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At least 109 records · Page 6

P2-Type Moisture-Stable and High-Voltage-Tolerable Cathodes for High-Energy and Long-Life Sodium-Ion Batteries

P2-Na 0.67 Ni 0.33 Mn 0.67 O 2 represents a promising cathode for Na-ion batteries, but it suffers from severe structural degradation upon storing in a humid atmosphere and cycling at a high cutoff voltage. Here we propose an in situ construction to achieve simultaneous material synthesis and Mg/Sn cosubstitution of Na 0.67 Ni 0.33 Mn 0.67 O 2 via one-pot solid-state sintering. Here, the materials exhibit superior structural reversibility and moisture insensitivity. In-operando XRD reveals an essential correlation between cycling stability and phase reversibility, whereas Mg substitution suppressed the P2–O2 phase transition by forming a new Z phase, and Mg/Sn cosubstitution enhanced the P2–Z transition reversibility benefiting from strong Sn–O bonds. DFT calculations disclosed high chemical tolerance to moisture, as the adsorption energy to H 2 O was lower than that of the pure Na 0.67 Ni 0.33 Mn 0.67 O 2 . A representative Na 0.67 Ni 0.23 Mg 0.1 Mn 0.65 Sn 0.02 O 2 cathode exhibits high reversible capacities of 123 mAh g –1 (10 mA g –1 ), 110 mAh g –1 (200 mA g –1 ), and 100 mAh g –1 (500 mA g –1 ) and a high capacity retention of 80% (500 mA g –1 , 500 cycles).

25 ENERGY STORAGE↗

The NASA-Langley 20-inch supersonic wind tunnel

NASA Langley's new 20-inch supersonic wind tunnel is in the process of reassembly, following extensive modifications. These will result in its incorporation of such features as a 'quiet' flow control valve, thick sintered screens with very large pressure drops, special farings in the contraction section, an instantaneous relief hatch in the test section, and a switching exhaust system that permits flow into a vacuum sphere during startup and shutdown and to the atmosphere during data acquisition. Attention is given to the expected operating map of the new tunnel.

Dillon, J. L.↗

Upper Temperature Limit of Environmental Barrier Coatings Based on Mullite and BSAS

Current state-of-the-art environmental barrier coatings (EBCs) for Si-based ceramics consist of three layers: a silicon bond coat, an intermediate mullite (3Al2O3-2SiO2) or mullite + BSAS (1-xBaO-xSrO-Al2O3-2SiO2) layer, and a BSAS top coat. Areas of concern for long-term durability are environmental durability, chemical compatibility, silica volatility, phase stability, and thermal conductivity. Variants of this family of EBCs were applied to monolithic SiC and melt infiltrated SiC/SiC composites. Reaction between BSAS and silica results in low melting (approx. 1300 C) glasses at T > 1400 C, which can cause the spallation of the EBC. At temperatures greater than 1400 C, the BSAS top coat also degrades by formation of a porous structure, and it suffers significant recession via silica volatilization in water vapor-containing atmospheres. All of these degradation mechanisms can be EBC life-limiting factors. BSAS undergoes a very sluggish phase transformation (hexagonal celsian to monoclinic celsian), the implications of which are not fully understood at this point. There was evidence of rapid sintering at temperatures as low as 1300 C, as inferred from the sharp increase in thermal conductivity.

Lee, Kang N.↗

Opportunities and Strategies for Testing and Infusion of ISRU in the Evolvable Mars Campaign

