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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 703 records · Page 39
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Crystal Chemistry and Thermodynamics of HREE (Er, Yb) Mixing in a Xenotime Solid Solution

Rare earth elements (REEs), the 15 naturally occurring lanthanides plus yttrium and scandium, are ubiquitously used in modern life as they are critical components of many advanced devices and technologies. However, the demand for REEs is not equal, with the heavy rare earth elements (HREEs) having a higher demand. Xenotime (HREEPO 4 ) is an important HREE ore mineral and globally is an economical source of HREE. Most of the crystallographic and thermodynamic properties of xenotime endmembers have been elucidated by calorimetric, solubility, and high-pressure studies. Yet, in natural systems, endmembers are rarely encountered, and instead, REE solid solutions are more commonly observed. Here, we characterize the crystal chemistry, thermodynamics of HREE mixing, and high-temperature material behaviors and thermochemistry of a synthetic erbium (Er)-ytterbium (Yb) binary xenotime solid solution (Er (x) Yb (1-x) PO 4 ) using a suite of experimental techniques, including X-ray fluorescence spectroscopy, synchrotron X-ray powder diffraction implemented with Rietveld analysis, Fourier transform infrared spectroscopy coupled with attenuated total reflectance, Raman spectroscopy, thermogravimetric analysis coupled with differential scanning calorimetry, and high-temperature oxide melt drop solution calorimetry. Our results shed light on the formation of natural xenotimes and lay the foundation for their industrial applications as thermal coating materials.

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

A Porous Crystalline Nitrone-Linked Covalent Organic Framework

Herein, we report the synthesis of a nitrone-linked covalent organic framework, COF-115, by combining N, N', N', N'''-(ethene-1, 1, 2, 2-tetrayltetrakis(benzene-4, 1-diyl))tetrakis(hydroxylamine) and terephthaladehyde via a polycondensation reaction. In this study, the formation of the nitrone functionality was confirmed by solid-state 13 C multi cross-polarization magic angle spinning NMR spectroscopy of the 13 C-isotope-labeled COF-115 and Fourier-transform infrared spectroscopy. The permanent porosity of COF-115 was evaluated through low-pressure N 2 , CO 2 , and H 2 sorption experiments. Water vapor and carbon dioxide sorption analysis of COF-115 and the isoreticular imine-linked COF indicated a superior potential of N-oxide-based porous materials for atmospheric water harvesting and CO 2 capture applications. Density functional theory calculations provided valuable insights into the difference between the adsorption properties of these COFs. Lastly, photoinduced rearrangement of COF-115 to the associated amide-linked material was successfully demonstrated.

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

Probing the thermal decomposition of plutonium (III) oxalate with IR and Raman spectroscopy, X-ray diffraction, and electron microscopy

The thermal decomposition of Pu(III) oxalate was analyzed by Raman microspectroscopy, infrared spectroscopy, scanning electron microscopy, and powder X-ray diffraction. These data show that crystalline Pu 2 (C 2 O 4 ) 3 •9H 2 O progressively loses water and oxalate ligands as it is heated, which leads to a decrease in long-range lattice ordering, though minimal changes are observed in gross crystalline morphology. The onset of PuO 2 formation was observed between 200 - 250 °C. Thermal decomposition of oxalate ligands leads to the formation of CO 2 and plutonium oxalate-carbonate moieties, which had not been observed in previously published thermogravimetric measurements of Pu(III) oxalate. Formation of plutonium oxalate-carbonate moieties is believed to be associated with a change in the plutonium oxidation state from 3+ to 4+, which occurs prior to PuO 2 formation. The data provided herein demonstrate the rich spectroscopic nature of a rather underexplored, and technologically relevant, plutonium system. Ideally these results will further future investigations into the Pu(III) oxalate system both experimentally and computationally.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Discovering CO Adsorption and Desorption Pathways from Chemical Reaction Neural Network Modeling of Transient Kinetics Spectroscopy

