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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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All sourcesNASA NTRSDOE OSTI
NASA NTRS2019

Two-Phase Convection Heat Transfer Correlations for Liquid Hydrogen Pipe Chilldown

Recently, heat transfer correlations based on liquid nitrogen (LN2) and liquid hydrogen (LH2) pipe quenching data were developed to improve the predictive accuracy of lumped node codes like SINDA/FLUINT and the Generalized Fluid System Simulation Program (GFSSP). After implementing these correlations into both programs, updated model runs showed strong improvement in LN2 pipe chilldown modeling but only modest improvement in LH2 modeling. Due to large differences in thermal and fluid properties between the two fluids, results indicated a need to develop a separate set of LH2-only correlations to improve the accuracy of the simulations. This paper presents a new set of two-phase convection heat transfer correlations based on LH2 pipe quenching data. A correlation to predict the bulk vapor temperature was developed after analysis showed that high amounts of thermal nonequilibrium of the liquid and vapor phases occurred during film boiling of LH2. Implemented in a numerical model, the new correlations achieve a mean absolute error of 19.5 K in the predicted wall temperature when compared to recent LH2 pipe chilldown data, an improvement of 40% over recent GFSSP predictions. This correlation set can be implemented in simulations of the transient LH2 chilldown process. Such simulations are useful for predicting the chilldown time and boil-off mass of LH2 for applications such as the transfer of LH2 from a ground storage tank to the rocket vehicle propellant tank, or through a rocket engine feedline during engine startup.

critical heat flux↗
DOE OSTI2026

Hidden features in the OH-stretching spectra of amino acid decorated air–water interfaces

Chemical reactivity at the air–water interface is governed by the interfacial solvation of reactive species. For instance, during aqueous amino acid-based CO 2 absorption, water reorganizes around the reactive sites and couples dynamically with reaction pathways, facilitating the reaction. In this context, surface-sensitive vibrational sum-frequency generation (vSFG) spectroscopy can probe the OH stretch vibrations of interfacial water and determine the solvation structures around reactants and products, thereby furthering our understanding of the role of interfacial solvation. However, vSFG spectra of the air–water interface in the presence of charged species can be remarkably complex; key species-bound local water structures with distinct orientations may be hidden beneath prominent vSFG peaks arising from water–water hydrogen bonds and remain difficult to resolve. Here, we measure and compute vSFG spectra of the water OH stretch at air–water interfaces decorated with amino acids in their zwitterionic and anionic forms, as well as equimolar mixtures of these forms with bicarbonate. The latter represents post-CO 2 -absorption conditions. We find that computing depth- and frequency-dependent spectral densities—decomposed into contributions from water molecules hydrogen-bonded exclusively to other water molecules, exclusively to amines, exclusively to carboxylates, or shared between these polar/charged groups—is indispensable for accurate interpretation of the vSFG spectra. Key findings include orientational flip-flop in water sub-layers, strong carboxylate-water H-bonding, and water orientational ordering extending into the bulk aqueous phase induced by anionic amino acids. Here, this study provides a computational spectroscopic platform for improved understanding of interfacial solvation relevant to interfacial reactivity.

Air-water interface↗
DOE OSTI2024

A general flame aerosol route to high-entropy nanoceramics

High-entropy ceramics are an emerging class of materials with fascinating characteristics. However, elemental immiscibility and crystal complexity limit the development of a general synthesis strategy, and common methods yield bulk materials. Here, we introduce a transformative non-equilibrium flame aerosol technique for synthesizing high-entropy nanoceramics. This scalable, one-step process enables the production of high-entropy oxide nanoceramics with an unprecedented diversity of crystal structures, including fluorite-phase materials that integrate up to 22 distinct cation elements. The method’s capacity for entropic stabilization and grain refinement significantly improves the thermal stability of these nanostructures. In a representative application, a Pt-(MgCoNiCuZn)O high-entropy single-atom catalyst showed superior activity and long-term stability, maintaining constant CO 2 conversion over 670 h and dramatically outperforming conventional catalysts. Finally, the general approach opens a vast composition and structure space for the creation of high-entropy oxide nanomaterials for application across diverse fields, including catalysis, energy storage, sensing, and thermal management.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Experimental determinations of carbon and hydrogen isotope fractionations and methane clumped isotope compositions associated with ethane pyrolysis from 550 to 600°C

