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

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At least 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Early-stage uranium-hydrogen corrosion kinetics and mechanism

Research into the early-stage uranium-hydrogen degradation mechanism lacks unified interpretation and understanding due to inadequate temporal and spatial characterization resolution required to unify reaction observations. In this study, white-light interferometry was adapted to characterize the uranium-hydrogen reaction at a temperature of 50 °C and hydrogen pressure of 13.8 kPa. The uranium surface remained unchanged for 62 min during the hydride induction period before the first hydride blister appeared. This blister was monitored from induction through critical spallation and UH₃ powder release during rapid surface hydriding. The critical spallation dimensions measured for height, diameter, area, and perimeter of the first blister were 1.79 µm, 17.58 µm, 187.7 µm 2 and 59.79 µm. Hydriding growth kinetics were assessed by tracking the first hydride site over the reaction time. Analysis shows that the spall-front velocity of the hydride was changing at a rate of 0.91 µm/min which compares favorably with legacy Sievert’s experiments in literature. Total percentage of the surface area hydrided after 242 min was 42.7%, and post-characterization of the UH 3 powders shows both α-UH 3 and β-UH 3 . This work highlights the strength of characterizing the early-stage uranium-hydrogen reaction using white-light interferometry, but more importantly, unifying the understanding and mechanism of the uranium-hydrogen reaction kinetics.

Materials science↗
NASA NTRS1990

The effect of windshear during takeoff roll on aircraft stopping distance

A simulation of a Boeing 727 aircraft during acceleration on the runway is used to determine the effect of windshear on stopping distance. Windshears of various magnitudes, durations, and onset times are simulated to assess the aircraft performance during an aborted takeoff on five different runway surfaces. A windshear detection system, active during the takeoff roll and similar to the Honeywell Windshear Detection System is simulated to provide a discrete system to activate aircraft braking upon shear detection. The results of the simulation indicate that several factors effect the distance required to stop the aircraft. Notable among these are gross weight, takeoff flap position, runway characteristics, and pilot reaction time. Of the windshear parameters of duration, onset and magnitude, magnitude appears to have the most significant effect.

Zweifel, Terry↗
DOE OSTI2017

Effects of lignin structure on hydrodeoxygenation reactivity of pine wood lignin to valuable chemicals

Hydrodeoxygenation (HDO) of two dilute acid flow through pretreated softwood lignin samples, including residual lignin in pretreated solid residues (ReL) and recovered insoluble lignin in pretreated liquid (RISL), with apparent different physical and chemical structures, was comprehensively studied. A combination of catalysts (HY zeolite and Ru/Al 2 O 3 ) was employed to investigate the effects of lignin structures, especially condensed structures, on the HDO upgrading process. Results indicated that the condensed structure and short side chains in lignin hindered its HDO conversion under different reaction conditions, including catalyst loading and composition, hydrogen pressure, and reaction time. In addition to lignin structure, HY zeolite was found crucial for lignin depolymerization, while Ru/Al 2 O 3 and relatively high hydrogen pressure (4 MPa) were necessary for upgrading unstable oxy-compounds to cyclohexanes at high selectivity (>95 wt %). Since the lignin structure essentially affects its reactivity during HDO conversion, the yield and selectivity of HDO products can be predicted by detailed characterization of the lignin structure. Furthermore, the insights gained from this study in the fundamental reaction mechanisms based on the lignin structure will facilitate upgrading of lignin to high-value products for applications in the production of both fuels and chemicals.

09 BIOMASS FUELS↗
NASA NTRS1980

The preparation of calcium superoxide in a flowing gas stream and fluidized bed

Superoxides can be used as sources of chemically stored oxygen in emergency breathing apparatus. The work reported here describes the use of a low-pressure nitrogen gas sweep through the reactant bed, for temperature control and water vapor removal. For a given set of gas temperature, bed thickness, and reaction time values, the highest purity calcium superoxide, Ca(O2)2, was obtained at the highest space velocity of the nitrogen gas sweep. The purity of the product was further increased by flow conditions that resulted in the fluidization of the reactant bed. However, scale-up of the low-pressure fluidized bed process was limited to the formation of agglomerates of reactant particles, which hindered thermal control by the flowing gas stream. A radiofrequency flow discharge inside the reaction chamber prevented agglomeration, presumably by dissipation of the static charges on the fluidized particles.