Here, we demonstrate a data-driven approach to interpreting surface reactions by combining time-resolved gas pulsing infrared spectroscopy with chemical reaction neural networks (CRNNs). Using CO adsorption and desorption on Pd(111) at 460–490 K as a model system, we show how transient kinetic data can reveal detailed reaction mechanisms. Starting with a simple one-species model, we systematically evaluate increasingly complex mechanisms involving hollow and bridge site adsorption. Despite the similar goodness of fit to the same experimental absorbance data, our models predict distinct coverage dynamics for different adsorption sites. Through analysis of spectral peak stability and predicted dynamics, we identify a mechanism in which CO primarily adsorbs on bridge sites followed by rapid conversion to hollow sites as being the most physically consistent with experimental observations. This work provides a framework for extracting mechanistic insights from limited experimental data, demonstrating how machine learning can bridge the gap between transient kinetic measurements and a molecular-level understanding of surface reactions.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Direct Synthesis of Polyester from Biomass Derived 1,6-hexanediol using a Copper-Ceria Catalyst

Biomass derived polyesters are gaining attention due to their increased mechanical and thermal properties, and also because of their biodegradability. These polyesters are typically synthesized from polycondensation reactions between diols with dicarboxylic acids using catalysts. Other methods such as alcoholysis and acidolysis of low molecular weight esters and alcoholysis of acyl chlorides are also well known. Direct conversion of diol to ester without using dicarboxylic acid is not well known, and to our knowledge has not been reported over a solid catalyst. In this study, we report a direct synthesis of polyester from 1,6-hexanediol using a copper-ceria catalyst without using a dicarboxylic acid monomer. The copper-ceria catalysts were synthesized by incipient wetness impregnation method and characterized using X-ray photoelectron spectroscopy (XPS), X-ray diffraction analysis (XRD), Brunauer-Emmett-Teller (BET), and infrared spectroscopy (IR). Our initial studies show that 1,6-hexanediol can be converted to corresponding polyester at higher temperatures under atmospheric pressures of CO2 or N2. The reaction products were analyzed using nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC), high performance liquid chromatography (HPLC), and IR spectroscopy.

Biomass derived diols↗
NASA NTRS1995

Near-infrared and optical spectroscopy of FSC 10214+4724

New infrared and optical spectroscopic observations, obtained with the W. M. Keck Telescope, are reported for the highly luminous infrared source FSC 10214+4724. The rest frame optical spectrum shows new emission lines of (Ne III), (Ne V), (O I), (O II), (S II), and He(+), while the rest frame ultraviolet spectrum shows new lines of O IV) + Si IV, N III, N IV), Si II, Ne IV, and possibly N II and (Ne III), as well as clearly showing that Ly-alpha is self-absorbed. The emission-line spectrum is most characteristic of a Seyfert 2 nucleus. The preponderance of spectroscopic evidence strengthens the case for a dust-enshrouded Active galactic nuclei (AGN) powering much or most of the observed luminosity. The various spectral lines lead to a wide range in the inferred reddening and ionization parameter for this system, suggesting that we are viewing several environments through differing extinctions.

Soifer, B. T.↗
DOE OSTI2021

The preparation and characterization of chemically deuterium incorporated cotton fibers

Preparation of deuterium incorporated cellulose is a vital tool to investigate cellulose internal structure and to expand the application fields of cellulose materials. In this study, cellulosic cotton fibers with anti-rehydration (exchange-resistant) deuterium incorporated in cellulose were prepared by chemical hydrogen–deuterium exchange treatment. The chemical hydrogen–deuterium exchange process, along with exchange time, were characterized by nuclear magnetic resonance hydrogen spectroscopy (1H-NMR). The anti-rehydration deuterium incorporation was determined by Fourier Transform infrared spectroscopy (FTIR) and Stable Isotope Ratio Mass Spectrometer (IRSM). Here, the effect of the deuterium hydroxyl substitution on cotton fiber’s spectral data, microstructure, crystalline information, degree of polymerization, as well as it’s thermogravimetric analysis (charcoalization and combustion) are explored. Analysis of the chemical exchange process indicated that the hydrogen–deuterium exchange occurred preferentially in the amorphous cellulose component over the first several minutes. Deuterium exchange in the anti-rehydration crystalline phase took several hours. Increasing the treatment time, enhanced exchange-resistant deuterium incorporation to as high as about 60% of the cotton fibers’ cellulose hydroxyl groups was achieved. The characterization of FTIR, Fourier transform Raman (FT-Raman), and near-infrared spectra (NIR) all exhibited the deuterium spectral isotope effect on cellulose hydroxl groups. While, apart from the effect of reaction temperature, deuterium incorporation isotope effect did not affect the cellulose microstructure, crystalline index and the degree of polymerization properties. Furthermore, the thermogravimetric analysis of deuterated cotton fibers under N 2 and air atmosphere were both altered due to the thermodynamic isotope effect. These observations revealed the hydrogen–deuterium exchange treatment process and impacts on cellulose fiber properties, which helped us to better understand the cellulose internal structure and may facilitate the potential utilization of deuterated cellulosic materials.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1980