Methane clumped isotope compositions signify the relative natural abundances of rare, doubly substituted isotopic species of methane ( 13 CH 3 D and 12 CH 2 D 2 ) and have emerged as a new isotopic tool to trace the sources, sinks, and lifecycles of methane in the environment. Such measurements can identify equilibration (or reequilibration) temperatures if found to be in isotopic equilibrium or non-equilibrium processes (e.g., kinetically controlled reactions or mixing) if not in isotopic equilibrium. Naturally occurring thermogenic methane—formed by the thermally activated breakdown of larger organic molecules—has been found to have clumped isotope compositions consistent with equilibrium at reasonable gas formation temperatures in some settings and non-equilibrium processes occurring during either formation, migration, storage, or extraction in others. To explore the potential controls on the isotopic composition of thermogenic methane, we conducted isothermal time-series ethane pyrolysis experiments at 550 and 600 °C to measure methane and ethane 13 C/ 12 C and D/H fractionations and methane clumped isotope compositions (resolved 13 CH 3 D and 12 CH 2 D 2 ). We explore the effects of modifying the initial clumped isotope composition of ethane and the addition of water vapor to pyrolysis experiments. We observe that ethane and methane 13 C/ 12 C are controlled by kinetic isotope effects and Rayleigh distillation processes. In contrast, ethane and methane D/H and methane clumped isotope compositions appear to be controlled by a combination of these processes and hydrogen isotope exchange. The hydrogen isotope exchange processes lead to isotopic equilibrium as reaction completion is approached for both D/H (ethane/methane) and methane clumped isotope compositions. Here, we develop a chemical model based on a mass balance approach that accounts for inheritance vs. hydrogen-abstraction formation pathways for singly and doubly substituted isotopologues of ethane and methane that is compared to the experimental data. The model allows the determination of carbon and hydrogen kinetic isotope effects associated with ethane cracking and hydrogen abstraction reactions that, where applicable, we compare to prior theoretical constraints. From the comparison of the model to the experimental data, we infer that the kinetically controlled ethane and methane bulk isotope compositions and methane clumped isotope compositions are controlled by kinetic isotope effects (both primary and secondary) associated with both C–C bond and C–H bond cleavage reactions. Specifically, the methane clumped isotope compositions likely result from a combination of clumped isotope effects associated with ethane breakdown and/or assembly of methane isotopologues (expressed in terms of γ-factor parameters ≠ 1) and combinatorial effects that arise probabilistically. We discuss our experimental results in the context of recent pyrolysis experiments and observations of naturally occurring thermogenic methane. We consider a proposal consistent with observations from nature that the hydrogen isotope exchange reactions that promote equilibration of methane isotopic molecules at or near formation temperature may be facilitated by free radicals generated by pyrolysis reactions. In this framework, isotope exchange effectively ceases when pyrolysis effectively ceases locking in compositions that can be consistent with peak formation temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Anion Effects on the Interfacial Structure and Bulk Physical Properties in Choline-Based Hydrogen-Bonded Electrolytes

Electrolytes consisting of choline (Ch) salts with acetate (Ac) and oxalate (Ox) anions were studied in mixtures with ethylene glycol (EG), in comparison to chloride (Cl)- and bis(trifluorosulfonyl)imide (TFSI)-containing systems to understand the impact of anion size and charge density on the bulk electrolyte and interfacial properties. These represent hydrogen-bonded concentrated electrolytes where the Ch salts are the H-bond acceptors (HBAs) and EG is the H-bond donor (HBD) in 1:2 and 1:4 HBA:HBD ratios. Increased H-bonding in Ch 2 Ox with EG compacts the liquid compared to ChAc, consistent with the increased dissociation energies of the HBA:HBD clusters with Ox –2 calculated by density functional theory (DFT), thus leading to denser and more viscous liquids. Electrochemical impedance spectroscopy (EIS) and surface-enhanced Raman spectroscopy (SERS) were used to investigate interfacial charge density and the electrode surface species. Differential capacitance curves demonstrate weak dependence on potential except for ChAc:EG, where Ac – is found to adsorb on the Au surface, in particular at +0.055 V vs Ag quasi-reference while no specific adsorption was observed on glassy carbon (GC). In situ SERS measurement confirms the formation of a surface layer in the ChAc:EG systems resulting from a Au–acetate interaction. Despite the structural similarities, Ox –2 did not show specific binding or any dependence of capacitance on potential as a result of strongly solvating EG molecules via H-bonds. Furthermore, this study shows that the charge density of the HBAs impacts both bulk properties and the electrical double-layer formation in concentrated H-bonded electrolytes that is relevant to electrochemical kinetics and morphology in electrodeposition processes and energy storage applications.