Wood, P. C.↗
DOE OSTI2013

Self-assembled cabbage-like NaInS{sub 2} microstructures with efficient visible light photocatalytic performance

Cabbage-like NaInS{sub 2} microstructures have been synthesized by reacting In(NO{sub 3}){sub 3} with the alkaline sulfur aqueous solution of NaOH in a simple hydrothermal process without any shape-directing surfactants. The cabbage-like NaInS{sub 2} architectures are monodispersed in large quantities. The cabbage-like morphologies depend strongly on the different ratios of S powder to NaOH, the reaction temperature and reaction time. The possible growth mechanism for the formation of cabbage-like NaInS{sub 2} architectures is discussed. The cabbage-like NaInS{sub 2} architectures exhibit the superiority of photocatalytic performance for the photodegradation of RhB irradiation under visible light irradiation. It is believed that the photocatalytic superiority of the cabbage-like NaInS{sub 2} architectures is mainly due to their special surface areas and inner interconnected structural features. - Graphical abstract: Cabbage-like NaInS{sub 2} microstructures were facilely synthesized via simple hydrothermal reaction. The cabbage-like NaInS{sub 2} architectures exhibit the superiority of photocatalytic performance for the photodegradation of RhB irradiation under visible light irradiation. - Highlights: • Cabbage-like NaInS{sub 2} microstructures were facilely synthesized via a hydrothermal reaction. • Influencing parameters on the NaInS{sub 2} morphologies have been discussed in detail. • The cabbage-like NaInS{sub 2} architectures hold efficient photocatalytic performance. • The photocatalytic superiority is mainly due to their special structural features.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Developing the Oxidation Kinetic Model for Magnetite Pellet

Oxidation is a vital phenomenon for magnetite pellets in their excursion through the furnace during induration. One of the pre-requisites for magnetite pellets to achieve homogeneously structured good quality pellets is to have complete oxidation before sintering begins. Partially oxidized magnetite pellets, upon sintering, might result in inhomogeneous structured pellets which could be detrimental to pellet quality. It is necessary to understand the mechanisms responsible for magnetite oxidation, and hence, it is intended in this study to investigate experimentally as well as develop a mathematical model based on oxidation kinetics. Oxidation of pellets is largely influenced by the oxidation kinetics of particles and hence should be studied at particle as well as at pellet scale. The principles of the Grain Model have been adopted to develop the Oxidation Model at pellet scale, whereas the particles’ oxidation follows the Avrami Kinetic Model. Isothermal oxidation experiments performed Thermogravimetric Analyzer showed that oxidation rate of magnetite at pellet scale contained two peaks. They were complemented well by oxidation rates predicted from the model. Further, the pellet was investigated microstructurally at pellet and particle scale to substantiate the findings from the experiments and the model. The oxidation model developed is used to predict the progression of oxidation in the magnetite pellet with respect to the reaction time at three different temperatures (873 K, 973 K, and 1073 K (600 °C, 700 °C, and 800 °C)) and at four levels of oxygen (0.21, 0.30, 0.60, and 1.00 atm) in the oxidizing gas.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Electrolytes in Multiple-Phase Hydrogen Storage Reactions

Multiple-phase hydrogen storage materials such as metal alanates and borohydrides, and destabilized systems offer the possibility of high hydrogen storage capacity with favorable thermodynamics. However, the multiphase nature of these materials intrinsically limits the kinetics due to the required transport of species between phases, which are typically in dry powder form. To address this limitation, the influence of added electrolytes is explored. This approach is motivated by analogy with similar multiphase battery reactions that show reduced kinetic limitations while necessarily containing electrolytes. Previous experimental results showing improved kinetics for MgH2/Sn (using a LiBH4/KBH4 eutectic electrolyte) and NaAlH4 (using a diglyme electrolyte) are further analyzed in terms of this analogy. The results show that the analogy is useful and rate constants are increased. Importantly, the inclusion of an electrolyte also appears to alleviate the continuously decreasing rates with the extent of reaction, which is characteristic of many multiphase hydrides. Instead, reaction rates are approximately constant until near completion. Together, these effects can lead to >10× shorter overall reaction times. In addition, new results are presented for the hydrogenation of MgB2 using Li/K/CsI and Li/K/CsCl eutectic electrolytes, where >60% conversion to Mg(BH4)2 was demonstrated at 350 bar.

