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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 NTRS2010

Options to Accelerate Ozone Recovery: Ozone and Climate Benefits

The humankind or anthropogenic influence on ozone primarily originated from the chlorofluorocarbons and halons (chlorine and bromine). Representatives from governments have met periodically over the years to establish international regulations starting with the Montreal Protocol in 1987, which greatly limited the release of these ozone-depleting substances (DDSs). Two global models have been used to investigate the impact of hypothetical reductions in future emissions of ODSs on total column ozone. The investigations primarily focused on chlorine- and bromine-containing gases, but some computations also included nitrous oxide (N2O). The Montreal Protocol with ODS controls have been so successful that further regulations of chlorine- and bromine-containing gases could have only a fraction of the impact that regulations already in force have had. if all anthropogenic ODS emissions were halted beginning in 2011, ozone is calculated to be higher by about 1-2% during the period 2030-2100 compared to a case of no additional ODS restrictions. Chlorine- and bromine-containing gases and nitrous oxide are also greenhouse gases and lead to warming of the troposphere. Elimination of N 20 emissions would result in a reduction of radiative forcing of 0.23 W/sq m in 2100 than presently computed and destruction of the CFC bank would produce a reduction in radiative forcing of 0.005 W/sq m in 2100. This paper provides a quantitative way to consider future regulations of the CFC bank and N 20 emissions

Fleming, E. L.↗
DOE OSTI2026

Facet-Dependent Water Inhibition of Alkanol Dehydration on TiO2 via Distinct Water–Alkanol Complexes

Water is ubiquitous in biomass-derived feeds, yet its molecular impact on oxygen-elimination reactions remains poorly understood, particularly for catalysts exposing different facets. Here, we utilize well-defined TiO2 nanocrystals with dominant (101) and (001) facets to reveal a pronounced facet-dependent effect of water, where inhibition for dehydration of isopropanol (IPA) on the TiO2(001) surface is about four times more severe than TiO2(101). Through a combination of in situ solid state NMR, in situ infrared spectroscopy, kinetics studies, and theoretical calculations, we demonstrate that this disparity arises from the formation of distinct alkanol-water complex intermediates. On TiO2(001), IPA undergoes dissociative adsorption to form an isopropoxide-H2O complex that readily drives the surface into a complex-dominated regime. This pathway increases the activation barrier for C–H cleavage by 40 kJ mol-1 by inducing a disordered transition state. In contrast, TiO2(101) favors molecular IPA adsorption with weak hydrogen bonding to water, resulting in a smaller complex formation constant and a much smaller activation barrier increase (25 kJ mol-1). By quantitatively linking facet-dependent complex coverage to transition-state destabilization, this work moves beyond simple site-blocking models and provides a conceptual framework for designing catalysts that remain active in water-containing environments

Hu, Wenda↗
DOE OSTI2024

Mechanistic Insights into the Origins of Selectivity in a Cu-Catalyzed C–H Amidation Reaction

The catalytic transformation of C-H to C-N bonds offers rapid access to fine chemicals and high-performance materials, but achieving high selectivity from undirected aminations of unactivated C(sp 3 )-H bonds remains an outstanding challenge. Here, we report the origins of the reactivity and selectivity of a Cu-catalyzed C-H amidation of simple alkanes. Using a combination of experimental and computational mechanistic studies and energy decomposition techniques, we uncover a switch in mechanism from inner-sphere to outer-sphere coupling between alkyl radicals and the active Cu(II) catalyst with increasing substitution of the alkyl radical. The combination of computational predictions and detailed experimental validation shows that simultaneous minimization of both Cu-C covalency and alkyl radical size increases the rate of reductive elimination and that both strongly electron-donating and electron-withdrawing substituents on the catalyst accelerate the selectivity-determining C-N bond formation process as a result of a change in mechanism. These findings offer design principles for the development of improved catalyst scaffolds for radical C-H functionalization reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1990

Microhardness variations in II-VI semiconducting compounds as a function of composition

A comparison is made of microhardness variations as a function of composition in directionally solidified alloys of Hg(1-x)Cd(x)Te, Hg(1-x)Zn(x)Te, Hg(1-x)Cd(x)Se, and Hg(1-x)Zn(x)Se, using the same growth method for all four systems in order to eliminate preparation-induced mechanical property variations. In each case, compositional analysis was performed next to a microhardness indentation. Due to the 14-percent shorter bond length of ZnTe relative to HgTe, Zn-base alloy mechanical strength should exceed that of Cd-base systems. Experimental verification is furnished for this hardening effect in both Hg(1-x)Zn(x)Te and Hg(1-x)Zn(x)Se.

