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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 37 records · Page 2

Nanoscale Li, Na, and K ion-conducting polyphosphazenes by atomic layer deposition

A key trailblazer in the development of thin-film solid-state electrolytes has been lithium phosphorous oxynitride (LiPON), the success of which has led to recent progress in thin-film ion conductors. Here we compare the structural, electrochemical, and processing parameters between previously published LiPON and NaPON ALD processes with a novel ALD process for the K analogue potassium phosphorous oxynitride (KPON). In each ALD process, alkali tert-butoxides and diethylphosphoramidate are used as precursors. To understand the ALD surface reactions, this work proposes a reaction mechanism determined by in-operando mass spectrometry for the LiPON process as key to understanding the characteristics of the APON (A = Li, Na, K) family. As expected, NaPON and LiPON share similar reaction mechanisms as their structures are strikingly similar. KPON, however, exhibits similar ALD process parameters but the resulting film composition is quite different, showing little nitrogen incorporation and more closely resembling a phosphate glass. Due to the profound difference in structure, KPON likely undergoes an entirely different reaction mechanism. Furthermore, this paper presents a comprehensive summary of ALD ion conducting APON films as well as a perspective that highlights the versatility of ALD chemistries as a tool for the development of novel thin film ion-conductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparative Study of Lettuce and Radish Grown Under Red and Blue LEDs and White Fluorescent Lamps

Growing vegetable crops in space will be an essential part of sustaining astronauts during long-range missions. To drive photosynthesis, red and blue light-emitting diodes (LEDs) have attracted attention because of their efficiency, longevity, small size, and safety. In efforts to optimize crop yield, there is also recent interest in analyzing the subtle effects of additional wavelengths on plant growth. For instance, since plants often look purplish gray under red and blue LEDs, the addition of green light allows easy recognition of disease and the assessment of plant health status. However, it is important to know if wavelengths outside the traditional red and blue wavebands have a direct effect on enhancing or hindering the mechanisms involved in plant growth. In this experiment, a comparative study was performed on two short cycle crops of red romaine lettuce (Lactuca sativa cv. "Outredgeous") and radish (Raphanus sativa cv. 'Cherry Bomb'), which were grown under two light treatments. The first treatment being red (630 nm) and blue (450 nm) LEDs alone, while the second treatment consisted of daylight tri-phosphor fluorescent lamps (CCT approximately 5000 K) at equal photosynthetic photon flux (PPF). The treatment effects were evaluated by measuring the fresh biomass produced, plant morphology and leaf dimensions, leaf chlorophyll content, and adenosine triphosphate (ATP) within plant leaf/storage root tissues.

Food Production↗

Phosphine in the Venusian Atmosphere: A Strict Upper Limit from SOFIA GREAT Observations

The presence of phosphine (PH3) in the atmosphere of Venus was reported by Greaves et al. based on observations of the J = 1–0 transition at 267 GHz using ground-based, millimeter-wave spectroscopy. This unexpected discovery presents a challenge for our understanding of Venus's atmosphere, and has led to a reappraisal of the possible sources and sinks of atmospheric phosphorous-bearing gases. Here we present results from a search for PH3 on Venus using the German REceiver for Astronomy at Terahertz Frequencies instrument aboard the Stratospheric Observatory for Infrared Astronomy aircraft, over three flights conducted in November 2021. Multiple PH3 transitions were targeted at frequencies centered on 533 and 1,067 GHz, but no evidence for atmospheric PH3 was detected. Through radiative transfer modeling, we derived a disk-averaged upper limit on the PH3 abundance of 0.8 ppb in the altitude range 75–110 km, which is more stringent than previous ground-based studies.

M. A. Cordiner↗

High-Luminance LED Platform for Improved Efficacy in Directional Applications (Final Technical Report)

In this project, Lumileds developed a platform of high-luminance LEDs and LED light engines to increase efficacy and reduce energy consumption of directional lighting applications. The platform was developed through innovations in three key areas: (1) epi and device architectures optimized for high drive current density, breaking through the tradeoff in efficacy (lm/W) vs. emittance (lm/mm 2 ) exhibited by state-of-the-art products; (2) a compact chip-scale package allowing high packing density and thus high overall luminance in multi-emitter arrays; and (3) phosphor technology to enable correlated color temperature (CCT) tuning in multi-emitter arrays with optimized LED utilization, efficacy, color uniformity and color quality. Directional indoor and outdoor lighting applications make up a major portion of the total lighting energy consumption in the U.S, accounting for >40% of the energy savings potential of solid-state lighting. Success of this project helps accelerate the realization of these energy savings both through higher system efficacy and adoption due to new functionality, and thus contributes significantly to realizing the DOE Lighting program goals.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Achieving a blue-excitable yellow-emitting Ca-LMOF phosphor via water induced phase transformation