25 ENERGY STORAGE↗
NASA NTRS2000

Solar Power System Evaluated for the Human Exploration of Mars

The electric power system is a crucial element of any mission for the human exploration of the Martian surface. The bulk of the power generated will be delivered to crew life support systems, extravehicular activity suits, robotic vehicles, and predeployed in situ resource utilization (ISRU) equipment. In one mission scenario, before the crew departs for Mars, the ISRU plant operates for 435 days producing liquefied methane and oxygen for ascent-stage propellants and water for crew life support. About 200 days after ISRU production is completed, the crew arrives for a 500-day surface stay. In this scenario, the power system must operate for a total of 1130 days (equivalent to 1100 Martian "sols"), providing 400 MW-hr of energy to the ISRU plant and up to 18 kW of daytime user power. A photovoltaic power-generation system with regenerative fuel cell (RFC) energy storage has been under study at the NASA Glenn Research Center at Lewis Field. The conceptual power system is dominated by the 4000- m2 class photovoltaic array that is deployed orthogonally as four tent structures, each approximately 5 m on a side and 100-m long. The structures are composed of composite members deployed by an articulating mast, an inflatable boom, or rover vehicles, and are subsequently anchored to the ground. Array panels consist of thin polymer membranes with thin-film solar cells. The array is divided into eight independent electrical sections with solar cell strings operating at 600 V. Energy storage is provided by regenerative fuel cells based on hydrogen-oxygen proton exchange membrane technology. Hydrogen and oxygen reactants are stored in gaseous form at 3000 psi, and the water produced is stored at 14.7 psi. The fuel cell operating temperature is maintained by a 40-m2 deployable pumped-fluid loop radiator that uses water as the working fluid. The power management and distribution (PMAD) architecture features eight independent, regulated 600-Vdc channels. Power management and distribution power cables use various gauges of copper conductors with ethylene tetrafluoroethylene insulation. To assess power system design options and sizing, we developed a dedicated Fortran code to predict detailed power system performance and estimate system mass. This code also modeled the requisite Mars surface environments: solar insolation, Sun angles, dust storms, dust deposition, and thermal and ultraviolet radiation. Using this code, trade studies were performed to assess performance and mass sensitivities to power system design parameters (photovoltaic array geometry and orientation) and mission parameters (landing date and landing site latitude, terrain slope, and dust storm activity). Mission analysis cases were also run. Power results are shown in this graph for an analysis case with a September 1, 2012, landing date; 18.95 North latitude landing site; two seasonal dusts storms; and tent arrays. To meet user load requirements and the ISRU energy requirement, an 8-metric ton (MT) power system and 4000-m2 photovoltaic array area were required for the assumed advanced CuInS2 thin-film solar cell technology. In this figure, the top curve is the average daytime photovoltaic array power, the middle curve is average daytime user load power, and the bottom curve is nighttime power. At mission day 1, daytime user power exceeds 120 kW before falling off to 80 kW at the end of the mission. Throughout the mission, nighttime user power is set to the nighttime power requirement. In this analysis, "nighttime" is defined as the 13- to 15-hr period when array power output is below the daytime power requirement. During dust storms, power system capability falls off dramatically so that by mission day 900, a daily energy balance cannot be maintained. Under these conditions, the ISRU plant is placed in standby mode, and the regenerative fuel cell energy storage is gradually discharged to meet user loads.

Kerslake, Thomas W.↗
DOE OSTI2025

Nanoconfinement of High Hydrogen-to-Metal Ratio Lanthanum Hydrides in Functionalized Carbon Hosts

Metal hydrides with a high hydrogen content are important for materials-based hydrogen storage and high-temperature superconductivity. Nanoconfinement of metal hydrides in porous hosts is a promising strategy to tune the thermodynamic stability and control the hydrogen-to-metal ratio. However, lanthanum hydride (LaH x ) nanoconfinement in porous materials has been limited due to the challenges associated with isolating and stabilizing nanoparticles of La or La-hydrides. Here we successfully demonstrated the chemical reduction of La­(III) salts to La(0), and subsequent infiltration into pure CMK-3 and nitrogen-doped CMK-3 (NCMK-3) porous carbons. Transmission electron microscopy measurements revealed a uniform distribution of LaH x species within the carbon hosts, while X-ray absorption and photoelectron spectroscopy provided detailed information about the local chemical environment. Sieverts measurements indicate that LaH x @NCMK-3 could desorb up to 0.75 wt % hydrogen, which is higher than non-nitrogen-functionalized CMK-3 (0.43 wt % H). Density Functional Theory and ab initio molecular dynamics calculations indicate that host–guest interaction energies are favorable for porous carbon with nitrogen defects, which is supported by experimental evidence. Moreover, high-pressure synchrotron X-ray diffraction measurements were conducted using a diamond anvil cell up to 60 GPa and reveal that the nitrogen-functionalized nanoporous carbon host favors the formation of higher H:La ratios in the presence of ammonia borane compared to the pure CMK-3 host. This approach could serve as a suitable platform for developing nanoscale superconducting materials at lower pressures and temperatures compared to bulk.