08 HYDROGEN↗
DOE OSTI2020

Understanding the Deactivation of Ag–ZrO 2 /SiO 2 Catalysts for the Single-step Conversion of Ethanol to Butenes

Ag–ZrO 2 /SBA-16 has recently been found to be efficient for catalyzing the single-step conversion of ethanol to butene (1- and 2-butene mixtures) in the presence of H 2 . The reaction proceeds via a cascading sequence of reactions over mixed metal and Lewis sites, with the catalyst composition tuned to selectively favor butene formation. However, the catalyst slowly deactivates when evaluated over long reaction times. Here, we evaluated the lifetime of the Ag–ZrO 2 /SBA-16 catalyst system for ethanol-to-butene conversion at 325 °C for up to 800 hours on stream. Several characterization techniques were used to elucidate the mechanism(s) by which catalyst deactivation occurs. Coke deposition, Ag particle sintering, and Ag 0 -to-Ag + oxidation state change were identified to be the major causes of catalyst deactivation. Coke deposits cover primarily Lewis acid sites which are responsible for aldol condensation, Meerwein-Ponndorf-Verley (MPV) reduction, and dehydration reactions. Ag particle sintering and Ag oxidation state change leads to a reduction in the number of metallic Ag sites responsible for the dehydrogenation/hydrogenation steps. The fresh catalyst likely experiences hydrothermal sintering in the early stage of reaction and permanently loses some active Lewis acid sites before reaching a new structural steady state. The deactivation of Lewis acid sites leads to a decrease in overall ethanol conversion, whereas the deactivation of the metallic Ag sites decreases the butene selectivity. For catalyst regeneration, oxidative calcination (at 500 °C) followed by reduction (at 325 °C) successfully removes all the coke species on the catalyst surface and restores the metallic Ag particles of the 4Ag–4ZrO 2 /SBA-16 catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

TGA Study of the Reaction Kinetics of a CuFeMnAlO 4+δ Oxygen Carrier for Methane Chemical Looping Combustion under High Pressure and Atmospheric Pressure Conditions

Reduction and oxidation kinetics of a CuFeMnAlO 4+δ oxygen carrier for methane were studied using an atmospheric thermogravimetric analyzer (TGA) and a pressurized TGA. Important parameters such as temperature (500–900 °C), particle size distribution (150–650 μm), and partial pressures of reactants (methane and oxygen) were evaluated. Results showed that the reduction of the oxygen carrier was not affected by particle size distribution studied in this work, and that above 750 °C, the effect of the temperature on oxygen carrier reduction started to diminish. The reaction time approaches an asymptotic limit as methane partial pressure increases. For oxygen carrier oxidation, it was found that the rate of oxidation increased with increasing oxygen concentration. The effect of the oxygen concentration was more noticeable when the oxygen concentration was below 7.5%. Because of the inherent feature of the oxygen carrier, its chemical looping with oxygen uncoupling property was also assessed. A phase boundary-controlled shrinking sphere model was used to model the test data from the TGAs. Modeling results showed that the oxygen carrier reduction had a reaction order of 1 with an activation energy of ∼46 kJ/mol. Oxygen carrier oxidation demonstrated a reaction order of 1.1 with an activation energy of ∼55 kJ/mol. Additionally, the differences of the experimental results between the atmospheric pressure TGA and the pressurized TGA were discussed in detail and the limitations of the pressurized TGA were highlighted.

