SEARCH · Search NASA

Results for “limited hydrogenation ability”

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.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

107 records · Page 6

All sources NASA NTRS DOE OSTI

NASA NTRSDate not supplied

Lunabotics Robotic Mining Competition for Universities

Space Mining for resources such as water ice, and regolith, which contain many elements in the form of metals, minerals, volatiles and other compounds, is a necessary step for In-Situ Space Resource Utilization (ISRU). One of the primary goals is to extract propellants from the regolith and water ice, such as oxygen and hydrogen which could then be used for in-space transportation. In addition, the space mining system can be used for various construction tasks that can benefit human and robotic exploration as well as scientific investigations based on excavated exposed topography, such as the side walls of trenches. The National Aeronautics & Space Administration (NASA) “Lunabotics” Robotic Mining Competition (RMC) is a university-level competition designed to engage and retain students in science, technology, engineering and mathematics (STEM). NASA has directly benefited from the competition by encouraging the development of innovative lunar excavation concepts from universities which has resulted in clever ideas and solutions which could be applied to an actual lunar excavation device or payload. The challenge is for students to design and build a remote controlled or autonomous 80 kg mass lightweight excavator, called a “lunabot”, which can collect and deposit a minimum of 10 kilograms of lunar simulant within 15 minutes. In recent years the goal has been changed to excavate a minimum of 1 kg of simulated icy regolith which is found under an overburden of regolith simulant. The complexities of the challenge include the abrasive characteristics of the lunar regolith simulant, the weight and size limitations of the lunabot, and the ability to control the lunabot from a remote mission control center or operate it autonomously. This presentation will summarize the results of the Lunabotics Robotic Mining Competitions held in May 2022. Each year, since 2010, over 50 university teams have attended, resulting in over 500 lunabot designs and subsequent prototypes. Over 6,000 university students have been part of the on-site competition at KSC, and many are employed in the space sector today with thriving careers. Even more students and the public were engaged via internet broadcasting and social networking media. Examples of how this translates to hiring opportunities for commercial sponsors will also be discussed. Overall, this competition has proven to be popular with multi-disciplinary university senior design classes and a valuable tool for NASA and academia in educating and inspiring the next generation of space engineers.

Lunabotics↗

DOE OSTI2023

Surface oxygen exchange kinetics of mixed conducting oxides: Dilatometric vs electrical conductivity relaxation study

The surface oxygen exchange kinetics of mixed ionic-electronic conducting (MIEC) oxides play a crucial role in a variety of applications, including solid oxide fuel/electrolysis cells (SOFCs/SOECs), permeation membranes and sensors. To date, a variety of methods, including isotope exchange, electrical conductivity, optical absorptivity and thermogravimetry relaxation, and impedance spectroscopy have been used to measure the oxygen exchange coefficient of MIEC oxides. Each of these methods have their advantages and limitations, depending on the physical and chemical properties of the investigated materials and their sample dimensions and densities. Here, we demonstrate the ability to precisely measure the surface oxygen exchange coefficient (k chem ) of MIEC model material Pr 0.1 Ce 0.9 O 2-δ (PCO) by use of dilatometric relaxation measurements, particularly of interest for materials that exhibit larger chemical expansion coefficients. This is achieved by use of porous bulk specimens to ensure that the contribution of oxygen exchange to the overall kinetics is dominant. We demonstrate that k chem values extracted from chemical expansion relaxation measurements on PCO are nearly identical to those derived from electrical conductivity relaxation measurements. As a result, this provides the opportunity to precisely investigate the oxygen exchange and chemical expansion kinetics of a wide range of materials used in high-temperature applications, particularly where more conventional methods are difficult or inappropriate to apply.

(Pr,Ce)O2-x↗

DOE OSTI2022

Scalable Nano-Scaffold SOFC Anode Architecture Enabling Direct Hydrocarbon Utilization