Shivanna, Mohana↗
DOE OSTI2022

Smooth Modified Surfaces of Silicon for the Study of Ionic Liquid Interfaces by Neutron Reflectometry

Silicon surfaces with termination of hydrogen (H–Si), quartz, native silicon (native-Si), and chemically deposited (Au–Si) cd and sputtered gold (Au–Si) s were fabricated with roughness less than 6 Å to study the solid–liquid interface of the ionic liquid (IL) methyltrioctylammonium bis(trifluoromethylsulfonyl)imide, [N 1888 ][TFSI], by neutron reflectometry (NR). The modifications made to the silicon surface were to obtain a native positive or negative charge similar to a charged surface in electrochemical systems. The differences in scattering length density (SLD) based on mass density and composition of IL were examined. Perpendicular to the substrate surface, a distinct transition between the first ion layer and the bulk liquid is resolved out of the reflectivity data for the gold surfaces and in particular the chemically deposited Au–Si. Other interfaces are best described by a diffuse transition between regions of different SLDs. The diffuse transitions between SLDs observed here suggest that the interfacial structure of IL, while ordered, is best described by a continuous variation in composition as opposed to distinct layers of ions.

25 ENERGY STORAGE↗
DOE OSTI2020

Wettability of ultra-small pores of carbon electrodes by size-asymmetric ionic fluids

Recently, we studied the phase behavior of ionic fluids under confinement using the classical density functional theory within the framework of the restricted primitive model. Additionally, the theoretical results indicate that narrowing the pore size may lead to a drastic reduction in the electric double layer capacitance, while increasing the surface electrical potential would improve the ionic accessibility of micropores. In this work, we extend the theoretical investigation to systems containing size-asymmetric electrolytes that may exhibit a vapor-liquid like phase transition in the bulk phase. The effects of pore size and surface electric potential on the phase diagram and microscopic structures of the confined electrolytes were studied over a broad range of parameters. We found that decreasing the pore size or increasing the surface potential could destabilize the liquid phase in micropores, and capillary evaporation could occur regardless of the size asymmetry between cations and anions. Compared to that in a symmetric ionic system, the vapor-liquid phase separation is more likely to take place as the size asymmetry becomes more pronounced. The phase transition would alter the “accessibility” of ions to micropores and lead to coexisting micropores with different surface charge densities as identified by Monte Carlo simulation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2024

Filament Wound Composite Analysis Using the NASA Multiscale Analysis Tool (NASMAT) and Finite Element Analysis

Fiber reinforced composite materials, owing to their tailorable thermomechanical and functional properties, allow one to produce a structure that is stronger, stiffer, and lighter than its metal counterpart while performing the same function, yielding a more efficient structure. This not only allows for the improvement of current technologies like aircraft structures, but also enables new technologies like gaseous hydrogen storage for mobility applications, which are otherwise impractical when manufactured using traditional metals due to weight and space restrictions or material embrittlement. However, the use of composites imposes greater design and manufacturing challenges on an engineer, since they are heterogenous, having a distinct structure across multiple length scale, behave generally anisotropically at the structural level and require complex manufacturing and processing methods. Capturing this complex behavior requires detailed numerical simulations, including the modeling of microstructural features like undulations, voids, and fiber alignment. In this paper, multiple repeating unit cells (RUCs), representing filament wound composites, are developed (via a script provided in the Appendix) and analyzed. The refinement of these RUCs is varied, and the analyses are performed using both the Abaqus finite element software and the NASA Multiscale Analysis Tool (NASMAT). A study is undertaken to compare the predicted effective elastic properties of the wound RUC to a laminate representation of the wound RUC, which neglects the undulations. Additionally, two different sets of periodic boundary conditions (PBCs) have been examined. One approximates the real boundary conditions using a standard approach and the other represents the PBCs exactly through the use of an offset. Lastly, a comparison of the local elastic stress fields is made among the models and approaches. Since wound structures are often approximated as laminated structures, it is important to understand the degree to which this assumption is valid, namely by first comparing the elastic constants and local elastic fields. This will provide, on the one hand, information concerning the bulk mechanical behavior and, on the other hand, insights concerning local load distributions and likely damage initiation sites.

