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NASA NTRS1977

Reinforced Carbon Carbon (RCC) oxidation resistant material samples - Baseline coated, and baseline coated with tetraethyl orthosilicate (TEOS) impregnation

Reinforced carbon-carbon material specimens were machined from 19 and 33 ply flat panels which were fabricated and processed in accordance with the specifications and procedures accepted for the fabrication and processing of the leading edge structural subsystem (LESS) elements for the space shuttle orbiter. The specimens were then baseline coated and tetraethyl orthosilicate impregnated, as applicable, in accordance with the procedures and requirements of the appropriate LESS production specifications. Three heater bars were ATJ graphite silicon carbide coated with the Vought 'pack cementation' coating process, and three were stackpole grade 2020 graphite silicon carbide coated with the chemical vapor deposition process utilized by Vought in coating the LESS shell development program entry heater elements. Nondestructive test results are reported.

Gantz, E. E.↗

DOE OSTI2025

Vibrational Signatures of Electronic Properties in Renewable-Energy Catalysis

The objective of this research program is to discover and develop new approaches for ab initio computational simulations of molecular motion. Specifically, this program aims to decipher the connection between the underlying electronic structure and the accordant molecular vibrations in reactive ions and radicals for renewable-energy purposes. Recent experimental progress in ion sources and optical spectroscopies has unearthed considerable new inner-sphere detail for these complexes, but the connection between these spectral signatures and mechanistic information often remains elusive, to the continued frustration of experimentalists. For this purpose, new anharmonic vibrational frequency methods, along with a publicly deployed software package, will be developed. Working closely with committed experimental collaborators, this conceptual and computational framework will be used to explain the results of new spectroscopy experiments, focusing specifically on the inner-shell mechanisms of renewable-energy catalysis. The oxidation half of catalytic water-splitting chemistry will be a central focus, along with fundamental studies of the manner in which strong ions and radicals activate solvent as a chemical species. The resulting products of the research program will include openly available software and algorithms for the ab initio simulation of challenging vibrational spectra, as well as critical mechanistic insight into energy-focused catalytic processes that are opaque to other existing analytical techniques.

42 ENGINEERING↗

NASA NTRS1988

High throughput X-ray optics - An overview

Techniques for the production of high-throughput modular arrays of telescopes with net collecting areas exceeding 10 to the 5th sq cm and 20-arsec angular resolution are discussed. Techniques considered include the automated figuring of flats as parabolic reflectors, the replication of cylindrical shells, the alignment of thin lacquer-coated conical foils, electroforming, and the use of large diamond turning machines. High-throughput programs are described, and it is noted that future missions will emphasize high resolution spectroscopy.

Gorenstein, Paul↗

NASA NTRS1992

A burst from a thermonuclear runaway on an ONeMg white dwarf

Studies which examine the consequences of accretion, at rates of 10(exp -9) solar mass/yr and 10(exp -10) solar mass/yr, onto an ONeMg white dwarf with a mass of 1.35 solar masses are performed. In these studies, a Lagrangian, hydrodynamic, one-dimensional computer code was used. The code now includes a network with 89 nuclei up to Ca-40, elemental diffusion, new opacities, and new equation of state. The initial abundance distribution corresponded to a mixture that was enriched to either 25, 50, or 75 percent in products of carbon burning. The remaining material in each case is assumed to have a solar composition. The evolution of the thermonuclear runaway in the 1.35 solar mass white dwarf, with M = 10(exp -9) solar mass, produced peak temperatures in the shell source exceeding 300 million degrees. The sequence produced significant amounts of Na-22 from proton captures onto Ne-20 and significant amounts of Al-26 from proton captures on Mg-24. This sequence ejected 5.2 x 10(exp -6) solar mass moving with speeds from approximately 100 km/s to 2300 km/s. When the mass accretion rate was decreased to 10(exp -10) solar mass, the resulting thermonuclear runaway produced a shock that moved through the outer envelope of the white dwarf and raised the surface luminosity to L greater than 10(exp 7) solar luminosity and the effective temperature to values exceeding 10(exp 7) K. The interaction of the material expanding from off of the white dwarf with the accretion disk should produce a burst of gamma-rays.