This project is based on WVU’s pending patents, technology and aims to design and modify the internal surfaces of the Ni/YSZ anode from currently commercially viable Solid Oxide Fuel Cells (SOFCs) using the additive manufacturing process of Atomic Layer Deposition (ALD). The surface architecture/scaffold added onto the internal surface of the anode possesses an engineered nanostructure but it features only commonly-used oxide conductors and electro-catalyst materials. The surface layer possesses a minimum thickness of ~2-40 nm and is solely designed to control the surface reforming reactions and to increase catalytic activity. Three-dimensional (3D) nano scaffold architectures with the noble metal nano-catalyst, low-cost bimetallic catalytic alloys, and nano-scale ionic conducting oxide fully compatible with the state-of-the-art Ni/YSZ anode, were applied to the internal surface of the entire porous SOFC anode using ALD. In the present work, the surface scaffold architecture is essentially multi-functional at the nano-scale, facilitated by the multiple heterostructured interfaces. It will significantly enhance the power density and cell durability for direct hydrocarbon utilization by (1) increasing the number of electrochemical reaction sites to enhance the hydrogen/hydrocarbon oxidation reactions; (2) reducing carbon formation; (3) mitigating the coarsening of backbone Ni phase and the oxidation attack of Ni from oxidants (e.g., H2O, CO2); and (4) promoting the internal reforming capabilities, especially for natural gas applications. ALD is employed to generate stable anode surface architectures that are uniform, precisely controllable at the atomic scale, and accurately repeatable for processing. The engineered anode surface nano-scaffold architecture was cataloged and analyzed using High-resolution Transmission Electron Microscopy (TEM), and cell power/durability performance assessed via comprehensive electrochemical performance testing with commercial specimens and relevant environments using hydrocarbon fuels. To the best of our knowledge, this project is the First Report on ALD of Ni/YSZ. The actual achievement of this Project includes (1). Successful demonstration of 7 types of ALD layers on Ni/YSZ anode, including Co, Ni, Mn, Pt, Ru, ZrOx and multi-functional nano-composite. (1). Conformal coating and subsequently spontaneously pinning the discrete nano-catalyst, including the precious metal nano-catalyst and the Ni and Co catalysts, on the YSZ surface upon the electrochemical operation in the reduced atmosphere. Those nano-catalysts on the ionic-conducting YSZ provided excellent sites for promoting internal reforming; (2). Demonstrated ALD coating increased both catalytic activity and conductivity of Ni/YSZ. Conformal coating provided dopants and introduced additional electrical conducting pathways on the YSZ ionic conductor. The doped surface layer of YSZ with mixed conductivity thus further introduces the active triple phase boundaries adjacent to the ALD-coated nano-catalysts such as Pt, Co, and Ni that are pinned on the YSZ surface. The nano-composite ALD coating on Ni/YSZ anode has significantly increased cell durability; and (3). ALD coating of Ni/YSZ anode increased the power density of the entire cell by 300%. For a long time, the SOFC performance, such as the power density, was deemed hindered by the cathode. The sluggish oxygen reduction reaction (ORR) in the cathode was deemed as hindering the power density of the SOFCs. For the anode-supported commercial SOFCs, the cell performance is considered to be limited by the cathode's performance. For the first time in the field of SOFC, this project has demonstrated that (1). the performance of commercial SOFCs can be further increased by the ALD coating on Ni/YSZ anode backbone. (2). ALD coating on Ni/YSZ fuel electrodes results in the enhancement of power density, and increased reliability, robustness, and endurance of SOFCs, for their application using both hydrogen and hydrocarbon fuels over the entire operating temperature range of 650-800ºC for the inherently functional commercial cells. (3). ALD coating provides alternative approaches of exsolutions for introducing the stable catalyst onto the internal surface of the Ni/YSZ electrode. ALD coating could be much more versatile than exsolution in employing the catalysts with various chemistries onto the various backbones. (4). Due to the negligible amount of ALD materials coated onto the internal surface of the porous cathode of the as-fabricated cells, a peak power density increase up to 300 % induced by ALD coating was simultaneously achieved in terms of both power density and specific power. (5). The ALD coating developed through this project was applied to both the SOFC and Solid Oxide Electrolysis Cells (SOEC). SOEC’s face a similar but more demanding need to improve the fuel electrode's performance. It opens further research directions for electrocatalytic surface nanoionics with a wide range of chemistry. It will revolutionize our ability to render the formation of a nanostructured electrode that has been constantly pursued yet barely achieved for practical SOFC/SOEC applications. The research is also immediately transformative since both the preliminary data and the proposed work are on the direct implantation of nanoionics into the state-of-the-art inherently functional SOCs. It represents an immediate impact on the commercial sectors in SOC technology since the applied ALD processing is computer-controlled ALD coating using the commercial ALD systems, and it is scalable to both the single cells and SOC stacks.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Partial Wave Analysis of Strange Mesons Decaying to K+p+p- in the Reaction ¿p ¿ K+p+p-¿(1520) and the Commissioning of the GlueX DIRC Detector

Hadron spectroscopy is a cornerstone of our understanding of the strong nuclear interactions. Studying the hadron spectrum led to the postulation of quarks and gluons, and the development of Quantum Chromodynamics (QCD), the theory of the strong nuclear force. Today hadron spectroscopy provides an important test of QCD, particularly in the non-perturbative energy regime. One such test is the existence of hybrid hadrons that have gluonic degrees of freedom, e.g. q ?qg states, that are allowed by QCD but have remained elusive in experimental searches. The GlueX experiment located at Thomas Jefferson National Accelerator Facility, is designed to map the light meson spectrum, including hybrid mesons, produced by a linearly polarized photon beam that is scattered off of a liquid hydrogen target. This dissertation concerns the installation and commissioning of the GlueX DIRC upgrade and the analysis of three reactions measured by the GlueX experiment. The GlueX DIRC is a particle identification detector installed as an upgrade to the GlueX experiment in 2019 to improve the experiment?s ability to distinguish pions and kaons. The DIRC uses Cherenkov photons radiated by charged particles that travel faster than the speed of light in the detector medium to determine the velocity of said particles. The velocity measurement is used in conjunction with momentum measurements from other detectors to determine the mass of the particle. The DIRC will be essential to the future of strange meson spectroscopy in GlueX. The reactions ?p ? K+K??+??p, ?p ? K+K??0?0p, ?p ? K+K??0?p were initially chosen for this analysis to search for the hybrid meson candidate ?(2170) and related resonances. The ?(2170) has been observed in e+e? collider experiments decaying to K+K??+?? and K+K??0?0, among other final states. The ?(2170) was not observed in this analysis. The reaction ?p ? K+?+???(1520), a subset of the ?p ? K+K??+??p reaction, was analyzed with a Partial Wave Analysis (PWA) in order to study strange mesons that decay to K+?+??. In the PWA, a useful model for the angular distributions was found but no significant structures could be observed due to statistical limitations.