Composites↗
NASA NTRS1998

Vehicle and Mission Design Options for the Human Exploration of Mars/Phobos Using "Bimodal" NTR and LANTR Propulsion

The nuclear thermal rocket (NTR) is one of the leading propulsion options for future human missions to Mars because of its high specific impulse (Isp-850-1000 s) capability and its attractive engine thrust-to-weight ratio (approximately equal 3-10). To stay within the available mass and payload volume limits of a "Magnum" heavy lift vehicle, a high performance propulsion system is required for trans-Mars injection (TMI). An expendable TMI stage, powered by three 15 thousand pounds force (klbf) NTR engines is currently under consideration by NASA for its Design Reference Mission (DRM). However, because of the miniscule burnup of enriched uranium-235 during the Earth departure phase (approximately 10 grams out of 33 kilograms in each NTR core), disposal of the TMI stage and its engines after a single use is a costly and inefficient use of this high performance stage. By reconfiguring the engines for both propulsive thrust and modest power generation (referred to as "bimodal" operation), a robust, multiple burn, "power-rich" stage with propulsive Mars capture and reuse capability is possible, A family of modular "bimodal" NTR (BNTR) vehicles are described which utilize a common "core" stage powered by three 15 klbf BNTRs that produce 50 kWe of total electrical power for crew life support, an active refrigeration / reliquification system for long term, "zero-boiloff" liquid hydrogen (LH 2 ) storage, and high data rate communications. An innovative, spine-like "saddle truss" design connects the core stage and payload element and is open underneath to allow supplemental "in-line" propellant tanks and contingency crew consumables to be easily jettisoned to improve vehicle performance. A "modified" DRM using BNTR transfer vehicles requires fewer transportation system elements, reduces IMLEO and mission risk, and simplifies space operations. By taking the next logical step--use of the BNTR for propulsive capture of all payload elements into Mars orbit--the power available in Mars orbit grows to 150 kWe compared to 30 kWe for the DRM. Propulsive capture also eliminates the complex, higher risk aerobraking and capture maneuver which is replaced by a simpler reentry using a standardized, lower mass "aerodescent" shell. The attractiveness of the "all BNTR" option is further increased by the substitution of the lightweight, inflatable "TransHab" module in place of the heavier, hard-shell hab module. Use of TransHab introduces the potential for propulsive recovery and reuse of the BNTR/ERV. It also allows the crew to travel to and from Mar on the same BNTR transfer vehicle thereby cutting the duration of the ERV mission in half--from approximately 4.7 to 2.5 years. Finally, for difficult Mars options, such as Phobos rendezvous and sample return missions, volume (not mass) constraints limit the performance of the "all LH 2 " BNTR stage. The use of "LOX-augmented" NTR (LANTR) engines, operating at a modest oxygen-to-hydrogen mixutre ratio (MR) of 0.5, helps to increase "bulk" propellant density and total thrust during the TMI burn. On all subsequent burns, the bimodal LANTR engines operate on LH 2 only (MR=0) to maximize vehicle performance while staying within the lift capability of two Magnum launches.

Nuclear thermal rocket↗
NASA NTRS2002

Vehicle and Mission Design Options for the Human Exploration of Mars/Phobos Using "Bimodal" NTR and LANTR Propulsion

The nuclear thermal rocket (NTR) is one of the leading propulsion options for future human missions to Mars because of its high specific impulse (lsp~850-1000 s) capability and its attractive engine thrust-to-weight ratio (~3-10). To stay within the available mass and payload volume limits of a “Magnum” heavy lift vehicle, a high performance propulsion system is required for trans-Mars injection (TMI). An expendable TMI stage, powered by three 15 thousand pounds force (klbf) NTR engines is currently under consideration by NASA for its Design Reference Mission (DRM). However, because of the miniscule burnup of enriched uranium-235 during the Earth departure phase (~10 grams out of 33 kilograms in each NTR core), disposal of the TMI stage and its engines after a single use is a costly and inefficient use of this high performance stage. By reconfiguring the engines for both propulsive thrust and modest power generation (referred to as “bimodal” operation), a robust, multiple burn, “power-rich” stage with propulsive Mars capture and reuse capability is possible. A family of modular “bimodal” NTR (BNTR) vehicles are described which utilize a common “core” stage powered by three 15 klbf BNTRs that produce 50 kWe of total electrical power for crew life support, an active refrigeration / reliquification system for long term, zero-boiloff liquid hydrogen (LH 2 ) storage, and high data rate communications. An innovative, spine-like “saddle truss” design connects the core stage and payload element and is open underneath to allow supplemental “in-line” propellant tanks and contingency crew consumables to be easily jettisoned to improve vehicle performance. A “modified” DRM using BNTR transfer vehicles requires fewer transportation system elements, reduces IMLEO and mission risk, and simplifies space operations. By taking the next logical step—use of the BNTR for propulsive capture of all payload elements into Mars orbit—the power available in Mars orbit grows to 150 kWe compared to 30 kWe for the DRM. Propulsive capture also eliminates the complex, higher risk aerobraking and capture maneuver which is replaced by a simpler reentry using a standardized, lower mass “aerodescent” shell. The attractiveness of the “all BNTR” option is further increased by the substitution of the lightweight, inflatable “TransHab” module in place of the heavier, hard-shell hab module. Use of TransHab introduces the potential for propulsive recovery and reuse of the BNTR / Earth return vehicle (ERV). It also allows the crew to travel to and from Mars on the same BNTR transfer vehicle thereby cutting the duration of the ERV mission in half—from ~4.7 to 2.5 years. Finally, for difficult Mars options, such as Phobos rendezvous and sample return missions, volume (not mass) constraints limit the performance of the “all LH 2 ” BNTR stage. The use of “LOX-augmented” NTR (LANTR) engines, operating at a modest oxygen-to-hydrogen mixture ratio (MR) of 0.5, helps to increase “bulk” propellant density and total thrust during the TMI burn. On all subsequent burns, the bimodal LANTR engines operate on LH 2 only (MR=0) to maximize vehicle performance while staying within the mass limits of two Magnum launches.