Hydrocarbons↗
NASA NTRS1993

Effects of illumination on human nocturnal serum melatonin levels and performance

In humans, exposure to bright light at night suppresses the normal nocturnal elevation in circulating melatonin. Oral administration of pharmacological doses of melatonin during the day, when melatonin levels are normally minimal, induces fatigue. To examine the relationship between illumination, human pineal function, and behavior, we monitored the overnight serum melatonin profiles and behavioral performance of 24 healthy male subjects. On each of three separate occasions subjects participated in 13.5 h (1630-0800 h) testing sessions. Each subject was assigned to an individually illuminated workstation that was maintained throughout the night at an illumination level of approximately 300, 1500, or 3000 lux. Melatonin levels were significantly diminished by light treatment, F(2, 36) = 12.77, p < 0.001, in a dose-dependent manner. Performance on vigilance, reaction time, and other tasks deteriorated throughout the night, consistent with known circadian variations in these parameters, but independent of ambient light intensity and circulating melatonin levels.

NASA Program Space Physiology and Countermeasures↗
NASA NTRSDate not supplied

Evaluation of Performance, Fatigue and Workload During Real-time, Reactive Telerobotic Mission Control Operations

Real-time, reactive telerobotic mission control operations require personnel to actively operate and manage remotely controlled vehicles or robots in real time. Due to the physical separation of the vehicle from the operator, such operations present many additional factors that can influence fatigue (i.e., degraded mental performance) and workload (i.e., mental and physical cost of task requirements), making it difficult to assess how long an individual can safely and accurately conduct operations. The upcoming Volatiles Investigating Polar Exploration Rover (VIPER) mission involves remotely controlling a lunar vehicle from an Earth-based mission control station. METHODS: In order to determine how long personnel could successfully maintain alertness and performance while operating a rover, we studied seven trained operators (i.e., 5 drivers, 2 real-time scientists) in a simulated mission control environment. We further assessed workload in order to determine whether perceived workload levels would change relative to time on task and by time of day. Operators completed two five-hour simulations in a randomized order, beginning at noon and at midnight. Performance was evaluated every 30 minutes using the psychomotor vigilance task (PVT), Karolinska Sleepiness Scale (KSS), and NASA Task Load Index (NASA-TLX). RESULTS: On average, participants rated themselves as sleepier (5.06 ± 2.28) on the night drives compared to the day drives (3.12 ± 1.44; P < .0001). Workload was rated higher during the day drives (37.93 ± 20.09) compared to night (32.09 ± 21.74; P < .01). Lastly, participants had no change in average reaction time between the two drives. CONCLUSIONS: From the analysis, we observed performance began to degrade after approximately three hours of driving. Our findings suggest that rotating drivers at least every three hours would be prudent to allow for breaks, and to minimize performance degradation, particularly during night shifts.

fatigue↗
DOE OSTI2018

CO2 Injection Effect on Geomechanical and Flow Properties of Calcite-Rich Reservoirs

Geologic carbon storage is considered as a requisite to effectively mitigate climate change, so large amounts of carbon dioxide (CO2) are expected to be injected in sedimentary saline formations. CO2 injection leads to the creation of acidic solution when it dissolves into the resident brine, which can react with reservoir rock, especially carbonates. We numerically investigated the behavior of reservoir-caprock system where CO2 injection-induced changes in the hydraulic and geomechanical properties of Apulian limestone were measured in the laboratory. We found that porosity of the limestone slightly decreases after CO2 treatment, which lead to a permeability reduction by a factor of two. In the treated specimens, calcite dissolution was observed at the inlet, but carbonate precipitation occurred at the outlet, which was closed during the reaction time of three days. Additionally, the relative permeability curves were modified after CO2–rock interaction, especially the one for water, which evolved from a quadratic to a quasi-linear function of the water saturation degree. Geomechanically, the limestone became softer and it was weakened after being altered by CO2. Simulation results showed that the property changes occurring within the CO2 plume caused a stress redistribution because CO2 treated limestone became softer and tended to deform more in response to pressure buildup than the pristine rock. The reduction in strength induced by geochemical reactions may eventually cause shear failure within the CO2 plume affected rock. This combination of laboratory experiments with numerical simulations leads to a better understanding of the implications of coupled chemo-mechanical interactions in geologic carbon storage.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Oxidative Dehydrogenation of N ‐Heteroaromatic Alkyl Alcohols and Amines Facilitated by Dearomative Tautomerization

