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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 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
NASA NTRS1988

Computer simulation of multiple pilots flying a modern high performance helicopter

A computer simulation of a human response pilot mechanism within the flight control loop of a high-performance modern helicopter is presented. A human response mechanism, implemented by a low order, linear transfer function, is used in a decoupled single variable configuration that exploits the dominant vehicle characteristics by associating cockpit controls and instrumentation with specific vehicle dynamics. Low order helicopter models obtained from evaluations of the time and frequency domain responses of a nonlinear simulation model, provided by NASA Lewis Research Center, are presented and considered in the discussion of the pilot development. Pilot responses and reactions to test maneuvers are presented and discussed. Higher level implementation, using the pilot mechanisms, are discussed and considered for their use in a comprehensive control structure.

Zipf, Mark E.↗
NASA NTRS1991

A study of fault injection in multichannel spacecraft power systems

NASA/Marshall Space Flight Center proposes to implement fault injection into an electrical power system breadboard to study the reactions of the various control elements of this breadboard. Among the elements to be studied are the remote power controllers, the algorithms in the control computers, and the artificially intelligent control programs resident in this breadboard. To this end, a study of electrical power is being performed to yield a list of the most common power system faults. The results of this study are being applied to a multichannel high-voltage DC spacecraft power system called the Large Autonomous Spacecraft Electrical Power System Breadboard. Some of the reactions of the breadboard to some of the faults which have been encountered are presented along with the results of this study.

Dugal-Whitehead, Norma R.↗
NASA NTRS2003

Growth and Metabolism of the Green Alga, Chlorella Pyrenoidosa, in Simulated Microgravity

The effect of microgravity on living organisms during space flight has been a topic of interest for some time, and a substantial body of knowledge on the subject has accumulated. Despite this, comparatively little information is available regarding the influence of microgravity on algae, even though it has been suggested for long duration flight or occupancy in space that plant growth systems, including both higher plants and algae, are likely to be necessary for bioregenerative life support systems. High-Aspect-Ratio Rotating-Wall Vessel or HARV bioreactors developed at Johnson Space Center provide a laboratory-based approach to investigating the effects of microgravity on cellular reactions. In this study, the HARV bioreactor was used to examine the influence of simulated microgravity on the growth and metabolism of the green alga, Chlorella pyrenoidosa. After the first 2 days of culture, cell numbers increased more slowly in simulated microgravity than in the HARV gravity control; after 7 days, growth in simulated microgravity was just over half (58%) that of the gravity control and at 14 days it was less than half (42%). Chlorophyll and protein were also followed as indices of cell competence and function; as with growth, after 2-3 days, protein and chlorophyll levels were reduced in modeled microgravity compared to gravity controls. Photosynthesis is a sensitive biochemical index of the fitness of photosynthetic organisms; thus, CO2-dependent O2 evolution was tested as a measure of photosynthetic capacity of cells grown in simulated microgravity. When data were expressed with respect to cell number, modeled microgravity appeared to have little effect on CO2 fixation. Thus, even though the overall growth rate was lower for cells cultured in microgravity, the photosynthetic capacity of the cells appears to be unaffected. Cells grown in simulated microgravity formed loose clumps or aggregates within about 2 days of culture, with aggregation increasing over time. Presently, the basis for, or significance of, the cell aggregation is unknown. The results from this study suggest that cell growth and morphological characteristics of green algae may be altered by culture in simulated microgravity. The data obtained to date should provide a solid basis for additional experimentation regarding the influence of modeled microgravity on cell morphology, physiological activity, protein production and possibly gene expression in algal and plant cell systems. The final aim of the study is to provide useful information to elucidate the underlying mechanism for the biological effects of microgravity on cells.