Hurley, Andrew↗

NASA NTRS1995

Advanced Dependent Pressure Vessel (DPV) nickel-hydrogen spacecraft cell and battery design

The dependent pressure vessel (DPV) nickel-hydrogen (NiH2) battery is being developed as a potential spacecraft battery design for both military and commercial satellites. Individual pressure vessel (IPV) NiH2 batteries are currently flying on more than 70 Earth orbital satellites and have accumulated more than 140,000,000 cell-hours in actual spacecraft operation. The limitations of standard NiH2 IPV flight battery technology are primarily related to the internal cell design and the battery packaging issues associated with grouping multiple cylindrical cells. The DPV cell design offers higher specific energy and reduced cost, while retaining the established IPV NiH2 technology flight heritage and database. The advanced cell design offers a more efficient mechanical, electrical and thermal cell configuration and a reduced parts count. The internal electrode stack is a prismatic flat-plate arrangement. The flat individual cell pressure vessel provides a maximum direct thermal path for removing heat from the electrode stack. The cell geometry also minimizes multiple-cell battery packaging constraints by using an established end-plateltie-rod battery design. A major design advantage is that the battery support structure is efficiently required to restrain only the force applied to a portion of the end cell. As the cells are stacked in series to achieve the desired system voltage, this increment of the total battery weight becomes small. The geometry of the DPV cell promotes compact, minimum volume packaging and places all cell terminals along the length of the battery. The resulting ability to minimize intercell wiring offers additional design simplicity and significant weight savings. The DPV battery design offers significant cost and weight savings advantages while providing minimal design risks. Cell and battery level design issues will be addressed including mechanical, electrical and thermal design aspects. A design performance analysis will be presented at both the cell and battery level. The DPV is capable of delivering up to 76 Watt-hours per kilogram (Wh/kg) at the cell level and 70 Wh/kg at the full battery level. This represents a 40 percent increase in specific energy at the cell level and a 60 percent increase in specific energy at the battery level compared to current IPV NiH2 technology.

Coates, Dwaine↗

DOE OSTI2020

Re-evaluation of the TSL for Yttrium Hydride

Yttrium hydride (YH x ) is of interest as a high-temperature moderator material in advanced nuclear reactor systems because of its superior ability to retain hydrogen at elevated temperatures. Thermal neutron scattering laws (TSL) for hydrogen bound in yttrium hydride (H-YH 2 ) and yttrium bound in yttrium hydride (Y-YH 2 ) were previously evaluated by Naval Nuclear Laboratory using the ab initio approach and released in ENDF/B-VIII.0. In that work, density functional theory, incorporating the generalized gradient approximation (GGA) for the exchange-correlation energy, was used to simulate the face-centered cubic structure of YH 2 and calculate the interatomic Hellmann-Feynman forces for a 2×2×2 supercell containing 96 atoms. Lattice dynamics calculations using PHONON were used to determine the phonon density of states. The calculated phonon density of states for H and Y in YH 2 were then used to prepare H-YH 2 and Y-YH 2 TSL evaluations, in the incoherent approximation, using the LEAPR module of NJOY. In addition, elastic scattering was assumed to be incoherent for both H and Y. While the incoherent elastic scattering approximation is appropriate for H-YH 2 , it introduces an undesirable approximation for Y-YH 2 . In this work, we re-evaluate the TSL for Y-YH 2 using FLASSH (Full Law Analysis Scattering System Hub). Y-YH 2 is evaluated using the FLASSH generalized coherent elastic scattering capability in order to capture the Bragg peaks associated with the YH 2 crystal structure which were neglected in the prior NJOY-based evaluation due to limitations in LEAPR. An experimental approach to validate the Y-YH 2 TSL using neutron transmission measurements is discussed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

NASA NTRS2007

Technical Findings, Lessons Learned, and Recommendations Resulting from the Helios Prototype Vehicle Mishap

The Helios Prototype was originally planned to be two separate vehicles, but because of resource limitations only one vehicle was developed to demonstrate two missions. The vehicle consisted of two configurations, one for each mission. One configuration, designated HP01, was designed to operate at extremely high altitudes using batteries and high-efficiency solar cells spread across the upper surface of its 247-foot wingspan. On August 13, 2001, the HP01 configuration reached an altitude of 96,863 feet, a world record for sustained horizontal flight by a winged aircraft. The other configuration, designated HP03, was designed for long-duration flight. The plan was to use the solar cells to power the vehicle's electric motors and subsystems during the day and to use a modified commercial hydrogen-air fuel cell system for use during the night. The aircraft design used wing dihedral, engine power, elevator control surfaces, and a stability augmentation and control system to provide aerodynamic stability and control. At about 30 minutes into the second flight of HP03, the aircraft encountered a disturbance in the way of turbulence and morphed into an unexpected, persistent, high dihedral configuration. As a result of the persistent high dihedral, the aircraft became unstable in a very divergent pitch mode in which the airspeed excursions from the nominal flight speed about doubled every cycle of the oscillation. The aircraft s design airspeed was subsequently exceeded and the resulting high dynamic pressures caused the wing leading edge secondary structure on the outer wing panels to fail and the solar cells and skin on the upper surface of the wing to rip away. As a result, the vehicle lost its ability to maintain lift, fell into the Pacific Ocean within the confines of the U.S. Navy's Pacific Missile Range Facility, and was destroyed. This paper describes the mishap and its causes, and presents the technical recommendations and lessons learned for improving the design, analysis, and testing methods and techniques required for this class of vehicle.

Noll, Thomas E.↗

DOE OSTI2023

An extensive assessment of the performance of pairwise and many-body interaction potentials in reproducing ab initio benchmark binding energies for water clusters n = 2–25