Andrews, R. N.↗
NASA NTRS1999

In-Situ Optical Determination of Thermomechanical Properties of ZnSe and ZnTe Crystals

At temperatures above 1/2 T(sub m), the generation and movement of dislocations may result due to the load created by the weight of the crystal itself The deformation may be expected to increase the line defect density and may result in generation of low angle grain boundaries, especially in the regions of the crystal attached to the ampule. It has often been suspected that elimination of this effect in space can improve crystallinity of crystals grown under microgravity conditions, however, a direct experimental proof of such relation is still missing. In this work we have designed and built a system of in-situ optical detection and measurement of the mechanical deformations of a crystal wafer under its own weight, and studied the deformation effects as a function of temperature. The results of the measurements for ZnSe and ZnTe crystal wafers will be presented.

Burger, A.↗
NASA NTRS1971

Experiment S009: Nuclear Emulsion

The first exposure on a spacecraft of a nuclear emulsion apparatus designed to collect 1000 high quality tracks of heavy nuclei under a negligible thickness of matter (0.07 g/sq cm) is described. The cosmic ray detector consisted of a stack of nuclear emulsions that were designed to register at least 400 heavy nuclei tracks for each 10 hours of useful exposure. The spacecraft had to be oriented in a heads-up attitude during the 10-hour period to eliminate atmospheric albedo particles. The results are as follows: (1) a definite odd-even effect, with low abundances for elements of atomic number 7, 9, and 11; (2) a ratio O/C approximately 0.9; (3) Ne/C, Mg/C, and Si/C ratios between 0.2 and 0.3; (4) an abundance gap in the region 15 less than or equal to Z less than or equal to 19; and (5) a ratio (20 less than or equal to Z less than or equal to 28)/C 0.2, with a large concentration at Z = 26. These results are indicative that successful exposures of nuclear emulsions were obtained on the Gemini 11 mission.

Odell, F. W.↗
NASA NTRS1992

Electron acceleration by Alfven waves in the magnetosphere

The self-consistent electron kinetics of Alfven waves on the electron inertial scale is studied using a 2D hybrid-kinetic description. The ions follow a fluid description for Alfven waves at frequencies below the ion cyclotron frequency. The parallel electron dynamics is treated kinetically using particle-in-cell techniques. In this model, the electron plasma mode is eliminated, and only the physics of the Alfven waves is retained. At sufficiently large amplitudes, it is found that oblique Alfven waves break due to finite electron inertia in a cold plasma. The consequence of wave breaking is the formation of an electron beam which can be unstable to the beam-plasma instability. The electrons supporting the parallel current thermalize into a non-Maxwellian distribution with an energetic tail up to several keV, assuming a reasonable magnetospheric Alfven speed. In hot plasma simulations, electron trapping is the principal mechanism of electron acceleration. It is proposed that wave breaking or electron trapping of oblique Alfven waves at 1 R(E) can result in electron acceleration and may explain some observed auroral phenomena.