Mills, W. Ronald↗
NASA NTRS2007

Design, Fabrication, and Test of a LOX/LCH4 RCS Igniter at NASA

A workhorse liquid oxygen-liquid methane (LOX/LCH4) rocket igniter was recently tested at NASA Glenn Research Center s (GRC) Research Combustion Laboratory (RCL). These tests were conducted in support of the Reaction Control Engine (RCE) development task of the Propulsion and Cryogenics Advanced Development (PCAD) project. The igniter was a GRC in-house design used to evaluate the ignition processes for LOX/LCH4. The test matrix was developed to examine the flammability of LOX/LCH4 over a range of oxidizer-to-fuel mixture ratios, both in the core fuel flow and total flow. In addition, testing also examined the durability of the hardware by accumulating ignition pulses. Over the course of testing, a total of 1402 individual ignition pulses were successfully demonstrated over the range of mixture ratios. Testing was halted after the failure of the ceramic in the igniter spark plug.

Schneider, Steven J.↗
DOE OSTI2022

Impacts of ruthenium valence state on the electrocatalytic activity of ruthenium ion-complexed graphitic carbon nitride/reduced graphene oxide nanosheets towards hydrogen evolution reaction

Design and engineering of effective electrode catalysts represents a critical first step for hydrogen production by electrochemical water splitting. Nanocomposites based on ruthenium atomically dispersed within a carbon scaffold have emerged as viable candidates. In the present study, ruthenium metal centers are atomically embedded within graphitic carbon nitride/reduced graphene oxide nanosheets by thermal refluxing. Subsequent chemical reduction/oxidation leads to ready manipulation of the ruthenium valence state, as evidenced in microscopic and spectroscopic measurements, and hence enhancement/diminishment of the electrocatalytic activity towards hydrogen evolution reaction in both acidic and alkaline media. Further, this is largely ascribed to the increased/reduced contribution of the Ru valence electrons to the density of state near the Fermi level which dictates the binding and reduction of hydrogen. Results from this study highlight the significance of the valence state of metal centers in the manipulation and optimization of the catalytic performance of single atom catalysts.

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

Reactivity of Iridium Complexes of a Triphosphorus-Pincer Ligand Based on a Secondary Phosphine. Catalytic Alkane Dehydrogenation and the Origin of Extremely High Activity

The selective functionalization of alkanes and alkyl groups is a major goal of chemical catalysis. Toward this end, a bulky triphosphine with a central secondary phosphino group, bis(2-di-t-butyl-phosphinophenyl)phosphine ( tBu P H PP), has been synthesized. When complexed to iridium, it adopts a meridional (“pincer”) configuration. The secondary phosphino H atom can undergo migration to iridium to give an anionic phosphido-based–pincer ( tBu PPP) complex. Stoichiometric reactions of the ( tBu PPP)Ir complexes reflect a distribution of steric bulk around the iridium center in which the coordination site trans to the phosphido group is quite crowded; one coordination site cis to the phosphido is even more crowded; and the remaining site is particularly open. The ( tBu PPP)Ir precursors are the most active catalysts reported to date for dehydrogenation of n-alkanes, by about 2 orders of magnitude. The electronic properties of the iridium center are similar to that of well-known analogous ( R PCP)Ir catalysts. Accordingly, DFT calculations predict that ( tBu PPP)Ir and ( tBu PCP)Ir are, intrinsically, comparably active for alkane dehydrogenation. While dehydrogenation by ( R PCP)Ir proceeds through an intermediate trans-(PCP)IrH 2 (alkene), ( tBu PPP)Ir follows a pathway proceeding via cis-(PPP)IrH 2 (alkene), thereby circumventing unfavorable placement of the alkene at the bulky site trans to phosphorus. ( tBu PPP)Ir and ( tBu PCP)Ir, however, have analogous resting states: square planar (pincer)Ir(alkene). Alkene coordination at the crowded trans site is therefore unavoidable in the resting states. Furthermore, the resting state of the ( tBu PPP)Ir catalyst is destabilized by the architecture of the ligand, and this is largely responsible for its unusually high catalytic activity.