The oxidation of alcohols, amines, and halides is a fundamental transformation in organic chemistry with significant applications in the synthesis of fine chemicals, pharmaceuticals, and natural products. Here we show that a broad variety of N-heteroarenes bearing hydroxymethyl, aminomethyl, or halomethyl groups are oxidatively dehydrogenated to their respective aldehydes by simply heating them in acidic or basic aqueous solution under ambient atmosphere. The quantitative oxidation of 9-acridinemethanol to 9-acridinecarboxaldehyde serves as an illustrative example, proceeding to completion within 3 hours in refluxing 5% aqueous acetic acid or even household vinegar. Quinoline derivatives may be similarly oxidized but require higher temperatures and longer reaction times, while indole derivatives are oxidized under basic conditions. Based on comprehensive regioselectivity screens, internal kinetic isotope competition, and density functional theory (DFT) calculations, we propose a mechanism in which migration of a methylene hydrogen to the pyridinic nitrogen by acid-catalyzed dearomative tautomerization yields an unstable enol or enamine intermediate that then irreversibly loses two hydrogen atoms to atmospheric oxygen. In addition to the simplicity and environmentally benign nature of our method, we observe no indication of any over-oxidation to carboxylic acids. Finally, we demonstrate the synthetic utility of this reaction through two different one-pot formylations of acridine.

Chemistry↗
DOE OSTI2014

Investigating the Synthesis of Ligated Metal Clusters in Solution Using a Flow Reactor and Electrospray Ionization Mass Spectrometry

The scalable synthesis of subnanometer metal clusters containing an exact number of atoms is of interest due to the highly size-dependent catalytic, electronic and optical properties of these species. While significant research has been conducted on the batch preparation of clusters through reduction synthesis in solution, the processes of metal complex reduction as well as cluster nucleation, growth and post-reduction etching are still not well understood. Herein, we demonstrate a temperature-controlled flow reactor for studying cluster formation in solution at well-defined conditions. Employing this technique methanol solutions of a chloro(triphenylphosphine)gold precursor, 1,4-bis(diphenylphosphino)butane capping ligand and borane-tert-butylamine reducing agent were combined in a mixing tee and introduced into a heated capillary with an adjustable length. In this manner, the temperature dependence of the relative abundance of different ionic reactants, intermediates and products synthesized in real time was characterized using online mass spectrometry. A wide distribution of doubly and triply charged cationic gold clusters was observed as well as smaller singly charged metal-ligand complexes. The results demonstrate that temperature plays a crucial role in determining the relative population of cationic gold clusters and, in general, that higher temperature promotes the formation of doubly charged clusters and singly charged metal-ligand complexes while hindering the growth of triply charged clusters. Moreover, the distribution of clusters observed at elevated temperatures is found to be consistent with that obtained at longer reaction times at room temperature, thereby demonstrating that heating may be used to access cluster distributions characteristic of different stages of reduction synthesis in solution.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2014

Indium telluride nanotubes: Solvothermal synthesis, growth mechanism, and properties