Starrfield, S.↗

NASA NTRS2011

Assembly of 5.5-Meter Diameter Developmental Barrel Segments for the Ares I Upper Stage

Full scale assembly welding of Ares I Upper Stage 5.5-Meter diameter cryogenic tank barrel segments has been performed at the Marshall Space Flight Center (MSFC). One full-scale developmental article produced under the Ares 1 Upper Stage project is the Manufacturing Demonstration Article (MDA) Barrel. This presentation will focus on the welded assembly of this barrel section, and associated lessons learned. Among the MDA articles planned on the Ares 1 Program, the Barrel was the first to be completed, primarily because the process of manufacture from piece parts (barrel panels) utilized the most mature friction stir process planned for use on the Ares US program: Conventional fixed pin Friction Stir Welding (FSW). This process is in use on other space launch systems, including the Shuttle s External Tank, the Delta IV common booster core, the Delta II, and the Atlas V rockets. The goals for the MDA Barrel development were several fold: 1) to prove out Marshall Space Flight Center s new Vertical Weld Tool for use in manufacture of cylindrical barrel sections, 2) to serve as a first run for weld qualification to a new weld specification, and 3) to provide a full size cylindrical section for downstream use in precision cleaning and Spray-on Foam Insulation development. The progression leading into the welding of the full size barrel included sub scale panel welding, subscale cylinder welding, a full length confidence weld, and finally, the 3 seamed MDA barrel processing. Lessons learned on this MDA program have been carried forward into the production tooling for the Ares 1 US Program, and in the use of the MSFC VWT in processing other large scale hardware, including two 8.4 meter diameter Shuttle External Tank barrel sections that are currently being used in structural analysis to validate shell buckling models.

Carter, Robert W.↗

DOE OSTI2021

Biochar alters hydraulic conductivity and impacts nutrient leaching in two agricultural soils

Biochar is purported to provide agricultural benefits when added to the soil, through changes in saturated hydraulic conductivity (K sat ) and increased nutrient retention through chemical or physical means. Despite increased interest and investigation, there remains uncertainty regarding the ability of biochar to deliver these agronomic benefits due to differences in biochar feedstock, production method, production temperature, and soil texture. In this project, a suite of experiments was carried out using biochars of diverse feedstocks and production temperatures, in order to determine the biochar parameters which may optimize agricultural benefits. Sorption experiments were performed with seven distinct biochars to determine sorption efficiencies for ammonium and nitrate. Only one biochar effectively retained nitrate, while all biochars bound ammonium. The three biochars with the highest binding capacities (produced from almond shell at 500 and 800 °C (AS500 and AS800) and softwood at 500 °C (SW500)) were chosen for column experiments. Biochars were amended to a sandy loam and a silt loam at 0 % and 2 % (w/w), and K sat was measured. Biochars reduced K sat in both soils by 64 %–80 %, with the exception of AS800, which increased K sat by 98 % in the silt loam. Breakthrough curves for nitrate and ammonium, as well as leachate nutrient concentration, were also measured in the sandy loam columns. All biochars significantly decreased the quantity of ammonium in the leachate, by 22 % to 78 %, and slowed its movement through the soil profile. Ammonium retention was linked to high cation exchange capacity and a high oxygen-to-carbon ratio, indicating that the primary control of ammonium retention in biochar-amended soils is the chemical affinity between biochar surfaces and ammonium. Biochars had little to no effect on the timing of nitrate release, and only SW500 decreased total quantity, by 27 % to 36 %. The ability of biochar to retain nitrate may be linked to high micropore specific surface area, suggesting a physical entrapment rather than a chemical binding. Together, this work sheds new light on the combined chemical and physical means by which biochar may alter soils to impact nutrient leaching and hydraulic conductivity for agricultural production.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2019

Dreaming awake: disentangling the underlying physics in case of a SUSY-like discovery at the LHC