Far-infrared measurements of trace gases

A better detector system was developed for far infrared spectroscopy by usng cryogenic technology to cool bolometric detectors to approximately 0.4K. Technical assistance was provided to two submillimeter infrared balloon experiment (SIBEX) flights which demonstrated the diagnostic capability of far IR emission spectroscopy. It is estimated that more than a hundred spectral emission features were detected which are not due to the main emitting gases O3, O2, and H2O. The trace species sources for many features still remain unidentified and the spectra obtained during the SIBEX flights present a new source of information on stratospheric composition.

Nolt, I. G.↗
DOE OSTI2025

Dissolved CO 2 Modulates the Electrochemical Capacitance on Gold Electrodes

The presence of CO 2 at an electrified interface between an aqueous electrolyte and a metal electrode is the prerequisite for many electrochemical CO 2 capture technologies. To understand the behavior of dissolved CO 2 at an aqueous electrified interface, we characterized the electrochemical interface of planar gold electrodes with cyclic voltammetry, electrochemical impedance spectroscopy (EIS), electrochemical surface plasmon resonance (EC–SPR), and attenuated total reflectance surface-enhanced infrared spectroscopy (ATR–SEIRAS). Under all investigated conditions, we observed a decrease in the electrochemical capacitance upon saturation of the electrolyte with CO 2 , as compared to an electrolyte saturated with Ar. EIS and EC–SPR showed that this capacitance reduction was also potential dependent: it reached a minimum near the point of zero charge and became more significant as the applied potential moved further away from the point of zero charge. Hybrid quantum–classical simulations of the gold/aqueous electrolyte interface indicate that bicarbonate decreases the capacitance and modifies the composition of the electric double layer. In addition to the binding of bicarbonate under positive bias, we propose that molecular CO 2 can be induced by applied potential to concentrate in the diffuse layer of the electric double layer, leading to a reduction in the electrochemical capacitance under both negative and positive bias. Furthermore, this work advances the understanding of non-Faradaic effects of dissolved CO 2 at aqueous electrified interfaces of relevance for electrochemical CO 2 capture.

25 ENERGY STORAGE↗
DOE OSTI2025

Toward the Observation of Dimagnesocene

We have examined the electronic structure of C 5 H 5 MgMgC 5 H 5 , or dimagnesocene, using high-level coupled-cluster techniques. This research is suitable in light of the remarkable synthesis of the valence-isoelectronic diberyllocene by Boronski, Crumpton, Wales, and Aldridge. The Mg–Mg bond distance is predicted to be 2.758 Å, and the Mg–Mg bond dissociation energy is predicted to be 51.8 kcal/mol. Unique aspects to the present research is our characterization of the ionization energy and the electron affinity of this molecule, the energy of dissociation into two neutral cyclopentadienyl magnesium radicals, the determination of the neutral structure at the CCSD(T)/cc-pVTZ level, and the computation of the Raman intensities at the MP2/cc-pVDZ level. Apart from mass spectroscopy, the simplest means of experimental detection is gas-phase or matrix-isolated infrared spectroscopy, in which the A 2 ″ peak at 801 cm –1 should be the most prominent, with an intensity of 581 km/mol.

bond cleavage↗
NASA NTRS1992

The Quickest, Lowest-cost Lunar Resource Assessment Program: Integrated High-tech Earth-based Astronomy