Hui, C.-H.↗
NASA NTRS2000

Reconstruction algorithm for polychromatic CT imaging: application to beam hardening correction

This paper presents a new reconstruction algorithm for both single- and dual-energy computed tomography (CT) imaging. By incorporating the polychromatic characteristics of the X-ray beam into the reconstruction process, the algorithm is capable of eliminating beam hardening artifacts. The single energy version of the algorithm assumes that each voxel in the scan field can be expressed as a mixture of two known substances, for example, a mixture of trabecular bone and marrow, or a mixture of fat and flesh. These assumptions are easily satisfied in a quantitative computed tomography (QCT) setting. We have compared our algorithm to three commonly used single-energy correction techniques. Experimental results show that our algorithm is much more robust and accurate. We have also shown that QCT measurements obtained using our algorithm are five times more accurate than that from current QCT systems (using calibration). The dual-energy mode does not require any prior knowledge of the object in the scan field, and can be used to estimate the attenuation coefficient function of unknown materials. We have tested the dual-energy setup to obtain an accurate estimate for the attenuation coefficient function of K2 HPO4 solution.

NASA Center ARC↗
NASA NTRS1988

The 2.5-12 micrometers spectrum of comet Halley from the IKS-VEGA experiment

The infrared instrument IKS flown on board the VEGA space probes was designed for the detection of emission bands of parent molecules, and for a measurement of the size and temperature of the thermal emitting nuclear region. The instrument had three channels with cooled detectors: an "imaging channel" designed to modulate the signal of the nucleus and two spectroscopic channels operating at 2.5-5 and 6-12 micrometers, respectively, equipped with circular variable filters of resolving power approximately 50. This paper presents and discusses the results from the spectral channels. On VEGA 1, usable spectra were obtained at distances D from the comet nucleus ranging from 250,000 to 40,000 km corresponding to fields of view 4000 and 700 km in diameter, respectively. The important internal background signal caused by the instrument itself, which could not be cooled, had to be eliminated. Since no sky chopping was performed, we obtain difference spectra between the current spectrum and a reference spectrum with little or no cometary signal taken at the beginning of the observing sequence (D approximately 200,000 km). Final discrimination between cometary signal and instrumental background is achieved using their different time evolution, since the instrumental background is proportional to the slow temperature drift of the instrument, and the cometary signal due to parent molecules or dust grains is expected to vary in first order as D-1. The 2.5-5 micrometers IKS spectra definitely show strong narrow signals at 2.7 and 4.25 micrometers, attributed to the nu 3 vibrational bands of H2O and CO2, respectively, and a broader signal in the region 3.2-3.5 micrometers, which may be attributed to CH-bearing molecules. All these signals present the expected D-1 intensity variation. Weaker emission features at 3.6 and 4.7 micrometers could correspond to the nu 1 and nu 5 bands of H2CO and the (1 - 0) band of CO, respectively. Molecular production rates are derived from the observed emissions, assuming that they are due to resonance fluorescence excited by the Sun's infrared radiation. For the strong bands of H2O and CO2, the rovibrational lines are optically thick, and radiative transfer is taken into account. We derive production rates, at the moment of the VEGA 1 flyby, of approximately 10(30) sec-1 for H2O, approximately 2.7 x 10(28) sec-1 for CO2, approximately 5 x 10(28) sec-1 for CO, and 4 x 10(28) sec-1 for H2CO, if attributions to CO and H2CO are correct. The production rate of carbon atoms in CH-bearing molecules is approximately 9 x 10(29) sec-1 assuming fluorescence of molecules in the gas phase, but could be much less if the 3.2-3.5 micrometers emission is attributed to C-H stretch in polycyclic aromatic hydrocarbons or small organic grains. In addition, marginal features are present at 4.85 and 4.45 micrometers, tentatively attributed to OCS and molecules with the CN group, respectively. Broad absorption at 2.8-3.0 micrometers, as well as a narrow emission at 3.15 micrometers, which follow well the D-1 intensity variation, might be due to water ice. Emission at 2.8 micrometers is also possibly present, and might be due to OH created in vibrationally excited states after water photodissociation. The 6-12 micrometers spectrum does not show any molecular emission, nor emission in the 7.5-micrometers region. The spectrum is dominated by silicate emission showing a double structure with maxima at 9.0 and 11.2 micrometers, which suggests the presence of olivine.