The purpose of this review is to investigate what kind of physics can be extracted at the Large Hadron Collider (LHC), assuming a discovery is made in events with missing transverse momentum, as generically expected in supersymmetry (SUSY) with R-parity conservation. To set the scene, we first discuss the collider phenomenology of the six possible electroweakino benchmark scenarios, as they provide valuable insight into what one might be facing at the LHC. We review the existing methods for mass reconstruction from measured kinematic endpoints in the distributions of suitable variables, e.g. the invariant masses of various sets of visible decay products, as well as the M T2 and the M 2 types of variables. We propose to extend the application of these methods to the various topologies of fully hadronic final states, possibly with hadronically reconstructed massive bosons (W, Z or h). We test the idea with a simplified simulation of events in the main electroweakino benchmark scenarios. We find that the fully hadronic events allow the complete determination of the relevant mass spectrum. For comparison, we also review the potential of the standard kinematic endpoint methods for final states involving leptons from the decays of (on-shell or off-shell) sleptons. We find that with 300 fb -1 , the statistics for the leptonic events is very marginal and they look less promising than the fully hadronic channels. This corresponds to a complete reversal of the usual paradigm, where leptonic events comprised the gold-plated SUSY channels. Finally, we put together all available information and summarize what level of understanding of the underlying physics can be achieved. We show that, as a by-product of the mass reconstruction, it is also possible to determine the production cross sections and decay branching ratios, which in turn enable us to pinpoint the underlying model.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2021

Visible-Light-Enhanced Cobalt-Catalyzed Hydrogenation: Switchable Catalysis Enabled by Divergence between Thermal and Photochemical Pathways

The catalytic hydrogenation activity of the readily-prepared, coordinatively saturated cobalt(I) precatalyst, (R,R)-( iPr DuPhos)Co(CO) 2 H ((R,R)- iPr DuPhos = (+)-1,2-bis[(2R,5R)-2,5-diisopropylphospholano]benzene) is described. While efficient turnover was observed with a range of alkenes upon heating to 100 ºC, the catalytic performance of the cobalt catalyst was markedly enhanced upon irradiation with blue light at 35 °C. Here, this improved reactivity enabled hydrogenation of terminal, di- and trisubstituted alkenes, alkynes, and carbonyl compounds. A combination of deuterium labeling studies, hydrogenation of alkenes containing radical clocks and experiments probing relative rates support a hydrogen atom transfer pathway under thermal conditions that is enabled by a relatively weak cobalt–hydrogen bond of 56 kcal/mol. In contrast, data for the photocatalytic reactions support light-induced dissociation of a carbonyl ligand followed by a coordination-insertion sequence where the product is released by combination of a cobalt alkyl intermediate with the starting hy-dride, (R,R)-( iPr DuPhos)Co(CO) 2 H. These results demonstrate the versatility with catalysis with Earth-abundant metals as pathways involving open- versus closed-shell intermediates can be switched by the energy source.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C=X (X = O, N) Functionalities

Catalysis is the second largest application for V after its use as an additive to improve steel production. Molecular complexes of vanadium(V) are particularly useful and efficient catalysts for oxidation processes; however, their ability to catalyze reductive transformations has yet to be fully explored. Here we report the first examples of polar organic functionality reduction mediated by V. Open-shell V III complexes that feature a π-radical monoanionic 2,2':6',2"-terpyridine ligand (Rtpy • ) – functionalized at the 4'-position (R = (CH 3 ) 3 SiCH 2 , C 6 H 5 ) catalyze mild and chemoselective hydroboration and hydrosilylation of functionalized ketones, aldehydes, imines, esters, and carboxamides with turnover numbers (TONs) of up to ~1000 and turnover frequencies (TOFs) of up to ~500 h –1 . In conclusion, computational evaluation of the precatalyst synthesis and activation has revealed underappreciated complexity associated with the redox-active tpy chelate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1974