Science and technology applications for the Moon have not fully kept pace with technical advancements in sensor development and analytical information extraction capabilities. Appropriate unanswered questions for the Moon abound, but until recently there has been little motivation to link sophisticated technical capabilities with specific measurement and analysis projects. Over the last decade enormous technical progress has been made in the development of (1) CCD photometric array detectors; (2) visible to near-infrared imaging spectrometers; (3)infrared spectroscopy; (4) high-resolution dual-polarization radar imaging at 3.5, 12, and 70 cm; and equally important (5) data analysis and information extraction techniques using compact powerful computers. Parts of each of these have been tested separately, but there has been no programmatic effort to develop and optimize instruments to meet lunar science and resource assessment needs (e.g., specific wavelength range, resolution, etc.) nor to coordinate activities so that the symbiotic relation between different kinds of data can be fully realized. No single type of remotely acquired data completely characterizes the lunar environment, but there has been little opportunity for integration of diverse advanced sensor data for the Moon. Two examples of technology concepts for lunar measurements are given. Using VIS/near-IR spectroscopy, the mineral composition of surface material can be derived from visible and near-infrared radiation reflected from the surface. The surface and subsurface scattering properties of the Moon can be analyzed using radar backscattering imaging.

Pieters, Carle M.↗
NASA NTRS1994

Infrared Astronomy with Arrays: The Next Generation; Sunset Village, Los Angeles, CA, Oct. 1993

Conference papers on infrared array techniques and methods for infrared astronomy are presented. Topics covered include the following: infrared telescopes; infrared spectrometers; spaceborne astronomy; astronomical observatories; infrared cameras; imaging techniques; sky surveys; infrared photography; infrared photometry; infrared spectroscopy; equipment specifications; data processing and analysis; control systems; cryogenic equipment; adaptive optics; image resolution; infrared detector materials; and focal plane arrays.

Mclean, Ian S.↗
DOE OSTI2020

A Rotation Rate for the Planetary-mass Companion DH Tau b

DH Tau b is a young planetary-mass companion orbiting at a projected separation of 320 au from its ∼2 Myr old host star DH Tau. With an estimated mass of 8–22 M{sub Jup} this object straddles the deuterium-burning limit, and might have formed via core or pebble accretion, disk instability, or molecular cloud fragmentation. To shed light on the formation history of DH Tau b, we obtain the first measurement of rotational line broadening for this object using high-resolution (R ∼ 25,000) near-infrared spectroscopy from Keck/NIRSPEC. We measure a projected rotational velocity (v sin i) of 9.6 ± 0.7 km s{sup −1}, corresponding to a rotation rate that is between 9% and 15% of DH Tau b’s predicted breakup speed. This low rotation rate is in good agreement with scenarios in which magnetic coupling between the companion and its circumplanetary disk during the late stages of accretion reduces angular momentum and regulates spin. We compare the rotation rate of DH Tau b to published values for other planetary-mass objects with masses between 0.3 and 20 M{sub Jup} and find no evidence of a correlation between mass and rotation rate in this mass regime. Finally, we search for evidence of individual molecules in DH Tau b’s spectrum and find that it is dominated by CO and H{sub 2}O, with no evidence of the presence of CH{sub 4}. This agrees with expectations given DH Tau b’s relatively high effective temperature (∼2300 K).

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Two-dimensional electronic–vibrational spectroscopy: Exploring the interplay of electrons and nuclei in excited state molecular dynamics

Two-dimensional electronic-vibrational spectroscopy (2DEVS) is an emerging spectroscopic technique which exploits two different frequency ranges for the excitation (visible) and detection (infrared) axes of a 2D spectrum. In contrast to degenerate 2D techniques, such as 2D electronic or 2D infrared spectroscopy, the spectral features of a 2DEV spectrum report cross correlations between fluctuating electronic and vibrational energy gaps rather than autocorrelations as in the degenerate spectroscopies. The center line slope of the spectral features reports on this cross correlation function directly and can reveal specific electronic-vibrational couplings and rapid changes in the electronic structure, for example. The involvement of the two types of transition moments, visible and infrared, makes 2DEVS very sensitive to electronic and vibronic mixing. 2DEV spectra also feature improved spectral resolution, making the method valuable for unraveling the highly congested spectra of molecular complexes. The unique features of 2DEVS are illustrated in this paper with specific examples and their origin described at an intuitive level with references to formal derivations provided. Although early in its development and far from fully explored, 2DEVS has already proven to be a valuable addition to the tool box of ultrafast nonlinear optical spectroscopy and is of promising potential in future efforts to explore the intricate connection between electronic and vibrational nuclear degrees of freedom in energy and charge transport applications.