02 PETROLEUM↗
DOE OSTI2023

H 2 generation by the 10 B(n,α) 7 Li reaction in high temperature water

H 2 produced in water from the 10 B(n,α) 7 Li fission reaction has been measured up to 300 °C. Thermal energy neutrons from the Rhode Island Nuclear Science Center's 2 MW reactor interact with boric acid-containing water in temperature-controlled high-pressure cells made from tubing of either titanium or zirconium alloy. After exposure for a minimum of 1 h, the solution sample is extracted and sparged with argon. The H 2 entrained by the sparging gas is sampled with a small mass spectrometer. A small amount of sodium is included in the boric acid solution so that after sparging, samples can be collected for 24 Na activation measurements in a gamma spectrometer to determine the neutron exposure and thus the total energy deposited in solution. The G-value (μmol/J) for H 2 production is obtained for water at a pressure of 25 MPa, over a temperature range from 20 °C to 300 °C. The weak temperature dependence of this yield between 150 °C and 200 °C demonstrates that the bimolecular reaction of pairs of e$^{–}_{aq}$ is a very minor source of H 2 in high LET tracks.

10B↗
NASA NTRS1993

Laboratory studies of low-temperature reactions of C2H with C2H2 and implications for atmospheric models of Titan

Rate coefficients for the reaction C2H + C2H2 - C4H2 + H are measured over the temperature range 170-350 K. The reactions are carried out in a temperature variable flow cell. C2H radicals are produced by pulsed laser photolysis of C2H2 and a tunable infrared color-center laser is used to probe the transient removal of C2H in absorption to derive the rate coefficients. The rate coefficient is obtained and shown to be independent of temperature over the range 170-350 K. The reaction studied is of central importance for models of the photochemistry of the atmospheres of the outer planets, in particular for the satellite Titan, and the implications of the present results for these models are discussed.

Pedersen, Jens O. P.↗
DOE OSTI2025

Fullerene Promotes CO 2 Reduction to Methanol by a Cobalt(II) Phthalocyanine Electrocatalyst

Heterogenization of molecular electrocatalysts offers an attractive way to improve the catalytic selectivity and efficiency of CO 2 conversion to liquid fuels. Herein, we employ density functional theory to compare the mechanism of CO 2 RR by a cobalt(II) tetra(amino)phthalocyanine (Co(II)Pc(NH 2 ) 4 ) electrocatalyst with and without the presence of fullerene support. Our DFT calculations suggest that the CO 2 reduction mechanism is initiated by a metal-based electron reduction followed by subsequent CO 2 nucleophilic addition, electron transfer, proton transfer, water dissociation, and proton-coupled electron transfer steps that lead to CO and methanol formation. We show that graphitic interactions between the Co(II)Pc(NH 2 ) 4 electrocatalyst and C 60 support selectively improve the CO 2 RR to methanol at mild potentials. The undesirable hydrogen evolution reaction (HER) was also investigated for both electrocatalysts and proceeds via the protonation of the cobalt metal center over the nitrogen atom in the inner ring. The competition between the HER and the CO 2 RR was improved in favor of CO and methanol formation using the Co(II)Pc(NH 2 ) 4 @C 60 electrocatalyst. Overall, our results suggest C 60 as a promising graphitic support for molecular electrocatalysts integration for CO 2 catalysis.

Alcohols↗
DOE OSTI2023

Cationic Cobalt(II) Bisphosphine Hydroformylation Catalysis: In Situ Spectroscopic and Reaction Studies

[HCo(CO) x (bisphosphine)](BF 4 ), x = 1–3, is a highly active hydroformylation catalyst system, especially for internal branched alkenes. In situ infrared spectroscopy (IR), electron paramagnetic resonance (EPR), and nuclear magnetic resonance studies support the proposed catalyst formulation. IR studies reveal the formation of a dicationic Co(I) paramagnetic CO-bridged dimer, [Co 2 (μ-CO) 2 (CO)(bisphosphine) 2 ] 2+ , at lower temperatures formed from the reaction of two catalyst complexes via the elimination of H 2 . Here, DFT studies indicate a dimer structure with square-pyramidal and tetrahedral cobalt centers. This monomer–dimer equilibrium is analogous to that seen for HCo(CO) 4 , reacting to eliminate H 2 and form Co 2 (CO) 8 . EPR studies on the catalyst show a high-spin (S = 3/2) Co(II) complex. Reaction studies are presented that support the cationic Co(II) bisphosphine catalyst as the catalyst species present in this system and minimize the possible role of neutral Co(I) species, HCo(CO) 4 or HCo(CO) 3 (phosphine), as catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Search for in-band transitions in the candidate superdeformed band in Si 28