X-ray structure of the Cygnus loop

An X-ray surface brightness map of the Cygnus Loop in the energy range 0.15-0.85 keV is presented. The X-ray distribution is compared with the optical and radio pictures of the Loop. The location of the center of the supernova shell as derived from the X-ray data is in excellent agreement with the apparent optical and radio centers. We obtain a mean diameter for the X-ray shell of 2.75 (+ or - 0.2) deg. The X-ray spectral data yield a characteristic thermal temperature averaged over the Loop of 2.9 million (+ or - 1.5 million) K. We have calculated anew X-ray parameters for adiabatic blast waves using X-ray production spectra which include line radiation. These parameters are compared with the results of the present experiment. An age of 18,000 years, initial blast energy equal to 3 times 10 to the 50-th power ergs, and ambient interstellar density of 0.25 per cu cm are found.

Rappaport, S.↗

DOE OSTI2019

Nuclear level densities and γ -ray strength functions in samarium isotopes

The γ-strength functions and level densities in the quasicontinuum of 147,149 Sm isotopes have been extracted from particle-γ coincidences using the Oslo method. The nuclei of interest were populated via (p,d) reactions on pure 148,150 Sm targets and the reaction products were recorded by the Hyperion array. An upbend in the low-energy region of the γSF has been observed. The systematic analysis of the γSF for a range of Sm isotopes highlights the interplay between scissors mode and the upbend. In conclusion, shell-model calculations show reasonable agreement with the experimental γSFs and confirm the correspondence between the upbend and scissors mode.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

NASA NTRS1983

Relativistic calculation of atomic M-shell ionization by protons

Relativistic plane-wave Born-approximation calculations of cross sections for M-shell ionization of Ho-67, Au-79, U-92 by protons with incident energies from 0.05 to 1 MeV are reported. Dirac-Hartree-Slater wave functions were employed and binding-energy change and Coulomb deflection were taken into account. Associated X-ray production cross sections were also computed. Results are compared with previous theoretical predictions and with experimental data. Definite improvement in the theory has been attained by the use of realistic wave functions and consistent inclusion of the effects of relativity.

Chen, M. H.↗

DOE OSTI2023

Search for direct production of electroweakinos in final states with one lepton, jets and missing transverse momentum in pp collisions at $\sqrt{s} $ = 13 TeV with the ATLAS detector

Searches for electroweak production of wino-like chargino pairs, ${\overset{\sim }{\chi}}_1^{+}{\overset{\sim }{\chi}}_1^{-}$, and of wino-like chargino and next-to-lightest neutralino, ${\overset{\sim }{\chi}}_1^{\pm }{\overset{\sim }{\chi}}_2^0$, are presented. The models explored assume that the charginos decay into a W boson and the lightest neutralino, ${\overset{\sim }{\chi}}_1^{\pm}\to {W}^{\pm }{\overset{\sim }{\chi}}_1^0$. The next-to-lightest neutralinos are degenerate in mass with the chargino and decay to ${\overset{\sim }{\chi}}_1^0$ and either a Z or a Higgs boson, ${\overset{\sim }{\chi}}_2^0\to Z{\overset{\sim }{\chi}}_1^0$ or $h{\overset{\sim }{\chi}}_1^0$. The searches exploit the presence of a single isolated lepton and missing transverse momentum from the W boson decay products and the lightest neutralinos, and the presence of jets from hadronically decaying Z or W bosons or from the Higgs boson decaying into a pair of b-quarks. The searches use 139 fb –1 of $\sqrt{s}$ = 13 TeV proton-proton collisions data collected by the ATLAS detector at the Large Hadron Collider between 2015 and 2018. No deviations from the Standard Model expectations are found, and 95% confidence level exclusion limits are set. Chargino masses ranging from 260 to 520 GeV are excluded for a massless ${\overset{\sim }{\chi}}_1^0$ in chargino pair production models. Degenerate chargino and next-to-lightest neutralino masses ranging from 260 to 420 GeV are excluded for a massless ${\overset{\sim }{\chi}}_1^0$ for ${\overset{\sim }{\chi}}_2^0\to Z{\overset{\sim }{\chi}}_1^0$. For decays through an on-shell Higgs boson and for mass-splitting between ${\overset{\sim }{\chi}}_1^{\pm }/{\overset{\sim }{\chi}}_2^0$ and ${\overset{\sim }{\chi}}_1^0$ as small as the Higgs boson mass, mass limits are improved by up to 40 GeV in the range of 200–260 GeV and 280–470 GeV compared to previous ATLAS constraints.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2022