HE Evolvable Mars Campaign (EMC) is developing the plans and systems needed for a robust, evolutionary strategy to explore cis-lunar space, the Mars sphere of influence (including the moons of Mars), and the surface of Mars. Recently, the emphasis of NASA's plans has changed to focus on the prolonged pioneering of space, rather than focusing on a single crewed mission as the ultimate goal. A sustainable, pioneering vision of space would include in-situ resource utilization (ISRU) in multiple forms and at multiple destinations: atmospheric capture of Mars CO2 and/or volatiles for consumables and propellants, regolith for bulk and refined materials, and in-situ manufacturing at the Moon, Mars, and other bodies. These resources would enable a reduction in the logistical needs from Earth for future missions, thus preparing the way for a sustained presence on Mars. Although the EMC initially relies only on propellant production for the Mars ascent vehicle via ISRU, one of its primary objectives is to prospect at every EMC destination to understand the potential for ISRU; this will permit true pioneering to be enabled after the first crew arrives at Mars. Recent and ongoing analysis has considered the possible prospecting measurements that can be performed at the asteroid returned to cis-lunar space by the Asteroid Robotic Redirect Mission (ARRM), at the lunar surface, at Phobos and Deimos, and on the surface of Mars to identify available resources for future use. These opportunities will be available on missions currently in the Evolvable Mars Campaign construct, and will also facilitate the testing and demonstration of resource acquisition, processing, storage, and useage technologies that can play a role in later missions. This analysis has also led to the identification of several objectives that should be targeted during the missions building up to and including the initial crewed missions. These objectives are mapped to strategies for incorporating ISRU to support resource cycle closure and reduce mass requirements from Earth. This analysis has yielded engineering constraints, based on ISRU, that impact the evaluation of landing sites for missions to the surface of Mars. The terrain of a particular site must be sufficiently flat to permit ISRU systems, as well as ancillary systems such as power and propellant storage tanks, to be landed, moved into position, set up, and operated. Water must be accessible in a form that can be acquired via ISRU, in quantities that align with demands. The chosen method of acquiring and processing water should align with the available resources at a particular site, and that site must have sufficient quantities to meet the requirements (based on crew consumables and propellant demands). Lower altitude landing sites are preferred, as the increase in density can facilitate carbon dioxide acquisition from the atmosphere. Another preference is for sites with a greater ability to move regolith for civil engineering purposes; for example, this would be conducive to both bulk regolith uses (such as the manufacture of berms), and processed regolith uses (such as microwave sintering).

Evolvable Mars Campaign↗

Regolith-Derived Heat Shield for Planetary Body Entry and Descent System with In Situ Fabrication

In this paper we will discuss a new mass-efficient and innovative way of protecting high-mass spacecraft during planetary Entry, Descent & Landing (EDL). Heat shields fabricated in situ can provide a thermal-protection system (TPS) for spacecraft that routinely enter a planetary atmosphere. By fabricating the heat shield with space resources from regolith materials available on moons and asteroids, it is possible to avoid launching the heat-shield mass from Earth. Two regolith processing and manufacturing methods will be discussed: 1) Compression and sintering of the regolith to yield low density materials; 2) Formulations of a High-temperature silicone RTV (Room Temperature Vulcanizing) compound are used to bind regolith particles together. The overall positive results of torch flame impingement tests and plasma arc jet testing on the resulting samples will also be discussed.