Nuclear thermal rocket↗
DOE OSTI2020

Consequences of long-term water exposure for bulk crystal structure and surface composition/chemistry of nickel-rich layered oxide materials for Li-ion batteries

Water exposure of layered nickel-rich transition metal oxide electrodes, widely used in high-energy lithium-ion batteries, has detrimental effects on the electrochemical performance, which complicates electrode handling and prevents implementation of environmentally benign aqueous processing procedures. Elucidating the degradation mechanisms in play may help rationally mitigate/circumvent key challenges. Here, the bulk structural consequences of long-term (>2.5 years) deuterated water (D2O) exposure of intercalation materials with compositions Li x Ni 0.5 Co 0.2 Mn 0.3 O 2 (NCM523) and Li x Ni 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) are studied by neutron powder diffraction (NPD). Detailed inspection of the NPD data reveals gradual formation of a secondary crystalline phase in all exposed samples, not previously reported for this system. This unknown phase forms faster in liquid- compared to vapor-exposed compounds. Structural modelling of the NPD data shows a stable level of Li/Ni anti-site defects and does not indicate any significant changes in lattice parameters or hydrogen-lithium (D + /Li + ) exchange in the structure. Consequently, the secondary phase formation must take place via transformation rather than modification of the parent material. X-ray photoelectron spectroscopy data indicate formation of LiHCO 3 /Li 2 CO 3 at the surface and a Li-deficient oxide in the sub-surface region of the pristine compounds, and the presence of adsorbed water and transition metal hydroxides at the exposed sample surfaces.

25 ENERGY STORAGE↗
NASA NTRS1991

Oxygen extraction from lunar soil by fluorination

Mining and processing of lunar material could possibly lead to more cost-efficient scenarios for permanent presence of man in space and on the Moon. Production of oxygen for use as propellant seems especially important. Different candidate processes for oxygen-extraction from lunar soil were proposed, of which the reduction of ilmenite by hydrogen was studied most. This process, however, needs the concentration of ilmenite from lunar regolith to a large extent and releases oxygen only with low efficiency. Another possibility - the fluorination method - which works with lunar bulk material as feedstock is discussed. Liberation of oxygen from silicate or oxide materials by fluorination methods has been applied in geoscience since the early sixties. The fact that even at moderate temperatures 98 to 100 percent yields can be attained, suggests that fluorination of lunar regolith could be an effective way of propellant production. Lunar soil contains about 50 percent oxygen by weight which is gained nearly completely through this process as O2 gas. The second-most element Si is liberated as gaseous SiF4. It could be used for production of Si-metal and fluorine-recycling. All other main elements of lunar soil will be converted into solid fluorides which also can be used for metal-production and fluorine-recycling. Preliminary results of small scale experiments with different materials are discussed, giving information on specific oxygen-yields and amounts of by-products as functions of temperature. These experiments were performed with an already existing fluorine extraction and collection device at the University of Bonn, normally used for determination of oxygen-isotopic abundances. Optimum conditions, especially concerning energy consumption, are investigated. Extrapolation of the experimental results to large industrial-type plants on the Moon is tried and seems to be promising at first sight. The recycling of the fluorine is, however, crucial for the process. It might be achieved by means of electrolysis. This needs further investigation. The technical problem of transport and handling of the toxic and corrosive fluorine seems to be solvable and could be done by inert storage vessels.