We assess the performance of 7 pairwise additive (TIP3P, TIP4P, TIP4P-ice, TIP5P, OPC, SPC, SPC/E) and 8 families of many-body potentials (q-AQUA, HIPPO, AMOEBA, EFP, TTM, WHBB, MB-pol, MB-UCB) in reproducing high-level ab initio benchmark values, CCSD(T) or MP2 at the complete basis set (CBS) limit for the binding energy and the many-body expansion (MBE) of water clusters n = 2–11, 16–17, 20, 25. By including a large range of cluster sizes having dissimilar hydrogen bonding networks, we obtain an understanding of how these potentials perform for different hydrogen bonding arrangements that are mostly outside of their parameterization range. While it is appropriate to compare the results of ab initio based many-body potentials directly to the electronic binding energies (D e 's), the pairwise additive ones are compared to the enthalpies at T = 298 K, ΔH(298 K), as the latter class of force fields are parametrized to reproduce enthalpies (implicitly accounting for zero-point energy corrections) rather than binding energies. We find that all pairwise additive potentials considered overestimate the reference ΔH values for the n = 2–25 clusters by >13%. For the water dimer (n = 2) in particular, the errors are in the range 83–119% for the pairwise additive potentials studied since these are based on an effective rather than the true 2-body interaction specifically designed as a means of partially accounting for the missing many-body terms. This stronger 2-body interaction is achieved by an enhanced monomer dipole moment that mimics its increase from the gas phase monomer to the condensed phase value. Indeed, for cluster sizes n ≥ 4 the percent deviations become slightly smaller (albeit all exceeding 13%). In contrast, we find that the many-body potentials perform more accurately in reproducing the electronic binding energies (D e 's) throughout the entire cluster range (n = 2–25), all reproducing the ab initio benchmark binding energies within ±7% of the respective CBS values. We further assess the ability of a subset of the many-body potentials (MB-UCB, q-AQUA, MB-pol, and TTM2.1-F) to also reproduce the magnitude of the ab initio many-body energy terms for water cluster sizes n = 7, 10, 16 and 17. The potentials show an overall good agreement with the available benchmark values. However, we identify characteristic differences upon comparing the many-body terms at both the ab initio-optimized geometries and the respective potential-optimized geometries to the reference ab initio values. Additionally, by applying this analysis to a wide range of cluster sizes, trends in the MBE of the potentials with increasing cluster size can be identified. Finally, in an attempt to draw a parallel between the pairwise additive and many-body potentials, we report the analysis of the individual molecular dipole moments for water clusters with 1 to ~4 solvation shells with the TTM2.1-F potential. We find that the internally solvated water molecules have in general a larger molecular dipole moment ranging from 2.6–3.0 D. This justifies the use of an enhanced, with respect to the gas-phase value, molecular dipole moment for the pairwise additive potentials, which is intended to fold in the many body terms into an effective (enhanced) pairwise interaction through the choice of the charges. These results have important implications for the development of future generations of efficient, transferable, and highly accurate classical interaction potentials in both the pairwise additive and many-body categories.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1994

Ways to Increase Launch Velocities of 2-Stage Gas Guns

The amount of space debris is rapidly increasing and the debris is distributed over a wide variety of orbits. Satellites, manned space vehicles and space stations will have to pay increasing attention to the dangers of impacts with space debris. Various armoring techniques (i.e., double or triple layer armor) will have to tested extensively to determine the most effective armor per unit weight. Intersecting near-earth orbits can lead to impact velocities up to 15 km/sec. Conventional two-stage light gas guns can launch intact, controlled-shape projectiles with a density of 1.2 gm/cc and length- to-diameter ratios of 0.5-1.0 at velocities up to 8-9 km/sec. Higher velocities (10-11 km/sec) can be obtained' for very light projectiles. The higher launch velocities tend to be very severe on the high pressure coupling and barrel of the gun and lead to short component lifetimes. Clearly, the ability to raise the launch velocity of a gun (for reasonably massive projectile shapes) from 8-9 km/sec to 11-13 km/sec (or higher), without reduction of component lifetimes, would have significant benefits. This would allow much better simulation of the higher velocity debris impacts as well as better simulation of high speed re-entry into planetary atmospheres. Several techniques for increasing the launcher muzzle velocity above 8-9 km/sec have been studied using CFD simulations and appear to offer the potential for significant gains. The first technique is to use multiple compressions, instead of a single compression, in the pump tube of the light gas gun. In a sense, this is a kind of pre-heating of the gas in the pump tube; other types of pre-heating have yielded disappointing results in the past. The dynamics of the multiple compression pump tube is very different, however, from the earlier techniques, where the pump tube was typically heated ohmically before the gun 2 cycle was started. In this paper, we present CFD calculations that show that significant increases in muzzle velocity can be obtained with multiple compressions in the pump tube. With a conventional two-stage gun, an important limitation to obtaining higher velocities is friction and heat transfer to the barrel, which typically has a length- to- diameter ratio of 200-400. These viscous losses greatly reduce the effectiveness of the regions of the barrel far removed from the second stage breech. We have studied computationally the effect of adding an additional breech (or breeches) along the barrel to reduce these viscous losses. Velocity increases from 6.5 to 7.2 km/sec have been obtained using the main breech and one additional breech. In these results, both breeches were operated with hydrogen, heated electrothermally. We have also studied a gun geometry where the main breech is operated in the conventional manner, using piston compression. The additional breech is operated either with electrothermal heating or heating by using a high explosive charge in a novel geometry. The latter option provides very effective compression, heating and acceleration of the hydrogen working gas and is fully reusable. Calculations are presented which show that very substantial increases in muzzle velocity can be obtained this way, without overstressing the projectile or the 'gun. The third technique studied is to add a section of ram accelerator tube after the barrel to further accelerate the projectile. The ram accelerator used here is not the conventional premixed gas ram accelerator, but a new technique using high explosive as the energy source and pure hydrogen as the working gas in a geometry which can be made fully reusable. Preliminary results with this new rain accelerator geometry were presented and showed that stable ram accelerator drive can be established. Herein, detailed calculations axe presented which show that substantial velocity increases can be obtained using this ram accelerator technique in tandem with a conventional light gas gun.