Hogue, Michael D.↗

The Surfaces of Pluto and Charon

Much of the surface of Pluto consists of high-albedo regions covered to an unknown depth by Beta-N2, contaminated with CH4, CO, and other molecules. A portion of the exposed surface appears to consist of solid H2O. The remainder is covered by lower albedo material of unknown composition. The N2 ice may occur as polar caps of large extent, leaving ices and other solids of lower volatility in the equatorial regions. The low-albedo material found primarily in the equatorial regions may consist in part of solid hydrocarbons and nitriles produced from N2 and CH4 in the atmosphere or in the surface ices. Alternatively, it may arise from deposition from impacting bodies and/or the chemistry of the impact process itself. Charon's surface is probably more compositionally uniform than that of Pluto, and is covered by H2O ice with possible contaminants or exposures of other materials that are as yet unidentified. The molecular ices discovered on Pluto and Charon have been identified from near-infrared spectra obtained with Earth-based telescopes. The quantitative interpretation of those data has been achieved through the computation of synthetic spectra using the Hapke scattering theory and the optical constants of various ices observed in the laboratory. Despite limitations imposed by the availability of laboratory data on ices in various mixtures, certain specific results have been obtained. It appears that CH4 and CO are trace constituents, and that some fraction of the CH4 (and probably the CO) on Pluto is dissolved in the matrix of solid N2. Pure CH4 probably also occurs on Pluto's surface, allowing direct access to the atmosphere. Study of the nitrogen absorption band at 2.148 micrometers shows that the temperature of the N2 in the present epoch is 40 +/-2 K. The global temperature regime of Pluto can be modeled from observations of the thermal flux at far-infrared and millimeter wavelengths. The low-albedo equatorial regions must be significantly warmer than the polar regions covered by N2 (at T = 40 K) to account for the total thermal flux measured. At the present season, the diurnal skin depth of the insolation-driven thermal wave is small, and the observed mm-wave fluxes may arise from a greater depth. Alternatively, the mm-wave flux may arise from the cool, sublimation source region. The surface microstructure in the regions covered by N2 ice is likely governed by the sintering properties of this highly volatile material. The observed nitrogen infrared band strength requires that expanses of the surface be covered with cm-sized crystals of N2. Grains of H2O ice on Charon, in contrast, are probably of order 50 micrometers in size, and do not metamorphose into larger grains at a significant rate. Because of the similarities in size, density, atmosphere and surface composition between Pluto and Neptune's satellite Triton, the surface structures observed by Voyager on Triton serve as a plausible paradigm for what might be expected on Pluto. Such crater forms, tectonic structures, aeolian features, cryovolcanic structures, and sublimation-degraded topography as are eventually observed on Pluto and Charon by spacecraft will give information on their interior compositions and structures, as well as on the temperature and wind regimes over the planet's extreme seasonal cycle.

Cruikshank, Dale P.↗

Three-Dimensional (3D) Additive Construction: Printing with Regolith

Three dimensional (3D) printing is a new and booming topic in many realms of research and engineering technology. When it comes to space science and aerospace engineering, it can be useful in numerous ways. As humans travel deeper into space and farther from Earth, sending large quantities of needed supplies from Earth for a mission becomes astronomically expensive and less plausible. In order to reach further to new places, In Situ Resource Utilization (ISRU), a project that pushes for technologies to use materials already present in the destination's environment, is necessary. By using materials already available in space such as regolith from the Moon, Mars, or an asteroid's surface, fewer materials need to be brought into space on a launched vehicle. This allows a vehicle to be filled with more necessary supplies for a deep space mission that may not be found in space, like food and fuel. This project's main objective was to develop a 3D printer that uses regolith to "print" large structures, such as a dome, to be used as a heat shield upon a vehicle's reentry into the atmosphere or even a habitat. 3D printing is a growing technology that uses many different methods to mix, heat, and mold a material into a specific shape. In order to heat the regolith enough to stick together into a solid shape, it must be sintered at each layer of material that is laid. Sintering is a process that heats and compresses a powdered material until it fuses into a solid, which requires a lot of energy input. As an alternative, a polymer can be mixed with the regolith before or as it is sent to the 3D printer head to be placed in the specific shape. The addition of the polymer, which melts and binds at much lower temperatures than sintering temperatures, greatly decreases the required heating temperature and energy input. The main task of the project was to identify a functional material for the printer. The first step was to find a miscible. polymer/solvent solution. This solution was added to the regolith and the solvent was evaporated essentially leaving polymer-coated regolith particles. This material would be sent through the printer head and heated layer by layer to melt the polymer and bind the regolith. This method was one of many in a large goal to utilize materials in space with a custom-made 3D printer that builds dome-shaped habitats and other essential equipment for future deep space missions.