Permeability-Engineered Compartmentalization Enables In Vitro Reconstitution of Sustained Synthetic Biology Systems

In nature, biological compartments such as cells rely on dynamically controlled permeability for matter exchange and complex cellular activities. Likewise, the ability to engineer compartment permeability is crucial for in vitro systems to gain sustainability, robustness, and complexity. However, rendering in vitro compartments such a capability is challenging. Here, a facile strategy is presented to build permeability-configurable compartments, and marked advantages of such compartmentalization are shown in reconstituting sustained synthetic biology systems in vitro. Through microfluidics, the strategy produces micrometer-sized layered microgels whose shell layer serves as a sieving structure for biomolecules and particles. In this configuration, the transport of DNAs, proteins, and bacteriophages across the compartments can be controlled an guided by a physical model. Through permeability engineering, a compartmentalized cell-free protein synthesis system sustains multicycle protein production; ≈100 000 compartments are repeatedly used in a five-cycle synthesis, featuring a yield of 2.2 mg mL -1 . Further, the engineered bacteria-enclosing compartments possess near-perfect phage resistance and enhanced environmental fitness. In a complex river silt environment, compartmentalized whole-cell biosensors show maintained activity throughout the 32 h pollutant monitoring. It is anticipated that permeability-engineered compartmentalization should pave the way for practical synthetic biology applications such as green bioproduction, environmental sensing, and bacteria-based therapeutics.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2021

Tracking the phase changes in micelle-based NiGa nanocatalysts for methanol synthesis under activation and working conditions

The hydrogenation of CO 2 into high energy density fuels such as methanol, where the required H 2 is obtained from renewable sources, is of utmost importance for a sustainable society. In recent years, NiGa alloys have attracted attention as promising catalyst material systems for the hydrogenation of CO 2 into methanol at ambient pressures. They thus represent an energy-saving alternative to the Cu-based catalysts employed in today's catalytic industry that require high pressures for the CO 2 hydrogenation. However, the underlying reaction mechanisms for the NiGa system are still under debate. One of the challenges here is to unravel the evolution and coexistence of the different species in the heterogeneous NiGa catalyst system under activation and reaction conditions. To shed light on their evolution under activation in H 2 and their catalytic roles under CO 2 hydrogenation working conditions on well-defined Ni 3 Ga 1 and Ni 5 Ga 3 nanoparticle (NP) catalysts, we employed a multi-probe approach in this study. It included advanced machine learning-based analysis of operando X-ray absorption spectroscopy data combined with operando powder X-ray diffraction and near ambient pressure X-ray photoelectron spectroscopy measurements, as well as reactivity studies using bed-packed mass flow reactors. In addition, we employed atomic force microscopy and scanning transmission electron microscopy for structural characterization. Under H 2 activation at 1 bar total pressure, we concluded the formation of metallic Ni, starting for Ni 3 Ga 1 at 300 °C, and for Ni 5 Ga 3 at 400 °C. At higher temperatures, the formation of NiGa alloys follows. The α'-Ni 3 Ga 1 alloy phase is predominantly formed for the Ni 3 Ga 1 NPs, while the coexistence of α'-Ni 3 Ga 1 , δ-Ni 5 Ga 3 and Ga 2 O 3 phases is observed for the Ni 5 Ga 3 NPs after the H 2 activation. The formation of the Ga 2 O 3 phase also results in the presence of excess metallic Ni. Under CO 2 hydrogenation reaction conditions, Ga partially oxidizes again to form a Ga 2 O 3 -rich particle shell for both NP compositions, yet, to a larger extent for the Ni 3 Ga 1 NPs, which, in turn, feature a higher amount of excess Ni. We reveal that metallic Ni is responsible for the high selectivity of the Ni 3 Ga 1 NPs towards the production of methane in our catalytic tests. In contrast, the Ni 5 Ga 3 NPs display a strong selectivity toward methanol production (>92%), more than one order of magnitude higher than that for the Ni 3 Ga 1 NPs, which we ascribe to the presence of the δ-Ni 5 Ga 3 phase.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2019