Background: Superdeformed (SD) bands are suggested by theory around Ca 40 and in lighter alpha-conjugate nuclei such as Mg 24 , Si 28 , and S 32 . Such predictions originate from a number of theoretical models including mean-field models and antisymmetrized molecular dynamics (AMD) calculations. While SD bands have been identified in Ca 40 and its near neighbors, evidence of their existence in the lighter, midshell nuclei is circumstantial at best. Additionally, the key evidence of superdeformation would be the observation of transitions with high B ( E 2 ) transition strengths connecting states in a rotational sequence. This is challenging information to obtain since the bands lie at a high excitation energy and competition from out-of-band decay is dominant. Purpose: The purpose of the present study is to establish a new methodology to circumvent the difficulties in identifying and quantifying in-band transitions through directly populating candidate states in the SD band in Si 28 through inelastic alpha scattering, selecting such states with a spectrometer, and measuring their gamma-ray decay with a large array of high-purity germanium detectors, allowing direct access to electromagnetic transition strengths. Methods: Excited states in Si 28 were populated in the Si 28 ( α , α ' ) reaction using a 130-MeV He 4 beam from the K140 AVF cyclotron at the Research Center for Nuclear Physics. Outgoing alpha particles were analyzed using the Grand Raiden spectrometer positioned at an angle of 9 . 1 ° to favor the population of states with J ≈ 4 . Coincident gamma rays were detected with the CAGRA array of 12 HPGe clover detectors augmented by a set of four large LaBr 3 detectors. Results: Data analysis showed that it was possible to identify additional low-energy transitions in competition with high-energy decays from excited states in Si 28 in the vicinity of 10 MeV. However, while the candidate 4 + SD state at 10.944 MeV was populated, a 1148-keV transition to the candidate 2 + SD state at 9.796 MeV was not observed, and only an upper limit for its transition strength of B ( E 2 ) < 43 W.u. could be established. This contradicts AMD predictions of ≈ 200 W.u. for such a transition. Conclusion: The present study strongly rejects the hypothesis that the candidate set of states identified in Si 28 represents an SD band, which demonstrates the potential of the methodology devised here.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Short-lived metal-centered excited state initiates iron-methionine photodissociation in ferrous cytochrome c

Abstract The dynamics of photodissociation and recombination in heme proteins represent an archetypical photochemical reaction widely used to understand the interplay between chemical dynamics and reaction environment. We report a study of the photodissociation mechanism for the Fe(II)-S bond between the heme iron and methionine sulfur of ferrous cytochrome c . This bond dissociation is an essential step in the conversion of cytochrome c from an electron transfer protein to a peroxidase enzyme. We use ultrafast X-ray solution scattering to follow the dynamics of Fe(II)-S bond dissociation and 1 s 3 p (Kβ) X-ray emission spectroscopy to follow the dynamics of the iron charge and spin multiplicity during bond dissociation. From these measurements, we conclude that the formation of a triplet metal-centered excited state with anti-bonding Fe(II)-S interactions triggers the bond dissociation and precedes the formation of the metastable Fe high-spin quintet state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

A Stable Site‐Isolated Mono(phosphine)‐Rhodium Catalyst on a Metal‐Organic Layer for Highly Efficient Hydrogenation Reactions