Bogdanoff, David W.↗

NASA NTRS2010

Potential Lunar In-Situ Resource Utilization Experiments and Mission Scenarios

The extraction and use of resources on the Moon, known as In-Situ Resource Utilization (ISRU), can potentially reduce the cost and risk of human lunar exploration while also increasing science achieved. By not having to bring all of the shielding and mission consumables from Earth and being able to make products on the Moon, missions may require less mass to accomplish the same objectives, carry more science equipment, go to more sites of exploration, and/or provide options to recover from failures not possible with delivery of spares and consumables from Earth alone. The concept of lunar ISRU has been considered and studied for decades, and scientists and engineers were theorizing and even testing concepts for how to extract oxygen from lunar soil even before the Apollo 11 mission to the Moon. There are four main areas where ISRU can significantly impact how human missions to the Moon will be performed: mission consumable production, civil engineering and construction, energy production, storage, and transfer, and manufacturing and repair. The area that has the greatest impact on mission mass, hardware design and selection, and mission architecture is mission consumable production, in particular, the ability to make propellants, life support consumables, and fuel cell reagents. Mission consumable production allows for refueling and reuse of spacecraft, increasing power production and storage, and increased capabilities and failure tolerance for crew life support. The other three areas allow for decreased mission risk due to radiation and plume damage, alternative power systems, and failure recover capabilities while also enabling infrastructure growth over Earth delivered assets. However, while lunar ISRU has significant potential for mass, cost, and risk reduction for human lunar missions, it has never been demonstrated before in space. To demonstrate that ISRU can meet mission needs and to increase confidence in incorporating ISRU capabilities into mission architectures, terrestrial laboratory and analog field testing along with robotic precursor missions are required. A stepwise approach with international collaboration is recommended. The first step is to understand the resources available through orbital and surface exploration missions. Resources of particular interest are hydrogen, hydroxyl, water, and other polar volatile resources recently measured by Chandrayaan, Lunar Reconnaissance Orbiter (LRO), and the Lunar Crater Observation and Sensing Satellite (LCROSS). The second step is to demonstrate critical aspects of ISRU systems to prove ISRU is feasible under lunar environmental and resource conditions (ex. subscale oxygen extraction from regolith). The third step is to perform integrated missions with ISRU and other connected systems, such as power, consumable storage, surface mobility, and life support at a relevant mission scale to demonstrate ISRU capabilities as well as the critical interfaces with other exploration systems. If possible, the mission should demonstrate the use of ISRU products (ex. in a rocket engine or fuel cell). This dress rehearsal mission would be the final step before full implementation of ISRU into human missions, and may be performed during human lunar exploration activities. This stepwise approach is the most conservative approach, and may only be possible with international cooperation due to the limited number of robotic missions each nation/space agency can perform within their budget.

Sanders, Gerald B.↗

DOE OSTI2023

Pulsed Light Synthesis of High Entropy Nanocatalysts with Enhanced Catalytic Activity and Prolonged Stability for Oxygen Evolution Reaction

The ability to synthesize compositionally complex nanostructures rapidly is a key to high-throughput functional materials discovery. In addition to being time-consuming, a majority of conventional materials synthesis processes closely follow thermodynamics equilibria, which limit the discovery of new classes of metastable phases such as high entropy oxides (HEO). Herein, a photonic flash synthesis of HEO nanoparticles at timescales of milliseconds is demonstrated. By leveraging the abrupt heating and cooling cycles induced by a high-power-density xenon pulsed light, mixed transition metal salt precursors undergo rapid chemical transformations. Hence, nanoparticles form within milliseconds with a strong affinity to bind to the carbon substrate. Oxygen evolution reaction (OER) activity measurements of the synthesized nanoparticles demonstrate two orders of magnitude prolonged stability at high current densities, without noticeable decay in performance, compared to commercial IrO 2 catalyst. This superior catalytic activity originates from the synergistic effect of different alloying elements mixed at a high entropic state. It is found that Cr addition influences surface activity the most by promoting higher oxidation states, favoring optimal interaction with OER intermediates. The proposed high-throughput method opens new pathways toward developing next-generation functional materials for various electronics, sensing, and environmental applications, in addition to renewable energy conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Low Temperature CO 2 Hydrogenation on Unsupported Mo 2 C Catalysts

CO 2 hydrogenation to methanol, a key reaction for decarbonizing the fuel and chemical industries, requires catalyst formulations that hydrogenate CO 2 selectively to methanol at temperatures where methanol conversion is not significantly equilibrium limited (<423 K). Herein we report continuous CO 2 hydrogenation at low temperatures (348-408 K, H 2 /CO 2 = 0.1-50, 5-35 bar) with high selectivity to methanol (up to ca. 80%) over unsupported β-Mo 2 C catalysts. Active site density quantification via titration with trifluoroacetic acid at reaction temperatures enables an assessment of site-specific rates. Methanation and reverse water gas shift (RWGS) occur concurrently with methanol synthesis during CO 2 hydrogenation over Mo 2 C. Reaction pathway analysis, product cofeeds, and reversibility formalisms show that all products form through primary reaction pathways from CO 2 , but secondary reactions of CO contribute significantly to rates of methanation. Dependences of forward rates on reactant and product concentration determined by independently varying the CO 2 , H 2 , CO, H 2 O, CH 3 OH, and CH 4 pressure in conjunction with reversibility formalisms reveal that all products form through H-assisted CO 2 activation and involve partially hydrogenated CO 2 -derived intermediates. Here, these inferences were verified by quantitative agreement between measured site-time yields and site-time yields predicted by closed form kinetic rate expressions in an integral reactor model over widely varying conditions (85-2000 kPa H 2 , 80-1500 kPa CO 2 , 0-45 kPa H 2 O, 0-21 kPa CO, 0-25 kPa CH 3 OH, 0-75 kPa CH 4 , 5-87 mol Mo s s mol CO 2 -1 ). Coverages calculated based on the kinetic model reveal that the Mo 2 C surface is covered with bidentate CO- and CO 2 -derived intermediates of the stoichiometry H 2 CO 2 and H 2 CO, indicating that H 2 and CO x do not compete for surface occupancy but instead adsorb cooperatively to form partially hydrogenated intermediates. Hydrogenation of the CO-derived H 2 CO** intermediate favors methanation, while hydrogenation of CO 2 -derived H 2 CO 2 ** favors methanol synthesis. Together, these findings demonstrate the ability of unsupported Mo 2 C to catalyze the hydrogenation of CO 2 to methanol at low temperatures and provide insight into the reaction network and mechanisms involved in its formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1993