Probing microstructure and electrolyte concentration dependent cell chemistry via operando small angle neutron scattering

The key to understanding the cycling mechanism of lithium-ion battery electrodes is to develop methods to monitor the dynamic cell chemistry, but the complexity of the problem has continued to pose an obstacle. Here we describe the use of operando small-angle neutron scattering (SANS) to show directly how the use of concentrated LiTFSI electrolyte in Li/ordered mesoporous carbon (OMC) half-cells influences the mechanism of solid electrolyte interphase (SEI) formation, lithium intercalation, and carbon framework expansion. We find that a complex interplay between the viscosity, lithium solvation shell and electrode microstructure in the concentrated 4 M electrolyte changes the dynamics of SEI formation and pore filling at a given applied potential. Both the filling of micropores and co-intercalation are found to drive the expansion of the carbon framework. Lithium-rich reduction products form at much higher potentials in the micropores of the 4 M electrolyte system, while on mesopore surfaces the lithium-rich salts form quickly before giving way to carbonaceous products. As a result, this study reveals operando SANS as a unique method for providing microstructure dependent information on the dynamics of electrochemical processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1993

Segregation of gas and stars in shell galaxies

Using a code which is capable of evolving composite systems of collisionless matter and gas, we explore mergers like those thought responsible for the shells seen around many elliptical galaxies. If a small companion containing both gas and stars is accreted by a more massive primary, the stellar and gaseous debris are rapidly segregated: while the stars are free to oscillate back and forth in the primary's potential, thereby forming shells, the oppositely directed flows near the center of the primary effectively dissipate the orbital kinetic energy of the gas. Consequently, the gas settles into compact disks or rings in the nucleus of the primary, depending on orbital parameters. We note implications of these findings for the production of polar rings and the onset of nuclear activity in galaxies.

Weil, Melinda L.↗

NASA NTRS1993

AGB stars as a source of short-lived radioactive nuclei in the solar nebula

The purpose is to estimate the possible contribution of some short-lived nuclei to the early solar nebula from asymptotic giant branch (AGB) sources. Low mass (1 to 3 solar mass) AGB stars appear to provide a site for synthesis of the main s process component for solar system material with an exponential distribution of neutron irradiations varies as exp(-tau/tau(sub 0)) (where tau is the time integrated neutron flux with a mean neutron exposure tau(sub 0)) for solar abundances with tau(sub 0) = 0.28 mb(sup -1). Previous workers estimated the synthesis of key short-lived nuclei which might be produced in AGB stars. While these calculations exhibit the basic characteristics of nuclei production by neutron exposure, there is need for a self-consistent calculation that follows AGB evolution and takes into account the net production from a star and dilution with the cloud medium. Many of the general approaches and the conclusions arrived at were presented earlier by Cameron. The production of nuclei for a star of 1.5 solar mass during the thermal pulsing of the AGB phase was evaluated. Calculations were done for a series of thermal pulses with tau(sub 0) = 0.12 and 0.28 mb(sup -1). These pulses involve s nucleosynthesis in the burning shell at the base of the He zone followed by the ignition of the H burning shell at the top of the He zone. After about 10-15 cycles the abundances of the various nuclei in the He zone become constant. Computations of the abundances of all nuclei in the He zone were made following Gallino. The mass of the solar nebula was considered to consist of some initial material of approximately solar composition plus some contributions from AGB stars. The ratios of the masses required from the AGB He burning zone to the ISM necessary to produce the observed value of Pd-107/Pd-108 in the early solar system were calculated and this dilution factor was applied to all other relevant nuclei.

Wasserburg, G. J.↗