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

Damage-free Analysis of Biological Materials by Vibrational Spectroscopy in the EM

In summary, vibrational spectroscopy in the electron microscope promises to probe biological materials in a way that is similar to infrared spectroscopy, at a spatial resolution of about 30-50 nm, while circumventing radiation damage. Herein we are now focused on developing this technique fully, using a side-entry cryotransfer holder in a Nion HERMES electron microscope equipped with a fast and efficient EELS direct detector [10], and capable of 5 meV (and better) energy resolution. The results of these investigations will be reported at the meeting.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Cascade Reaction of Ethanol to Butadiene over Multifunctional Silica-Supported Ag and ZrO 2 Catalysts

Although butadiene is currently a by-product of naphtha cracking, interest in producing butadiene from bio-based ethanol has increased because of the lower environmental impact of the ethanol to butadiene reaction. Furthermore, this work explores a multifunctional catalyst system composed of silica-supported Ag and ZrO 2 used for the cascade reaction of ethanol to butadiene at 573 K. The Ag and ZrO 2 components were synthesized on separate support particles enabling characterization of each component without interference from the other. High selectivity to butadiene (65%) at high ethanol conversion (75%) was achieved with an appropriate ratio of Ag and ZrO 2 in the reactor. Silver catalyzed the initial dehydrogenation of ethanol to acetaldehyde while ZrO 2 catalyzed the C-C coupling and subsequent dehydration reactions. The silica-supported ZrO 2 exhibited superior selectivity relative to bulk ZrO 2 in the Ag-promoted ethanol to butadiene reaction. Results from Zr K-edge X-ray absorption spectroscopy and UV-Vis spectroscopy showed that ZrO 2 was highly dispersed on the silica support over a range of loadings. Infrared spectroscopy of adsorbed pyridine, CO, and CO 2 , and kinetics of probe reactions 1-butene double bond isomerization, 2-propanol decomposition, and ethanol hydrogenation of acetone were used to compare the acid-base nature and chemical reactivity of silica-supported ZrO 2 to bulk ZrO 2 .

09 BIOMASS FUELS↗
NASA NTRS1991

Infrared variability of Jupiter and Saturn

Infrared spectroscopy provides unique insights into the chemistry and dynamics of the atmospheres of Jupiter and Saturn, and of the enigmatic satellite of Saturn, Titan. The 5 micron spectral region of these objects is transparent to deep levels, and is therefore particularly useful for the identification of molecules that are present at very low (parts per billion) concentrations. In Titan, 5 micron observations probe atmospheric layers at or near the surface. Ground-based spectroscopy complements Voyager, Galileo, and Cassini measurements. The spectroscopy is sensitive to lower mixing ratios for selected molecules, while the on-board mass and infrared spectrometers probe molecules and levels that are inaccessible form the ground. The observations also provide time-based data for preparation of the upcoming missions.

Knacke, Roger↗
NASA NTRS2006

A Model Study of the Thermal Evolution of Astrophysical Ices

We address the question of the evolution of ices that have been exposed to radiation from stellar sources and cosmic rays. We studied in the laboratory the thermal evolution of a model ice sample: a mixture of water, hydrogen peroxide, dioxygen, and ozone produced by irradiating solid H2O2 with 50 keV H(+) at 17 K. The changes in composition and release of volatiles during warming to 200 K were monitored by infrared spectroscopy, mass spectrometry, and microbalance techniques. We find evidence for voids in the water component from the infrared bands due to dangling H bonds. The absorption from these bands increases during heating and can be observed at temperatures as high as approx. 155 K. More O2 is stored in the radiolyzed film than can be retained by codeposition of O2 and H2O. This O2 remains trapped until approx. 155 K, where it desorbs in an outburst as water ice crystallizes. Warming of the ice also drastically decreases the intrinsic absorbance of O2 by annealing defects in the ice. We also observe loss of O3 in two stages during heating, which correlates with desorption and possibly chemical reactions with radicals stored in the ice, triggered by the temperature increase.

Loeffler, M. J.↗