NASA Discipline Number 52-10↗
DOE OSTI2025

Radiation-Induced Chemical Yields of Carbon-Centered Radicals and Hydrogen Atoms from the Gamma Irradiation of n -Dodecane

Here, this study investigates the radiolytic yields of carbon-centered radicals and hydrogen atoms in n-dodecane under gamma irradiation. Utilizing molecular iodine (I 2 ) and 2,4,6-tri-tert-butylnitrosobenzene (3tBNB) as radical scavengers, we quantified the yields of molecular hydrogen and various carbon-centered radicals formed from bond scission of the solvent excited states. The yield of primary alkyl radicals was significantly lower than that of the secondary radicals, aligning with expected stabilities and bond dissociation energies. For the overall loss of n-dodecane, total yields of 0.598 ± 0.004 species/100 eV for C–C bond scission, 1.648 ± 0.012 species/100 eV for C–H bond scission, and 3.20 ± 0.10 species/100 eV for unimolecular H 2 elimination were determined. Notably, the I 2 scavenging data provided robust estimates, while the 3tBNB displayed lower efficiency in radical trapping. This research enhances our understanding of radiolytic processes in n-dodecane and offers insights for future studies on the behavior of hydrocarbons under ionizing radiation, with implications for improving UNF reprocessing strategies.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗
DOE OSTI2023

Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis

Carbon–carbon bond cleavage reactions, adapted to deconstruct aliphatic hydrocarbon polymers and recover the intrinsic energy and carbon value in plastic waste, have typically been catalysed by metal nanoparticles or air-sensitive organometallics. Metal oxides that serve as supports for these catalysts are typically considered to be inert. Here we show that Earth-abundant, non-reducible zirconia catalyses the hydrogenolysis of polyolefins with activity rivalling that of precious metal nanoparticles. To harness this unusual reactivity, our catalytic architecture localizes ultrasmall amorphous zirconia nanoparticles between two fused platelets of mesoporous silica. Macromolecules translocate from bulk through radial mesopores to the highly active zirconia particles, where the chains undergo selective hydrogenolytic cleavage into a narrow, C18-centred distribution. Calculations indicated that C–H bond heterolysis across a Zr–O bond of a Zr(O) 2 adatom model for unsaturated surface sites gives a zirconium hydrocarbyl, which cleaves a C–C bond via β-alkyl elimination.

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

C sp 2 –H/F bond activation and borylation with iron

Reduction of [K 2 {( tBu pyrr 2 pyr)Fe} 2 (μ-N 2 )] (1) with two equiv. of KC 8 in the presence of crown-ether 18-C-6 yields the N 2 adduct [{K(18-C-6)} 2 ( tBu pyrr 2 pyr)Fe(N 2 )] (2). Complex 2 heterolytically splits the C sp 2 –H bond of benzene to form [{K(18-C-6)}( tBu pyrr 2 pyr)Fe(C 6 H 5 )] (3), whereby usage of a diboron B 2 pin 2 promotes hydride elimination to form the salt [K(18-C-6)HB 2 Pin 2 ] (4). Similarly, 3 can also be formed by cleavage of the C–F bond of fluorobenzene. Reaction of 3 with ClBcat yields [K(18-C-6)(thf) 2 ][( tBu pyrr 2 pyr)FeCl] (5) and PhBcat and the former can be reduced to 2 to complete a synthetic cycle for heterolytic benzene C–H activation and borylation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Erratum: Centrality-Dependent Modification of Jet-Production Rates in Deuteron-Gold Collisions at $\sqrt{𝑠_{𝑁⁢𝑁}}$ = 200 GeV [Phys. Rev. Lett. 116, 122301 (2016)]

We previously reported jet-production rates in 𝑝 + 𝑝 and 𝑑 + Au collisions at $\sqrt{𝑠_{𝑁⁢𝑁}}$ = 200 GeV recorded in 2008 with the PHENIX detector at the Relativistic Heavy Ion Collider. Subsequently, we found that electronic noise in the electromagnetic calorimeter was not completely removed by the tower-timing cuts used in the analysis. We have conducted an independent re-analysis of the data that eliminated noisy towers by removing them completely from the analysis. These cuts remove any contributions from instrumental noise, but reduce the overall acceptance for electromagnetic clusters by ≈16% and hence the overall statistical power of the data. Finally, this re-analysis found that instrumental noise in the electromagnetic calorimeter led to an artificial increase in the jet yield for both the 𝑝 + 𝑝 and 𝑑 + Au collisions.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS1987