Luminescent metal-organic frameworks (LMOFs) with diverse structural features and promising fluorescence-based applications have attracted wide attention in the past two decades. In this work, a LMOF with the formula [Ca 4 (tcbpe-F) 2 (H 2 O) 3 ] (1, LMOF-411) has been constructed from calcium (Ca) and 1,1,2,2-tetrakis(4-(4-carboxyphenyl)phenyl)ethene (H 4 tcbpe-F). Compound 1 features a three-dimensional framework with a 10-nodal net topology. Due to the relatively high hydration energy of Ca 2+ , compound 1 readily transforms into a new phase formulated as [Ca(H 2 tcbpe-F)(H 2 O) 2 ] (1') upon exposure to water. Combining experimental characterization and theoretical calculations, we elucidated the mechanism of H 2 O-induced phase transition from 1 to 1'. Notably, the water induced phase transformation can be detected visibly from the change in luminescence, which originates from the fluorescent linker. Compound 1 emits green light ( λ em = 490 nm) under UV excitation, while compound 1' emits bright yellow light ( λ em = 550 nm) under blue excitation (450 nm). Compound 1' represents the first Ca based LMOF yellow phosphor and its luminescence quantum yield reaches 68%. It can be coated directly onto a commercial blue light-emitting-diode (LED) chip to fabricate a white LED (WLED).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Readying for a Color-Mixed Future Luminous Efficacy on the Horizon

If history repeats itself, lighting 20 years from now will be substantially different than what it is today. Twenty years ago, LEDs were a novelty, not quite ready for use in architectural lighting systems. A little more than 20 years before that, rare-earth tri-phosphor T8 fluorescent lamps were beginning to replace broadband halophosphate T12 fluorescent lamps, which themselves became the predominant source of lumens in the United States around the middle of the last century. At each step in this evolution, new lighting metrics have been developed to address differences in performance, and they in turn guided technology development. For example, in the 1960s, it was CRI and CCT, and more recently it has been LM-79 and TM-30.

Royer, Michael P.↗

Analysis and design of a refractive virtual image system

The optical performance of a virtual image display system is evaluated. Observation of a two-element (unachromatized doublet) refractive system led to the conclusion that the major source of image degradation was lateral chromatic aberration. This conclusion was verified by computer analysis of the system. The lateral chromatic aberration is given in terms of the resolution of the phosphor dots on a standard shadow mask color cathode ray tube. Single wavelength considerations include: astigmatism, apparent image distance from the observer, binocular disparities and differences of angular magnification of the images presented to each of the observer's eyes. Where practical, these results are related to the performance of the human eye. All these techniques are applied to the previously mentioned doublet and a triplet refractive system. The triplet provides a 50-percent reduction in lateral chromatic aberration which was the design goal. Distortion was also reduced to a minimum over the field of view. The methods used in the design of the triplet are presented along with a method of relating classical aberration curves to image distance and binocular disparity.

Kahlbaum, W. M.↗

Hydrotreating pine-derived catalytic fast pyrolysis oil to jet fuel: Process durability and impact of operating conditions

Hydrotreating woody biomass-derived catalytic fast pyrolysis (CFP) oil to jet fuel has the potential to enhance energy security due to the large abundance of forest and woody resources. CFP oil produced from pine over ZSM-5 was hydrotreated over sulfided NiMo/Al 2 O 3 for 410 h to study the impact of hydrotreating conditions (pressure, temperature, and weight hourly space velocity (WHSV)). The degree of deoxygenation remained high across the tested hydrotreating conditions, and the products contained < 0.01 wt% oxygen. Increasing hydrotreating pressure from 84 to 125 bar enhanced hydrogenation of aromatic rings and the formation of cycloalkanes and increasing the temperature from 385 to 400 degrees C enhanced cracking and the formation of jet-range molecules. Decreasing the weight hourly space velocity from 0.2 to 0.1 g/(g cat h) further enhanced cracking and led to higher gasoline- and lower jet fuel-range fractions. The highest jet fuel fraction (49 wt%) was obtained at 400 degrees C, 125 bar, 0.2 g/(g cat h) WHSV. CFP oils produced from pine over phosphorous-modified ZSM-5 were hydrotreated at this condition for 588 h to investigate the process durability. The hydrogenation performance of the catalyst gradually stabilized in approximately 300 h after which the product composition remained constant. Of the final hydrotreated CFP oil, 53 wt% fell in the jet fuel range with most of the tested fuel properties meeting ASTM D4054 and/or ASTM D7566 specifications. The freeze points were < -50 degrees C vs. guideline of < -40 degrees C and the viscosities at -20 degrees C were 3.8-4.1 mm 2 /s vs guideline of 8 mm 2 /s. Increasing the fraction of cycloalkanes could increase the cetane number and heating value, which did not meet the guidelines.

