550, the best titanium alloy tested to date, and it was far superior to other metals, especially at higher impact velocities (greater than 1100 ft/sec). Because this material could be ideal for fan containment applications in supersonic aircraft as a replacement for titanium, impact tests were also conducted at 371 oC and compared with results from alloys tested at elevated temperature under previous programs (i.e., Inconel 718, Ti-6242, M-152, Timetal 21S, and Aeromet 100). Although cobalt-base alloys are used in some high-temperature engine applications, to our knowledge they are not used in any containment systems. Advantages of cobalt over titanium include lower cost, easier processing, better high-temperature strength, and no fire hazard if tip rub occurs. Future plans include testing of lightweight sandwich panels with Haynes 25 as a core material in the form of a foam or lattice block structure and scaling up the current tests by using blade-simulating projectiles impacting large plates and half rings.

Hebsur, Mohan G.↗

Amorphous-crystalline transition-driven synthesis of Co single-atom catalysts on MoO 3 for enhanced hydrogen evolution in acidic and alkaline media

Single atom catalysts (SACs) dispersed in metal oxide supports offer not only maximized catalyst utilization but also extended modulation capabilities through interactions between the SA and its support. However, achieving facile preparation and ensuring electrochemical durability of such SACs, particularly for hydrogen evolution reaction (HER) applications, remain formidable challenges. Here, our study addresses these issues by employing an amorphous-to-crystalline phase transition in MoO 3 to synthesize a cobalt (Co) SA catalyst. This method facilitates the production of highly selective SA catalysts at low temperatures and ensures their enhanced stability in HER applications. The Co SA MoO 3 catalyst exhibits superior performance in HER, operating effectively in both acidic and alkaline environments. Significantly, it maintains stable HER activity across these diverse electrolytic conditions. Our Density Functional Theory (DFT) calculations provide insights into the exceptional HER performance of Co SA MoO 3 . These calculations reveal that the strong affinity for hydrogen and water, facilitated by the modulation of the p-band orbitals at specific oxygen sites adjacent to the Co SA, establishes a thermoneutral pathway for HER. This study represents a pivotal advancement, showcasing a highly practical and robust single-atom catalyst, marking a significant stride towards sustainable energy solutions.

36 MATERIALS SCIENCE↗