Composite grid and finite-volume LU implicit scheme for turbine flow analysis

A composite grid was generated in an attempt to improve grid quality for a typical turbine blade with large camber in terms of mesh control, smoothness, and orthogonality. This composite grid consists of the C grid (or O grid) in the immediate vicinity of the blade and the H grid in the upstream region and in the middle of the blade passage between the C grids. It provides a good boundary layer resolution around the leading edge region for viscous calculation, has orthogonality at the blade surface and slope continuity at the C-H (or O-H) interface, and has flexibility in controlling the mesh distribution in the upstream region without using excessive grid points. This composite grid eliminates the undesirable qualities of a single grid when generated for a typical turbine geometry. A finite-volume lower-upper (LU) implicit scheme can be used in solving for the turbine flows on the composite grid. This grid has a special grid node that is connected to more than four neighboring nodes in two dimensions and to more than six nodes in three dimensions. But the finite-volume approach poses no problem at the special point because each interior cell has only four neighboring cells in two dimensions and only six cells in three dimensions. The finite-volume LU implicit scheme was demonstrated to be robust and efficient for both external and internal flows in a broad flow regime.

Choo, Yung K.↗
NASA NTRS1987

Composite grid and finite-volume LU implicit scheme for turbine flow analysis

A composite grid was generated in an attempt to improve grid quality for a typical turbine blade with large camber in terms of mesh control, smoothness, and orthogonality. This composite grid consists of the C grid (or O grid) in the immediate vicinity of the blade and the H grid in the upstream region and in the middle of the blade passage between the C grids. It provides a good boundary layer resolution around the leading edge region for viscous calculation, has orthogonality at the blade surface and slope continuity at the C-H (or O-H) interface, and has flexibility in controlling the mesh distribution in the upstream region without using excessive grid points. This composite grid eliminates the undesirable qualities of a single grid when generated for a typical turbine geometry. A finite-volume lower-upper (LU) implicit schemes can be used in solving for the turbine flows on the composite grid. This grid has a special grid node that is connected to more than four neighboring nodes in two dimensions and to more than six nodes in three dimensions. But the finite-volume approach poses no problem at the special point because each interior cell has only four neighboring cells in two dimensions and only six cells in three dimensions. The finite-volume LU implicit scheme was demonstrated to be robust and efficient for both external and internal flows in a broad flow regime.

Choo, Yung K.↗
NASA NTRS2004

Did a Gamma-Ray Burst Initiate the Late Ordovician Mass Extinction?

Gamma-ray bursts (hereafter GRB) produce a flux of radiation detectable across the observable Universe. A GRB within our own galaxy could do considerable damage to the Earth's biosphere; rate estimates suggest that a dangerously near GRB should occur on average several times per billion years. At leastfive times in the history of lfe, the Earth experienced mass extinctions that eliminated a large percentage of the biota. Many possible causes have been documented, and GRB may also have contributed. The late Ordovician mass extinction approximately 440 million years ago may be at least partly the result of a GRB. Due to severe depletion of the ozone layer, intense solar ultraviolet radiation is expected to result from a nearby GRB, and some of the patterns of extinction and survivorship at this time may be attributable to elevated levels of UV radiation reaching the Earth. In addition a GRB could trigger the global cooling which occurs at the end of the Ordovician period that follows an interval of relatively warm climate. Intense rapid cooling and glaciation at that time, previously identijied as the probable cause of this mass extinction, may have resultedfiom a GRB.