Seboldt, W.↗
DOE OSTI2025

Tailoring the structural durability and proton conductivity of electrolytes for highly fuel-flexible and reversible ceramic cells

A durable and high ionic conducting electrolyte is critical for achieving fuel-flexible and reversible protonic ceramic cells (PCCs) at reduced temperatures since the developed electrolyte materials are vulnerable to steam, CO 2 , or coking deterioration. Here, we report a fast-conducting electrolyte material BaZr 0.06 Ce 0.7 Y 0.06 Yb 0.06 Hf 0.06 Gd 0.06 O 3−δ (BZCYYbHG), demonstrating excellent durability against CO 2 and H 2 O under the realistic electrolysis operations, and a high conductivity of 0.017 S cm −1 at 550 °C for lowering the PCC operating temperature. Further, density functional theory calculations indicate that the higher configurational entropy of mixing at the B-site cations slightly reduces the hydrogen adsorption energy, suggesting a higher incorporation rate of protons or hydrogen atoms into the electrolyte bulk. Ultimately, single cells with the BZCYYbHG electrolyte deliver peak power densities of 1.39, 1.12, and 0.7 W cm −2 in H 2 , NH 3 , and wet CH 4 at 550 °C with promising durability. In addition, the PCCs achieve a current density of −1.61 A cm −2 at 1.3 V and 550 °C with a high faradaic efficiency of 91.3% at −0.5 A cm −2 , enabling stable operations in steam electrolysis mode under humid air (30% H 2 O), wet air containing CO 2 (up to 10%), and reversible cycling.

25 ENERGY STORAGE↗
DOE OSTI2022

Engineering Nanostructured Interfaces of Hexagonal Boron Nitride-Based Materials for Enhanced Catalysis

Hexagonal boron nitrides (h-BNs) are attractive two-dimensional (2D) nanomaterials that consist of alternating B and N atoms and layered honeycomb-like structures similar to graphene. They have exhibited unique properties and promising application potentials in the field of energy storage and transformation. Recent advances in utilizing h-BN as a metal-free catalyst in the oxidative dehydrogenation of propane have triggered broad interests in exploring h-BN in catalysis. However, h-BN-based materials as robust nanocatalysts in heterogeneous catalysis are still underexplored because of the limited methodologies capable of affording h-BN with controllable crystallinity, abundant porosity, high purity, and defect engineering, which played important roles in tuning their catalytic performance. Here, in this account, our recent progress in addressing the above issues will be highlighted, including the synthesis of high-quality h-BN-based nanomaterials via both bottom-up and top-down pathways and their catalytic utilization as metal-free catalysts or as supports to tune the interfacial electronic properties on the metal nanoparticles (NPs). First, we will focus on the large-scale fabrication of h-BN nanosheets (h-BNNSs) with high crystallinity, improved surface area, satisfactory purity, and tunable defects. h-BN derived from the traditional approaches using boron trioxide and urea as the starting materials generally contains carbon/oxygen impurities and has low crystallinity. Several new strategies were developed to address the issues. Using bulk h-BN as the precursor via gas exfoliation in liquid nitrogen, single- or few-layered h-BNNS with abundant defects could be generated. Amorphous h-BN precursors could be converted to h-BN nanosheets with high crystallinity assisted by a magnesium metallic flux via a successive dissolution/precipitation/crystallization procedure. The as-fabricated h-BNNS featured high crystallinity and purity as well as abundant porosity. An ionothermal metathesis procedure was developed using inorganic molten salts (NaNH 2 and NaBH 4 ) as the precursors. The h-BN scaffolds could be produced on a large scale with high yield, and the as-afforded materials possessed high purity and crystallinity. Second, utilization of the as-prepared h-BN library as metal-free catalysts in dehydrogenation and hydrogenation reactions will be summarized, in which they exhibited enhanced catalytic activity over the counterparts from the previous synthesis method. Third, the interface modulation between metal NPs with the as-prepared defects’ abundant h-BN support will be highlighted. The h-BN-based strong metal–support interaction (SMSI) nanocatalysts were constructed without involving reducible metal oxides via the ionothermal procedure we developed by deploying specific inorganic metal salts, acting as robust nanocatalysts in CO oxidation. Under conditions simulated for practical exhaust systems, promising catalytic efficiency together with high thermal stability and sintering resistance was achieved. Across all of these examples, unique insights into structures, defects, and interfaces that emerge from in-depth characterization through microscopy, spectroscopy, and diffraction will be highlighted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