Tsoras, Alexandra↗

The influence of the processing parameters on the reactive flash sintering of ZrO 2 -CeO 2

Reactive flash sintering (RFS) is a method that was recently developed to produce dense single-phase bulk ceramic parts through solid-state reactions in a single-step that only takes a few minutes. The influence of the RFS parameters on the phase purity of a simple mixed oxide, (Zr 0.8 ,Ce 0.2 )O 2 , was investigated. Parameters such as furnace temperature, furnace atmosphere, electric current density, and alternating current (AC) or direct current (DC) were examined. It was found that (Zr 0.8 ,Ce 0.2 )O 2 pellets with high densities, above 90% of its theoretical density, can be produced by RFS in a few minutes when RFS occurs under oxidizing atmospheres, AC fields with current densities of 100 mA·mm –2 , and at a furnace temperature of 1200°C. Reducing conditions such as Ar-H 2 atmosphere and DC fields, low furnace temperatures, and low current densities resulted in phase impurities and poor reactions between the ZrO 2 and the CeO 2 powders. These results show that RFS is a useful method to produce mixed oxides, but it is very sensitive to the processing parameters. This is the first time that the influence of most of the RFS processing parameters has been studied systematically. Thus, the present work aims to provide guidelines on selecting the right processing parameters when exploring RFS.

36 MATERIALS SCIENCE↗

Fluid Dynamics of a Pressure Reducing Inlet

Instruments for the monitoring of hazardous gases in and near the space shuttle collect sample gas at pressures on the order of one atmosphere and analyze their properties in an ultra-high vacuum by means of a quadrupole-mass-spectrometer partial pressure transducer. Sampling systems for such devices normally produce the required pressure reduction through combinations of vacuum pumps, fluid Tees and flow restrictors (e.g. orifices, sintered metal frits or capillaries). The present work presents an analytical model of the fluid dynamics of such a pressure reduction system which enables the calculation of the pressure in the receiver vessal in terms of system parameters known from the specifications for a given system (e.g. rated pumping speeds of the pumping hardware and the diameters of two orifices situated in two branches of a fluid Tee). The resulting formulas will expedite the fine tuning of instruments now under development and the design of later generations of such devices.

Russell, John M.↗

Exploring the Effect of EBC Composition on CMAS Wetting Behavior

Rare-earth disilicate (REDS) materials are existing materials used in environmental barrier coating (EBC) for the protection of structural materials in the hot-section of turbine engines. REDS interactions with molten calcium-magnesium-aluminosilicate (CMAS) debris are of interest to understand molten CMAS attack and improve CMAS mitigation strategies. This work assesses the effect of REDS composition on CMAS wetting by investigating wetting angle, spreading, and reactivity. Freestanding atmospheric plasma spray (APS) REDS coatings (for RE = Y, La, Nd, Gd, Yb, Lu) were exposed to 10 mg of CMAS (Ca33-Mg9-Al13-Si45 in single cation mol%) in stagnant lab air at 1250C. APS YbDS was compared to a dense spark plasma sintered (SPS) phase-pure Yb2Si2O7 and a nominal 20 vol% phase-mixture of Yb 2 SiO 5 in Yb 2 Si 2 O 7 (20YbMS/YbDS). CMAS mass was held constant but specimen surface areas varied, yielding a range of loading between ~6 and 10 mg/cm2. CMAS was loaded as a cylindrical rod atop the specimen surface, polished to 4000 grit, and heated to temperature in a Linseis L74/HS/1700 heating microscope. The heating microscope measured the evolution of molten CMAS diameter, height, and contact angle. Molten CMAS diameter at 1150C and contact angle measurements after two hours of exposure at 1250C yielded a positive trend with rare-earth cation size. There was no statistically significant difference in CMAS wetting behavior between SPS YbDS and 20YbMS/YbDS. Post-exposure specimens were examined in plan view and cross-section with XRD, SEM, and EDS. CMAS spreading was cross-examined using plan view SEM, while reactivity utilized plan view XRD and cross-sectional SEM/EDS.