09 BIOMASS FUELS↗

Gallium phosphide energy converters

Betavoltaic power supplies based on gallium phosphide can supply long term low-level power with high reliability. Results are presented for GaP devices powered by Ni-63 and tritiarated phosphors. Leakage currents as low as 1.2 x 10(exp -17) A/cm(exp 2) have been measured and the temperature dependence of the reverse saturation current is found to have ideal behavior. A small demonstration system has been assembled that generates and stores enough electricity to light up an LED.

Sims, P. E.↗

Does mycorrhizal symbiosis determine the climate niche for Populus as a bioenergy feedstock?

This is the final technical and scientific report for DE-SC0016097, in which we investigated the role of symbiotic fungi in determining the climatic niche of trees. While microbes have long been viewed as agents of disease, recent explorations of the microbiome have led biologists to recognize that beneficial microbes play an equally vital role in maintaining the health of plants and animals. Perhaps the most ubiquitous form of beneficial interaction in terrestrial ecosystems occurs between fungi and plant roots. These fungus-root, or “mycorrhizal”, symbioses involve the reciprocal exchange of plant sugars for soil nutrients obtained by the fungus, such as nitrogen and phosphorous, which are critical for plant growth. It is known that mycorrhizal associations are widespread - occurring in approximately 90% of plant species - and diverse, with single plants able to associate simultaneously with over 100 species of fungi. Despite this, the ecological factors that control large-scale distribution and abundance of mycorrhizal symbioses are still poorly known, making it challenging to predict how mycorrhizal symbioses may change in future climate conditions or how these fungal communities might be manipulated to improve regional agriculture or forestry projects. In this research project we focused on a native North American tree with strong biofuel potential – Populus – to answer fundamental questions about the role of climate, soil environment, and mycorrhizal interactions in determining growth and competition in plant communities. Populus provides a unique opportunity for ecologically relevant experiments because of its widespread distribution across North America and its natural variability in mycorrhizal association types.

59 BASIC BIOLOGICAL SCIENCES↗

Catalyst and electrode research for phosphoric acid fuel cells

An account is given of the development status of phosphoric acid fuel cells' high performance catalyst and electrode materials. Binary alloys have been identified which outperform the baseline platinum catalyst; it has also become apparent that pressurized operation is required to reach the desired efficiencies, calling in turn for the use of graphitized carbon blacks in the role of catalyst supports. Efforts to improve cell performance and reduce catalyst costs have led to the investigation of a class of organometallic cathode catalysts represented by the tetraazaannulenes, and a mixed catalyst which is a mixture of carbons catalyzed with an organometallic and a noble metal.

Antoine, A. C.↗

Hypersonic Boundary-Layer Trip Development for Hyper-X

Boundary layer trip devices for the Hper-X forebody have been experimentally examined in several wind tunnels. Five different trip configurations were compared in three hypersonic facilities, the LaRC 20-Inch Mach 6 Air Tunnel, the LaRC 31 -Inch Mach 10 Air Tunnel, and in the HYPULSE Reflected Shock Tunnel at GASL. Heat transfer distributions, utilizing the phosphor thermography and thin-film techniques, shock system details, and surface streamline patterns were measured on a 0.333-scale model of the Hyper-X forebody. Parametric variations include angles-of-attack of 0-deg, 2-deg, and 4-deg; Reynolds numbers based on model length of 1.2 to 15.4 million: and inlet cowl door simulated in both open and closed positions. Comparisons of transition due to discrete roughness elements have led to the selection of a trip configuration for the Hyper-X Mach 7 flight vehicle.