Pigs in cyberspace

Exploration and colonization of the universe awaits, but Earth-adapted biological humans are ill-equipped to respond to the challenge. Machines have gone farther and seen more, limited though they presently are by insect-like behavior inflexibility. As they become smarter over the coming decades, space will be theirs. Organizations of robots of ever increasing intelligence and sensory and motor ability will expand and transform what they occupy, working with matter, space and time. As they grow, a smaller and smaller fraction of their territory will be undeveloped frontier. Competitive success will depend more and more on using already available matter and space in ever more refined and useful forms. The process, analogous to the miniaturization that makes today's computers a trillion times more powerful than the mechanical calculators of the past, will gradually transform all activity from grossly physical homesteading of raw nature, to minimum-energy quantum transactions of computation. The final frontier will be urbanized, ultimately into an arena where every bit of activity is a meaningful computation: the inhabited portion of the universe will be transformed into a cyberspace. Because it will use resources more efficiently, a mature cyberspace of the distant future will be effectively much bigger than the present physical universe. While only an infinitesimal fraction of existing matter and space is doing interesting work, in a well developed cyberspace every bit will be part of a relevant computation or storing a useful datum. Over time, more compact and faster ways of using space and matter will be invented, and used to restructure the cyberspace, effectively increasing the amount of computational spacetime per unit of physical spacetime. Computational speed-ups will affect the subjective experience of entities in the cyberspace in a paradoxical way. At first glimpse, there is no subjective effect, because everything, inside and outside the individual, speeds up equally. But, more subtly, speed-up produces an expansion of the cyber universe, because, as thought accelerates, more subjective time passes during the fixed (probably lightspeed) physical transit time of a message between a given pair of locations - so those fixed locations seem to grow farther apart. Also, as information storage is made continually more efficient through both denser utilization of matter and more efficient encodings, there will be increasingly more cyber-stuff between any two points. The effect may somewhat resemble the continuous-creation process in the old steady-state theory of the physical universe of Hoyle, Bondi and Gold, where hydrogen atoms appear just fast enough throughout the expanding cosmos to maintain a constant density.

Moravec, Hans↗

NASA NTRS2001

Chemical Engineering in Space

The aerospace industry has long been perceived as the domain of both physicists and mechanical engineers. This perception has endured even though the primary method of providing the thrust necessary to launch a rocket into space is chemical in nature. The chemical engineering and chemistry personnel behind the systems that provide access to space have labored in the shadows of the physicists and mechanical engineers. As exploration into the cosmos moves farther away from Earth, there is a very distinct need for new chemical processes to help provide the means for advanced space exploration. The state of the art in launch systems uses chemical propulsion systems, primarily liquid hydrogen and liquid oxygen, to provide the energy necessary to achieve orbit. As we move away from Earth, there are additional options for propulsion. Unfortunately, few of these options can compare to the speed or ease of use provided by the chemical propulsion agents. It is with great care and significant cost that gaseous compounds such as hydrogen and oxygen are liquefied and become dense enough to use for rocket fuel. These low-temperature liquids fall within a specialty area known as cryogenics. Cryogenics, the science and art of producing cold operating conditions for use on Earth, in orbit, or on some other nonterrestrial body, has become increasingly important to our ability to travel within our solar system. The production of cryogenic fuels and the long-term storage of these fluids are necessary for travel. As our explorations move farther away from Earth, we need to address how to produce the necessary fuels to make a round-trip. The cost and the size of these expeditions are extreme at best. If we take everything necessary for our survival for the round-trip, we invalidate any chance of travel in the near future. As with the early explorers on Earth, we need to harvest much of our energy and our life support from the celestial bodies. The in situ production of these energy sources is paramount to success. We are currently working on several processes to produce the propellants that would allow us to visit and explore the surface of Mars. The capabilities currently at our disposal for launching and delivering equipment to another planet or satellite dictate that the size and scale of any hardware must be extremely small. The miniaturization of the processes needed to prepare the in situ propellants and life support commodities is a real challenge. Chemical engineers are faced with the prospect of reproducing an entire production facility in miniature so the complex can be lifted into space and delivered to our destination. Another area that does not normally concern chemical engineers is the extreme physical aspects payloads are subjected to with the launch of a spacecraft. Extreme accelerations followed by the sudden loss of nearly all gravitational forces are well outside normal equipment design conditions. If the equipment cannot survive the overall trip, then it obviously will not be able to yield the needed products upon arrival. These launch constraints must be taken into account. Finally, we must consider both the effectiveness and efficiencies of the processes. A facility located on the Moon or Mars will not have an unlimited supply of power or other ancillary utilities. For a Mars expedition, the available electric power is severely limited. The design of both the processes and the equipment must be considered. With these constraints in mind, only the most efficient designs will be viable. Cryogenics, in situ resource utilization, miniaturization, launchability, and power/process efficiencies are only a few of the areas that chemical engineers provide support and expertise for the exploration of space.