Clark Luckhardt↗

Mullite fiber reinforced reaction bonded Si3N4 composites

Fracture toughnesses of brittle ceramic materials have been improved by introducing reinforcements and carefully tailored interface layers. Silicon carbide and Si3N4 have been emphasized as matrices of structural composites intended for high temperature service because they combine excellent mechanical, chemical, thermal and physical properties. Both matrices have been successfully toughened with SiC fibers, whiskers and particles for ceramic matrix composite (CMC) parts made by sintering, hot pressing or reaction forming processes. These SiC reinforced CMCs have exhibited significantly improved toughnesses at low and intermediate temperature levels, as well as retention of properties at high temperatures for selected exposures; however, they are vulnerable to attack from elevated temperature dry and wet oxidizing atmospheres after the matrix has cracked. Property degradation results from oxidation of interface layers and/or reinforcements. The problem is particularly acute for small diameter (-20 tim) polymer derived SiC fibers used for weavable toes. This research explored opportunities for reinforcing Si3N4 matrices with fibers having improved environmental stability; the findings should also be applicable to SiC matrix CMCs.

Saleh, T.↗

Evolution of Ni-Mo/MgO during catalytic methane pyrolysis to produce base-growth nanotubes

Catalytic pyrolysis of methane is a promising approach for affordable hydrogen production without CO 2 emissions. While this process is thermodynamically appealing compared to steam reforming, the high stability of methane requires severe conditions, making catalyst stability challenging. Here, we report the behavior of a highly promising Ni-Mo/MgO catalyst, which greatly outperforms its Ni/MgO, Mo/MgO, and Ni-Mo/SiO 2 counterparts at atmospheric pressure. At 800°C, nearly 229 g of carbon nanotubes per gram of Ni are produced. We propose that this superior performance results from the phase evolution of the catalyst, which exsolves stable nickel catalyst particles under reaction conditions. We further reveal that molybdenum carbide formation reduces sintering and adheres the active catalytic particles to the support throughout the reaction, enabling catalyst reuse. Several characterization techniques (same-spot TEM, XPS, XRD, and Raman) are employed to examine catalyst morphology at every step, fostering a deeper understanding of its catalytic activity and stability.

36 MATERIALS SCIENCE↗

Improved reaction sintered silicon nitride

Processing treatments were applied to as-nitrided reaction sintered silicon nitride (RSSN) with the purposes of improving strength after processing to above 350 MN/m2 and improving strength after oxidation exposure. The experimental approaches are divided into three broad classifications: sintering of surface-applied powders; impregnation of solution followed by further thermal processing; and infiltration of molten silicon and subsequent carburization or nitridation of the silicon. The impregnation of RSSN with solutions of aluminum nitrate and zirconyl chloride, followed by heating at 1400-1500 C in a nitrogen atmosphere containing silicon monoxide, improved RSSN strength and oxidation resistance. The room temperature bend strength of RSSN was increased nearly fifty percent above the untreated strength with mean absolute strengths up to 420 MN/m2. Strengths of treated samples that were measured after a 12 hour oxidation exposure in air were up to 90 percent of the original as-nitrided strength, as compared to retained strengths in the range of 35 to 60 percent for untreated RSSN after the same oxidation exposure.

Baumgartner, H. R.↗

Fractographic and microstructural evaluation of 3500-hour durability specimens

Long term durability testing of candidate ceramic materials for advanced gas turbine applications was performed. Specimens of the materials were exposed to combustion atmospheres under temperature cyclic conditions for times up to 3500 hours and at peak temperatures of 1200 and 1370 C. The specimen strengths after exposure were measured at room temperature and at 1200 C. In addition, a number of physical measurements were taken; however, no microstructural examination of the specimens was performed. Materials examined include: sintered alpha silicon carbide, sintered silicon nitride, and reaction bonded silicon nitride. Sample preparation techniques were developed to provide high quality thin-section specimens which can be examined by transmitted light or thinned using an ion mill for subsequent transmission electron microscopic examination. Specimen preparation techniques and the results of optical and electron microscopic examination of the reaction interfaces of the selected specimens are presented.