A convenient solvothermal approach was applied for the first time to synthesize In{sub 2}Te{sub 3} nanotubes. The morphology of the resultant nanotubes was studied by scanning electron microscopy and transmission electron microscopy. Nanotubes with a relatively uniform diameter of around 500 nm, tube wall thickness of 50–100 nm, and average length of tens of microns were obtained. X-ray diffraction, X-ray photoelectron spectroscopy, and Raman spectroscopy were used to study the crystal structures, composition, and optical properties of the products. To understand the growth mechanism of the In{sub 2}Te{sub 3} nanotubes, we studied the influences of temperature, reaction time, and polyvinylpyrrolidone (PVP) and ethylene diamine (EDA) dosages on the final products. Based on the experimental results, a possible growth mechanism of In{sub 2}Te{sub 3} nanotubes was proposed. In this mechanism, TeO{sub 3}{sup −2} is first reduced to allow nucleation. Circumferential edges of these nucleated molecules attract further deposition, and nanotubes finally grow rapidly along the c-axis and relatively slowly along the circumferential direction. The surface area of the products was determined by BET and found to be 137.85 m{sup 2} g{sup −1}. This large surface area indicates that the nanotubes may be suitable for gas sensing and hydrogen storage applications. The nanotubes also showed broad light detection ranging from 300 nm to 1100 nm, which covers the UV–visible–NIR regions. Such excellent optical properties indicate that In{sub 2}Te{sub 3} nanotubes may enable significant advancements in new photodetection and photosensing applications. -- Graphical abstract: A convenient solvothermal approach was applied to synthesize In{sub 2}Te{sub 3} nanotubes, which has not been reported in the literature for our knowledge. Surface area of this material is 137.85 m{sup 2} g{sup −1} from the BET testing, and such a high value makes it probably suitable for gas sensing and hydrogen storage, compared with the nanowires. The nanotube device also has a broad light detection range from 300 nm to 1100 nm, covering the UV–visible–NIR region. This good performance of In{sub 2}Te{sub 3} nanotubes may enable significant advancements of new photodetection and photosensing applications. Highlights: • The In{sub 2}Te{sub 3} nanotube device also has a broad light detection range from 300 nm to 1100 nm. • The nanotube is 137.85 m{sup 2} g{sup −1}, which makes it suitable for gas sensing and hydrogen storage. • A possible growth mechanism of the indium telluride nanotubes was proposed. • In addition, no In{sub 2}Te{sub 3} nanotubes have been reported until now.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Machine Learning Analysis of Direct Dynamics Trajectory Outcomes for Thermal Deazetization of 2,3-Diazabicyclo[2.2.1]hept-2-ene

Experimentally, the thermal gas-phase deazetization of 2,3-diazabicyclo[2.2.1]hept-2-ene (1) results in the loss of N2 and the formation of bicyclo products 3 (exo) and 4 (endo) in a nonstatistical ratio, with preference for the exo product. Here, we report unrestricted M06-2X quasiclassical trajectories initialized from the concerted N2 ejection transition state that were able to replicate the experimental preference to form 3. We found that the 3:4 ratio results from the relative amounts of very fast (ballistic) exotype trajectories versus trajectories that lead to the 1,3-diradical intermediate 2. These quasiclassical trajectories provided a set of transition-state vibrational, velocity, momenta, and geometric features for the machine learning analysis. Additionally, a selection of popular supervised classification algorithms (e.g., random forest) provided poor prediction of trajectory outcomes based on only transition-state vibrational quanta and energy features. However, these machine learning models provided more accurate predictions using atomic velocities and atomic positions, attaining ~70% accuracy using initial conditions and between 85 and 95% accuracy at later reaction time steps. This increased accuracy allowed the feature importance analysis to reveal that, at the later-time analysis, the methylene bridge out-of-plane bending is correlated with trajectory outcomes for the formation of either the exo product or toward the diradical intermediate. Possible reasons for the struggle of machine learning algorithms to classify trajectories based on transition-state features is the heavily overlapping feature values, the finite but very large possible vibrational mode combinations, and the possibility of chaos as trajectories propagate. We examined this chaos by comparing a set of nearly identical trajectories that differed by only a very small scaling of the kinetic energies resulting from the transition-state reaction coordinate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2009

Orion Emergency Mask Approach

Emergency mask approach on Orion poses a challenge to the traditional Shuttle or Station approaches. Currently, in the case of a fire or toxic spill event, the crew utilizes open loop oxygen masks that provide the crew with oxygen to breath, but also dumps the exhaled oxygen into the cabin. For Orion, with a small cabin volume, the extra oxygen will exceed the flammability limit within a short period of time, unless a nitrogen purge is also provided. Another approach to a fire or toxic spill event is the use of a filtering emergency masks. These masks utilize some form of chemical beds to scrub the air clean of toxic providing the crew safe breathing air for a period without elevating the oxygen level in the cabin. Using the masks and a form of smoke-eater filter, it may be possible to clean the cabin completely or to a level for safe transition to a space suit to perform a cabin purge. Issues with filters in the past have been the reaction time, breakthroughs, and high breathing resistance. Development in a new form of chemical filters has shown promise to make the filtering approach feasible.

Tuan, George C.↗