Lobmeyer, Dennis A.↗

DOE OSTI2021

Oxygen Electrocatalysis on Mixed-Metal Oxides/Oxyhydroxides: From Fundamentals to Membrane Electrolyzer Technology

Catalyzing the oxygen evolution reaction (OER) is important for key energy-storage technologies, particularly water electrolysis and photoelectrolysis for hydrogen fuel production. Under neutral-to-alkaline conditions, first-row transition-metal oxides/(oxy)hydroxides are the fastest-known OER catalysts and have been the subject of intense study for the past decade. Critical to their high performance is the intentional or accidental addition of Fe to Ni/Co oxides that convert to layered (oxy)hydroxide structures during the OER. Unraveling the role that Fe plays in the catalysis and the molecular identity of the true “active site” has proved challenging, however, due to the dynamics of the host structure and absorbed Fe sites as well as the diversity of local structures in these disordered active phases. In this Account, we highlight our work to understand the role of Fe in Ni/Co (oxy)hydroxide OER catalysts. We first discuss how we characterize the intrinsic activity of the first-row transition-metal (oxy)hydroxide catalysts as thin films by accounting for the contributions of the catalyst-layer thickness (mass loading) and electrical conductivity as well as the underlying substrate’s chemical interactions with the catalyst and the presence of Fe species in the electrolyte. We show how Fe-doped Ni/Co (oxy)hydroxides restructure during catalysis, absorb/desorb Fe, and in some cases degrade or regenerate their activity during electrochemical testing. We highlight the relevant techniques and procedures that allowed us to better understand the role of Fe in activating other first-row transition metals for OER. We find several modes of Fe incorporation in Ni/Co (oxy)hydroxides and show how those modes correlate with activity and durability. We also discuss how this understanding informs the incorporation of earth-abundant transition-metal OER catalysts in anion-exchange-membrane water electrolyzers (AEMWE) that provide a locally basic anode environment but run on pure water and have advantages over the more-developed proton-exchange-membrane water electrolyzers (PEMWE) that use platinum-group-metal (PGM) catalysts. We outline the key issues of introducing Fe-doped Ni/Co (oxy)hydroxide catalysts at the anode of the AEMWE, such as the oxidative processes triggered by Fe species traveling through the polymer membrane, pH-gradient effects on the catalyst stability, and possibly limited catalyst utilization in the compressed stack configuration. We also suggest possible mitigation strategies for these issues. Lastly, we summarize remaining challenges including the long-term stability of Fe-doped Ni/Co (oxy)hydroxides under OER conditions and the lack of accurate models of the dynamic active surface that hinder our understanding of, and thus ability to design, these catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1999

Instrumentation Working Group Summary

The Instrumentation Working Group compiled a summary of measurement techniques applicable to gas turbine engine aerosol precursors and particulates. An assessment was made of the limits, accuracy, applicability, and technology readiness of the various techniques. Despite advances made in emissions characterization of aircraft engines, uncertainties still exist in the mechanisms by which aerosols and particulates are produced in the near-field engine exhaust. To adequately assess current understanding of the formation of sulfuric acid aerosols in the exhaust plumes of gas turbine engines, measurements are required to determine the degree and importance of sulfur oxidation in the turbine and at the engine exit. Ideally, concentrations of all sulfur species would be acquired, with emphasis on SO2 and SO3. Numerous options exist for extractive and non-extractive measurement of SO2 at the engine exit, most of which are well developed. SO2 measurements should be performed first to place an upper bound on the percentage of SO2 oxidation. If extractive and non-extractive techniques indicate that a large amount of the fuel sulfur is not detected as SO2, then efforts are needed to improve techniques for SO3 measurements. Additional work will be required to account for the fuel sulfur in the engine exhaust. Chemical Ionization Mass Spectrometry (CI-MS) measurements need to be pursued, although a careful assessment needs to be made of the sampling line impact on the extracted sample composition. Efforts should also be placed on implementing non-intrusive techniques and extending their capabilities by maximizing exhaust coverage for line-of-sight measurements, as well as development of 2-D techniques, where feasible. Recommendations were made to continue engine exit and combustor measurements of particulates. Particulate measurements should include particle size distribution, mass fraction, hydration properties, and volatile fraction. However, methods to ensure that unaltered samples are obtained need to be developed. Particulate speciation was also assigned a high priority for quantifying the fractions of carbon soot, PAH, refractory materials, metals, sulfates, and nitrates. High priority was also placed on performing a comparison of particle sizing instruments. Concern was expressed by the workshop attendees who routinely make particulate measurements about the variation in number density measured during in-flight tests by different instruments. In some cases, measurements performed by different groups of researchers during the same flight tests showed an order of magnitude variation. Second priority was assigned to measuring concentrations of odd hydrogen and oxidizing species. Since OH, HO2, H2O2, and O are extremely reactive, non-extractive measurements are recommended. A combination of absorption and fluorescence is anticipated to be effective for OH measurements in the combustor and at the engine exit. Extractive measurements of HO2 have been made in the stratosphere, where the ambient level of OH is relatively low. Use of techniques that convert HO2 to OH for combustor and engine exit measurements needs to be evaluated, since the ratio of HO2/OH may be 1% or less at both the combustor and engine exit. CI-MS might be a viable option for H2O2, subject to sampling line conversion issues. However, H2O2 is a low priority oxidizing species in the combustor and at the engine exit. Two candidates for atomic oxygen measurements are Resonance Enhanced Multi-Photon Ionization (REMPI) and Laser-Induced Fluorescence (LIF). Particulate measurement by simultaneous extractive and non-extractive techniques was given equal priority to the oxidizer measurements. Concern was expressed over the ability of typical ground test sampling lines to deliver an unaltered sample to a remotely located instrument. It was suggested that the sampling probe and line losses be checked out by attempting measurements using an optical or non-extractive technique immediately upstream of the sampling probe. This is a possible application for Laser Induced Incandescence (LII) as a check on the volume fraction of soot. Optical measurements of size distribution are not well developed for ultrafine particles less than about 20 nm in diameter, so a non-extractive technique for particulate size distribution cannot be recommended without further development. Carbon dioxide measurements need to be made to complement other extractive measurement techniques. CO2 measurements enable conversion of other species concentrations to emission indices. Carbon monoxide, which acts as a sink for oxidizing species, should be measured using non-extractive techniques. CO can be rapidly converted to CO2 in extractive probes, and a comparison between extractive and non-extractive measurements should be performed. Development of non-extractive techniques would help to assess the degree of CO conversion, and might be needed to improve the concentration measurement accuracy. Measurements of NO(x) will continue to be critical due to the role of NO and NO2 in atmospheric chemistry, and their influence on atmospheric ozone. Time-resolved measurements of temperature, velocity, and species concentrations were included on the list of desired measurement. Thermocouples are typically adequate for engine exit measurements. PIV and LDV are well established for obtaining velocity profiles. The techniques are listed in the accompanying table; are divided into extractive and non-extractive techniques. Efforts were made to include a measurement uncertainty for each technique. An assessment of the technology readiness was included.