Miller, A. D.↗

The PM-200 lubrication system

Plasma sprayed composite coating of metal-bonded chromium carbide with additions of silver and thermochemically stable fluorides were previously reported to be lubricative in pin on desk bench tests from room temperature to 900 C. An early coating formulation of this type, designated as PS-200, was successfully tested as a cylinder coating in a Stirling engine at a TRRT of 760 C in a hydrogen atmosphere, and as a backup lubricant for gas bearings to 650 C. A subsequent optimization program has shown that tribological properties are further improved by increasing the solid lubricant content. The improved coating is designated as PS-212. The same powder formulation was used to make free-standing powder metallurgy (PM-212) parts by sintering or hot isostatic pressing. The process is very attractive for making parts that cannot be readily plasma sprayed such as bushings and cylinders that have small bore diameters and/or high length to diameter ratios. The properties of coatings and free-standing parts fabricated from these powders are reviewed.

Sliney, Harold E.↗

Nitridation of silicon

Silicon powders with three levels of impurities, principally Fe, were sintered in He or H2. Non-densifying mechanisms of material transport were dominant in all cases. High purity Si showed coarsening in He while particle growth was suppressed in H2. Lower purity powder coarsened in both He and H2. The same three Si powders and Si /111/ single crystal wafers were nitrided in both N2 and N2/H2 atmospheres. Hydrogen increased the degree of nitridation of all three powders and the alpha/beta ratio of the lower purity powder. Some Si3N4 whiskers and open channels through the surface nitride layer were observed in the presence of Fe, correlating with the nitridation-enhancing effects of Fe. Thermodynamic calculations showed that when SiO2 is present on the Si, addition of H2 to the nitriding atmosphere decreases the amount of SiO2 and increases the partial pressure of Si-containing vapor species, that is, Si and SiO. Large amounts of NH3 and SiH4 were also predicted to form.

Shaw, N. J.↗

Additive Manufacturing and Working Fluid Characterization of Ceramic Heat Pipes

In this work, additively manufactured (AM) aluminum nitride (AlN) ceramic heat pipes were developed to improve spacecraft heat rejection capabilities beyond the current state-of-the-art metal systems. A low sintering temperature aluminum nitride slurry is developed for digital light processing printing (DLP) and the optimal debinding curves are examined. Printed AlN parts are characterized via SEM and optical profilometry. AlN 3D-printed parts are also tested for compatibility with aluminum bromide, aluminum chloride, and iodine, among other proposed working fluids at 350-600 K in an inert atmosphere, with reactivity measured via SEM and Fourier transform infrared spectroscopy (FTIR).

Thermal Management↗

The evolution of model Rh/Fe 3 O 4 (001) catalysts in hydrogen environments

Single metal atoms dispersed on oxides are a new emerging class of catalysts owing to their unique electronic and chemical properties. Here, in this study, we have prepared a series of model single-atom catalysts possessing well-characterized Rh sites that include Rh adatoms (Rh ad ), mixed surface layers with octahedrally-coordinated Rh (Rh oct ), as well as metallic Rh clusters and nanoparticles (Rh met ) on Fe 3 O 4 (001). Using X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM), we investigated the activity of such model systems towards H2 and their stability in reducing environments. Our results show that the atomically dispersed Rhad and Rhoct species do not activate H 2 , which would result in the formation of surface hydroxyls on Fe 3 O 4 (001). In contrast, the presence of Rh met in H 2 results in the formation of hydroxyls and subsequent etching of the Fe 3 O 4 (001) at higher temperatures (≥ 500 K) due to water formation via the Mars-van Krevelen mechanism. Additionally, such surface etching leads to the release of the Rh oct from the surface lattice and their sintering to Rh met . To bridge the material gap between the surface science models and high surface area catalysts, we perform parallel studies on powder Rh/Fe 3 O 4 catalysts. The XPS characterization shows remarkable similarities between these systems. Further, our surface science studies provide an atomistic picture of the behavior of high surface area catalysts in the H 2 atmosphere.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