Abstract Phosphine‐ligated transition metal complexes play a pivotal role in modern catalysis, but our understanding of the impact of ligand counts on the catalysis performance of the metal center is limited. Here we report the synthesis of a low‐coordinate mono(phosphine)‐Rh catalyst on a metal‐organic layer (MOL), P‐MOL • Rh, and its applications in the hydrogenation of mono‐, di‐, and tri‐substituted alkenes as well as aryl nitriles with turnover numbers (TONs) of up to 390000. Mechanistic investigations and density functional theory calculations revealed the lowering of reaction energy barriers by the low steric hindrance of site‐isolated mono(phosphine)‐Rh sites on the MOL to provide superior catalytic activity over homogeneous Rh catalysts. The MOL also prevents catalyst deactivation to enable recycle and reuse of P‐MOL • Rh in catalytic hydrogenation reactions.

Chemistry↗
DOE OSTI2026

A Short-Lived Isotope Counting System (SLICS) to measure reaction cross sections producing light, beta-decaying nuclei on OMEGA

A new activation detector optimized for short-lived isotopes was designed, installed, and tested on OMEGA. The Short-Lived Isotope Counting System (SLICS) can be positioned as close as 35 cm from the OMEGA target chamber center in a ten-inch-manipulator. Stable target samples can be mounted on the front end of the detector assembly to undergo triton-, deuteron-, or neutron-induced reactions that produce short-lived reaction products that beta decay. The emitted betas are detected in a phoswich configuration to eliminate the gamma background. The detector is optimized for isotopes with half-lives from 150 ms to 20 s, filling a gap in OMEGA’s current activation detectors for isotopes with half-lives >5 min. In a pilot study, SLICS achieved an efficiency of 24.5% ± 2.0% for counting 8Li, with a total of 505.8 ± 4.4 qualifying events. Using the existing triton laser-ion acceleration platform on OMEGA, this detector can be used to measure rarely studied tritium-induced reactions on light nuclei with an estimated uncertainty of 12%. As a result, the design of the detector and its performance during a first experiment employing deuterium as a surrogate will be discussed.

Beta spectrometry↗
NASA NTRS1980

The collective excitation of g-modes in the sun

Oscillations of the solar interior (linear g-modes) may be strongly driven by the collective influence of all the modes upon the nuclear reactions in the core. This heretofore neglected effect could couple the modes, reduce the effective amplitudes near the center, and spatially concentrate most of the oscillation energy into just a portion of the radiative interior. If operating at sufficient strength, this can reverse the conventional conclusion, drawn from single mode calculations, that almost all solar g-modes are damped. Furthermore, it would put the theory into rough harmony with three otherwise troubling observations: (1) the 'low' neutrino flux measured by Davis (1978), (2) the high correspondence found by Wolff (1976) between recurrence periods in solar activity and the rotational beat periods of g-modes, and (3) the fluctuations in the sun's diameter which imply g-mode activity at high angular harmonics (Hill and Caudell 1979). A nonlinear expression is derived for the local rate of work done on an array of oscillation modes by the nuclear reactions. Three additional tests of the model are suggested.