Zaller, Michelle↗

NASA NTRSDate not supplied

Effect of salinity on the preservation of biomarkers in hypersaline microbial mat kerogens

Kerogen is the residue that remains after the minerals and organic compounds have been extracted from a rock using acid and organic solvents, respectively [1]. It is not only the largest organic carbon sink in the geological record but the best-preserved fraction due to its recalcitrance and ability to retain syngenetic source information during deposition [2]. Due to the complex, macromolecular, cross-linked polymeric structure of kerogen, it is difficult to analyse intact, often requiring breakdown into smaller subunits through thermal (pyrolysis) or chemical treatment (chemolysis) [3]. Saline and hypersaline environments host diverse microbial communities, which can trap and bind organic matrices such as cellular components (e.g., extracellular polymeric substances, cell wall, peptidoglycan, sheath material, etc.) with sediments, forming layered, laminated structures called microbial mats. Here we present depth profiles of two hypersaline cores through a microbial mat with differing total salinities. We looked at the composition of organic compounds released from kerogen during high temperature, hydrogen-assisted, pyrolysis to understand the effect of salinity on the composition and timing of their incorporation [4]. Field Site: The Exportadora del Sal S. A. (ESSA) saltern of Guerrero Negro (Baja California Sur, Mexico) lies within a typical sabhka environment adjacent to Laguna Ojo de Liebre. Note the spatial extent of the 13 major ponds of the ESSA system. The GN ponds thrive under well-monitored and stable conditions with steady state accretion and degradation of mat layers (around 0.5–1.4 cm per year). Organic mats typically attain up to 10 cm in thickness, depending on the location, which represents about 60 years of growth since these ponds were established. Sedimentation rate is rapid in these non-lithifying and non-mineralising mats, 1–1.5 cm per year. This environment is ideal for investigating in situ lipid preservation and diagenesis without the influence of constantly changing physical parameters. Methods: P4n5 and P5AB cores were collected as ~9 cm and 6.5 cm fresh cores, respectively, in June 2001 and September 2010, respectively from the ESSA saltern. The P4n5 core (9-9.1% salinity) was taken from Pond 4 near 5 and sub-divided into 10 layers. The P5AB core (11.2% salinity) was taken from Pond 5A near 5B and sub-divided into 8 layers. Lyophilised microbial mat powders were solvent-extracted using a modified Bligh-Dyer method and analysed by gas chromatography-mass spectrometry (GC-MS). Additionally, a subset of layers—layer 4 and layer 7—which represented active biomass and sediment-processed, respectively, were subjected to mild-acid methanolysis. The respective residues from conventional solvent extraction and acid methanolysis were loaded with a molybdenum sulfide catalyst and placed into a stainless-steel reactor. Samples were run on the hydropyrolysis set up (heated to 500 °C with 13-15 MPa of H2 pressure), extracted, and analysed by GC-MS. Results: Molecular profiles from the two ponds were significantly different and reflect the contributions of different photosynthetic and respiratory microbial communities to preserved organic matter. For example, the higher salinity P5AB core showed evidence of greater archaeal inputs (similarly observed in lab culture experiments [5]) as well as potential kerogen-bound carotenoids/carotenoid rearranged products or fragments. A hydrophobic emulsion formed during the acid methanolysis processing of layer 4 from both P4n5 and P5AB and layer 7 of P5AB. Hydropyrolysis of this hydrophobic residues released a greater abundance of polycyclic lipids relative to the pre-extracted control. Implications and Future Work: Catalytic hydropyrolysis of kerogen can rapidly generate abundant saturated pyrolysate products from the bound biomarker pool without altering the structures or stereochemistries of the products [6]. Chemical processing of solvent-extractable residues indicated that cellular matrices such as extracellular polymeric substances (EPS) may play a role in the sequestration of polycyclic lipid biomarkers such as steranes and hopanes. Their higher relative abundance compared to the pre-extracted control in the higher salinity layers and cores preliminarily aligns with this hypothesis, although further experiments are required to confirm this. It has been well-documented that EPS plays an important role in mineralisation, specifically carbonate formation, in microbial ecosystems. EPS can enhance calcium carbonate precipitation by providing diffusion-limited sites that create alkalinity gradients in response to microbial processes [7]. It has been experimentally demonstrated that salinity influences the total amount of EPS (both loosely- and tightly-bound) which increases with increasing salinity [8]. The higher salinity at Guerrero Negro switches the microbial population from filamentous Microcoleus to being dominated by Phormidium, Oscillatoria, and unicellular cyanobacteria. We demonstrated that lipid binding into kerogen via strong covalent linkages occurs at the very earliest stages of sedimentary diagenesis. We are currently investigating the influence of salinity on organic preservation through experimental and modelling approaches. Understanding how key biomarkers transform into preserved organic matter (i.e., from precursor biolipids to bound geolipids) in brine ecosystems will aid the search for organic biosignatures on other planetary bodies, especially Icy Moons and modern Mars.

hypersaline↗