Melott, A. L.↗
NASA NTRS2005

The Accretion Disk of the Lithium-Depleted Young Binary St 34

We presented the infrared spectrum of the young binary system St 34 obtained with the Infrared Spectrograph (IRS) on the Spitzer Space Telescope. The IRS spectrum clearly shows excess dust emission, consistent with the suggestion of White & Hillenbrand that St 34 is accreting from a circumbinary disk. The disk emission of St 34 is low in comparison with the levels observed in typical T Tauri stars; silicate features at 10 and 20 microns are much weaker than typically seen in T Tauri stars; and excess emission is nearly absent at the shortest wavelengths observed. These features of the infrared spectrum suggest substantial grain growth (to eliminate silicate features) and possible settling of dust to the disk midplane (to reduce the continuum excess emission levels), along with a relatively evacuated inner disk, as expected due to gravitational perturbations by the binary system. Although the position of St 34 in the H-R diagram suggests an age of 8f Myr, assuming that it lies at the distance of the Taurus-Auriga molecular clouds, White & Hillenbrand could not detect any Li I absorption, which would indicate a Li depletion age of roughly 25 Myr or more. We suggest that St 34 is closer than the Taurus clouds by about 30-40 pc and has an age roughly consistent with Li depletion models. Such an advanced age would make St 34 the oldest known low-mass pre-main-sequence object with a dusty accretion disk. The persistence of optically thick dust emission well outside the binary orbit may indicate a failure to make giant planets that could effectively remove dust particles.

Hartmann, Lee↗
NASA NTRS2023

STXM-C-XANES, IR Microspectroscopy, and Raman Microspectroscopy Analysis of Organic Matter in the Chwichiya 002 C3.00-Ungrouped Chondrite

Chwichiya 002 is a C3.00-ungrouped carbonaceous chondrite discovered in Western Sahara in 2018. The presence of hydrated phases in Chwichiya 002 was not confirmed by XRD analysis, and only a faint water and Si-O band attributed to phyllosilicate were observed by infrared transmission spectroscopy, indicating a very low degree of aqueous alteration (Meteoritical Bulletin, 2020). The structural order of polycyclic aromatic hydrocarbons evaluated by Raman spectroscopy indicates that the effect of thermal metamorphism is less severe than in the Semarkona meteorite, an LL3.00 ordinary chondrite (Meteoritical Bulletin, 2020). Chiwichiya 002 is a very primitive carbonaceous chondrite and an important information source for the early stage of the evolution of organic matter in the solar system. In this study, we investigated the molecular structure and distribution of organic matter in Chiwichiya 002 by Carbon X-ray Absorption Near Edge Structure (C-XANES) analysis using a Scanning Transmission X-ray Microscope (STXM). The STXM-C-XANES analysis has a spatial resolution of 20~100 nm and can observe the spatial distribution of organic materials in microstructures. In addition, to investigate the degree of thermal metamorphism of the organic matter, micro-IR, and micro-Raman spectroscopic analyses were performed. In addition, the Murchison CM2 chondrite was also analyzed for comparison. To evaluate contamination during analytical procedures, antigorite, which was heated in air at 500°C for 5 hours to eliminate organic matter was also analyzed in the same manner. The samples were milled into 100 nm-thick, thin sections using a Focused Ion Beam (FIB), and C-XANES spectra were obtained using the STXM at the High Energy Accelerator Research Organization, Photon Factory (PF), BL-19B. The obtained C-XANES spectra were smoothed and then fitted with Gaussian functions using the method of Le Guillou et al. (2018). The C-XANES showed that the ratio of oxygenated functional group (ketone, phenolic) carbons in Chwichiya 002 was lower than in Murchison, whereas the ratio of aliphatic carbons was almost the same. This may reflect the low degree of aqueous alteration of Chwichiya 002. In addition, contamination peaks were detected at 287.3-287.7 eV and 288.3-288.7 eV in the C-XANES spectra of some of the antigorite samples. The source of these peaks is under investigation. Raman spectroscopic analysis showed that the intensity ratio of the D band to the G band of Chwichiya 002 was slightly higher than that of Murchison. IR absorption spectra showed aromatic absorption at 1630 cm -1 , but there was little absorption due to aliphatic C-H around 2900 cm -1 . These results suggest that the organic matter in Chwichiya 002 may be more heated than in Murchison.

Chwichiya 002↗