Wolff, C. L.↗
DOE OSTI2022

Yttrium-based Double Perovskite Nanorods for Electrocatalysis

In this work, we investigate the effect of chemical composition of double perovskite nanorods on their versatile electrocatalytic activity not only as supports for the oxidation of small organic molecules but also as catalysts for the oxygen evolution reaction. Specifically, Y 2 CoMnO 6 and Y 2 NiMnO 6 nanorods with average diameters of 300 nm were prepared by a two-step hydrothermal method, in which the individual effects of synthetic parameters, such as the pH, annealing temperature, and precursor ratios on both the composition and morphology, were systematically investigated. When used as supports for Pt nanoparticles, Y 2 CoMnO 6 /Pt catalysts exhibited an electrocatalytic activity for the methanol oxidation reaction, which is 2.1 and 1.3 times higher than that measured for commercial Pt/C and Y 2 NiMnO 6 /Pt. Similarly, the Co-based catalyst support material displayed an ethanol oxidation activity, which is 2.3 times higher than both Pt/C and Y 2 NiMnO 6 /Pt. This clear enhancement in the activity for Y 2 CoMnO 6 can largely be attributed to strong metal-support interactions, as evidenced by a downshift in the binding energy of the Pt 4f bands, measured by XPS, which is often correlated not only with a downshift in the d-band center but also to a decreased adsorption of poisoning adsorbates. Moreover, when used as catalysts for the oxygen evolution reaction, Y 2 CoMnO 6 displayed a much greater activity as compared with Y 2 NiMnO 6 . This behavior can largely be attributed not only to a preponderance of comparatively more favorable oxidation states and electronic configurations but also to the formation of an active layer on the surface of the Y 2 CoMnO 6 catalyst, which collectively give rise to improved performance metrics and greater stability as compared with both IrO 2 and Y 2 NiMnO 6 . Overall, these results highlight the importance of both the chemical composition and the electronic structure of double perovskites, especially when utilized in multi-functional roles as either supports or catalysts.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2024

Accessing metal-specific orbital interactions in C–H activation with resonant inelastic X-ray scattering

Photochemically prepared transition-metal complexes are known to be effective at cleaving the strong C–H bonds of organic molecules in room temperature solutions. There is also ample theoretical evidence that the two-way, metal to ligand (MLCT) and ligand to metal (LMCT), charge-transfer between an incoming alkane C–H group and the transition metal is the decisive interaction in the C–H activation reaction. What is missing, however, are experimental methods to directly probe these interactions in order to reveal what determines reactivity of intermediates and the rate of the reaction. Here, using quantum chemical simulations we predict and propose future time-resolved valence-to-core resonant inelastic X-ray scattering (VtC-RIXS) experiments at the transition metal L-edge as a method to provide a full account of the evolution of metal–alkane interactions during transition-metal mediated C–H activation reactions. For the model system cyclopentadienyl rhodium dicarbonyl (CpRh(CO) 2 ), we demonstrate, by simulating the VtC-RIXS signatures of key intermediates in the C–H activation pathway, how the Rh-centered valence-excited states accessible through VtC-RIXS directly reflect changes in donation and back-donation between the alkane C–H group and the transition metal as the reaction proceeds via those intermediates. We benchmark and validate our quantum chemical simulations against experimental steady-state measurements of CpRh(CO) 2 and Rh(acac)(CO)2 (where acac is acetylacetonate). Our study constitutes the first step towards establishing VtC-RIXS as a new experimental observable for probing reactivity of C–H activation reactions. More generally, the study further motivates the use of time-resolved VtC-RIXS to follow the valence electronic structure evolution along photochemical, photoinitiated and photocatalytic reactions with transition metal complexes.

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

Revealing Nanoscale Chemical Heterogeneities in Polycrystalline Mo-BiVO 4 Thin Films

The activity of polycrystalline thin film photoelectrodes is impacted by local variations of the material properties due to the exposure of different crystal facets and the presence of grain/domain boundaries. Here a multi-modal approach is applied to correlate nanoscale heterogeneities in chemical composition and electronic structure with nanoscale morphology in polycrystalline Mo-BiVO 4 . By using scanning transmission X-ray microscopy, the characteristic structure of polycrystalline film is used to disentangle the different X-ray absorption spectra corresponding to grain centers and grain boundaries. Comparing both spectra reveals phase segregation of V 2 O 5 at grain boundaries of Mo-BiVO 4 thin films, which is further supported by X-ray photoelectron spectroscopy and many-body density functional theory calculations. Theoretical calculations also enable to predict the X-ray absorption spectral fingerprint of polarons in Mo-BiVO 4 . After photo-electrochemical operation, the degraded Mo-BiVO 4 films show similar grain center and grain boundary spectra indicating V 2 O 5 dissolution in the course of the reaction. Overall, these findings provide valuable insights into the degradation mechanism and the impact of material heterogeneities on the material performance and stability of polycrystalline photoelectrodes.

36 MATERIALS SCIENCE↗