Testing of a Spray-Bar Zero Gravity Cryogenic Vent System for Upper Stages

The capability to vent in zero gravity without resettling is a fundamental technology need that involves practically all uses of subcritical cryogenics in space. Venting without resettling would extend cryogenic orbital transfer vehicle capabilities. However, the lack of definition regarding liquid/ullage orientation coupled with the somewhat random nature of the thermal stratification and resulting pressure rise rates, lead to significant technical challenges. Typically a zero gravity vent concept, termed a thermodynamic vent system (TVS), consists of a tank mixer to destratify the propellant, combined with a Joule- Thomson (J-T) valve to extract then-nal energy from the propellant. In a cooperative effort, Marshall Space Flight Center's (MSFC's) Multipurpose Hydrogen Test Bed (N4HTB) was used to test a unique "spray bar" TVS system developed by Boeing. A schematic of this system is included in Figure 1. The system consists of a recirculation pump, a parallel flow concentric tube, heat exchanger, and a spray bar positioned close to the longitudinal axis of the tank. In the mixing mode, the recirculation pump withdraws liquid from the tank and sprays it radially into the tank liquid, ullage, and exposed tank surfaces. When energy extraction is required, a small portion of the recirculated liquid is passed sequentially through the J-T expansion valve, the spray bar heat exchanger element, and is vented overboard. The vented vapor cools the circulated bulk fluid, thereby removing thermal energy and reducing tank pressure. Figure 2 is a plot of ullage pressure (P4) and liquid vapor pressure (PSAI) versus time. The pump operates alone, cycling on and off, to destratify the tank liquid and ullage until the liquid vapor pressure reaches the lower set point. At that point, the J-T valve begins to cycle on and off with the pump. Thus, for short duration missions, only the mixer may operate, thus minimizing or even eliminating boil-off losses. The primary advantage of the spray bar configuration is that pressure reduction is achieved independent of liquid and vapor location, thereby enhancing the applicability of normal gravity test data to zero gravity conditions. The in-tank components are minimized with the proposed TVS design. Because the recirculation pump is external to the tank, no electrical power penetration of the tank is required for pump or valve operation. This is especially desirable for L02 tanks since the presence of an electrical ignition source in oxygen represents a critical failure mode. Also, since the critical components (pump, motor, valve, orifice) are external to the tank, system checkout and ground servicing/replacement are easier. For zero-g operation, component replacement external to the tank may be a significant benefit. In addition to satisfying the zero g TVS design objectives, the TVS concept tested offers additional benefits to the integrated subcritical cryogenic storage and launch system.

Lak, Tibor↗
DOE OSTI2023

Milestone 1.2.15: Feasibility of In Situ Accelerated Aluminum Coupon Radiolysis by Synchrotron X-Rays

Extended dry storage of aluminum-clad spent nuclear fuel (ASNF) requires an assessment of the radiolytic generation of molecular hydrogen gas (H2) from the ASNF’s corrosion layers. H2 accumulation can potentially lead to storage canister embrittlement/rupture and the accumulation of flammable gas mixtures in accident scenarios. To date, computational models have been developed for the prediction of radiolytic H2 generation from samples exposed to lower absorbed dose regimes (up to ~3 MGy). However, greater accuracy is needed for higher absorbed doses (> 25 MGy) where the concentration of H2 ultimately reaches a steady-state. Data in this area is limited due to the amount of time taken (months) to accumulate such high gamma doses. Furthermore, a recent study observed radiation-induced damage to the surface of pre-corroded aluminum alloy coupons at high absorbed gamma doses. Despite this observation and its implications, there is currently no computational connection between the radiolytic formation of H2 and changes in the composition and morphology of the cladding’s corrosion layers with absorbed dose. To develop a better understanding of the processes and effects described above, the present study aimed to evaluate the feasibility of leveraging synchrotron x-ray capabilities for coupled accelerated irradiation and in situ surface characterization of ASNF alloys. To that end, National Synchrotron Light Source II (NSLS-II) beamtime was secured and a series of aluminum alloy 1100 (AA1100) wires, prepared under a variety of conditions, were interrogated using ex situ x-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques at Idaho National Laboratory (INL) and ex situ and in situ XRD capabilities at the NSLS-II x-ray powder diffraction (XPD) beamline. Results indicated that performing synchrotron XRD using the available XPD beamline configuration can provide sufficient radiation dose but cannot discern changes in the composition and morphology of sample corrosion layers. Additionally, ex situ XRD and SEM data from Idaho National Laboratory (INL) indicated that the pre-corrosion of AA1100 wires did not generate an appreciably thick corrosion layer, as compared with previous aluminum coupon studies. These thinner surface corrosion layers were not sufficient for detection by both ex situ and in situ synchrotron XRD, specifically under consideration of the NSLS-II XPD beamline’s configuration primarily capturing information from the sample’s bulk material, i.e., aluminum metal. In summary, the use of the NSLS-II XPD beamline for promoting accelerated radiolysis and in situ surface characterization is not appropriate for this program’s goals.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