Berry, Scott A.↗

Development of X-33/X-34 Aerothermodynamic Data Bases: Lessons Learned and Future Enhancements

A synoptic of programmatic and technical lessons learned in the development of aerothermodynamic data bases for the X-33 and X-34 programs is presented in general terms and from the perspective of the NASA Langley Research Center Aerothermodynamics Branch. The format used is that of the "aerothermodynamic chain," the links of which are personnel, facilities, models/test articles, instrumentation, test techniques, and computational fluid dynamics (CFD). Because the aerodynamic data bases upon which the X-33 and X-34 vehicles will fly are almost exclusively from wind tunnel testing, as opposed to CFD, the primary focus of the lessons learned is on ground-based testing. The period corresponding to the development of X-33 and X-34 aerothermodynamic data bases was challenging, since a number of other such programs (e.g., X-38, X-43) competed for resources at a time of downsizing of personnel, facilities, etc., outsourcing, and role changes as NASA Centers served as subcontractors to industry. The impact of this changing environment is embedded in the lessons learned. From a technical perspective, the relatively long times to design and fabricate metallic force and moment models, delays in delivery of models, and a lack of quality assurance to determine the fidelity of model outer mold lines (OML) prior to wind tunnel testing had a major negative impact on the programs. On the positive side, the application of phosphor thermography to obtain global, quantitative heating distributions on rapidly fabricated ceramic models revolutionized the aerothermodynamic optimization of vehicle OMLs, control surfaces, etc. Vehicle designers were provided with aeroheating information prior to, or in conjunction with, aerodynamic information early in the program, thereby allowing trades to be made with both sets of input; in the past only aerodynamic data were available as input. Programmatically, failure to include transonic aerodynamic wind tunnel tests early in the assessment phase led to delays in the optimization phase, as OMLs required modification to provide adequate transonic aerodynamic performance without sacrificing subsonic and hypersonic performance. Funding schedules for industry, based on technical milestones, also presented challenges to aerothermodynamics seeking optimum flying characteristics across the subsonic to hypersonic speed regimes and minimum aeroheating. This paper is concluded with a brief discussion of enhancements in ground-based testing/CFD capabilities necessary to partially/fully satisfy future requirements.

Miller, C. G.↗

The power of lanthanides: same composition, but different lanthanides leading to different interesting materials properties, from magnetocalorics to molecular magnets and phosphors

Commonly accepted design concepts for ionic liquids (ILs) state that the constituting ions must be large and carry low, well-dispersed charges. A series of ILs based of pentadeca charged ILs with pentanuclear linear {Ln 5 } units ([Ln 5 (C 2 H 5 -C 3 H 3 N 2 -CH 2 COO) 16 (H 2 O) 8 ](Tf 2 N) 15 (C 3 H 3 N 2 = imidazolium moiety, Tf 2 N = bis(trifluoromethanesulfonyl)amide) with Ln = Er, Ho, Tm) demonstrates that these criteria are not absolute. Highly charged ions can also support IL formation, provided they are sufficiently large. Expanding the series of these unconventional, record pentadeca charged with new lanthanide representatives, led to the discovery of additional unprecedented properties for ILs: The Gd compound exhibits a strong magnetocaloric effect (MCE) in the liquid state with a maximum magnetic entropy change of −ΔS M = −11 J⋅kg −1 ⋅K −1 at 2 K for Δμ 0 H = 7 T. Albeit the Dy representative shows slow magnetic relaxation, the relaxation times are not favorable for practical application as a molecular magnet. Lastly, for both the Gd and the Y compound, phosphorescence in the seconds time scale is observed, which is, to the best of our knowledge, the longest ever reported for an IL.

Ionic Liquids↗

Platinum-complexed phosphorous-doped carbon nitride for electrocatalytic hydrogen evolution

Sustainable hydrogen gas production is critical for future fuel infrastructure. Here, a series of phosphorous-doped carbon nitride materials were synthesized by thermal annealing of urea and ammonium hexafluorophosphate, and platinum was atomically dispersed within the structural scaffold by thermal refluxing with Zeise's salt forming Pt–N/P/Cl coordination interactions, as manifested in X-ray photoelectron and absorption spectroscopic measurements. The resulting materials were found to exhibit markedly enhanced electrocatalytic activity towards the hydrogen evolution reaction (HER) in acidic media, as compared to the P-free counterpart. This was accounted for by P doping that led to a significantly improved charge carrier density within C 3 N 4 , and the sample with the optimal P content showed an overpotential of only –22 mV to reach the current density of 10 mA cm –2 , lower than that of commercial Pt/C (–26 mV), and a mass activity (7.1 mA μg –1 Pt at –70 mV vs. reversible hydrogen electrode) nearly triple that of the latter. Finally, results from the present study highlight the significance of P doping in the manipulation of the electronic structures of metal/carbon nitride nanocomposites for high-performance HER electrocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing air-water interfaces of dibutyl phosphoric acid (HDBP) aqueous solutions using vibrational sum frequency generation (vSFG) spectroscopy

Liquid-liquid extraction is a separation technique implemented in a wide variety of areas, achieving particular success in both the nuclear and biomedical fields. In this work, vibrational sum frequency generation spectroscopy (VSFG) and surface tension measurements were used to investigate the adsorption of dibutyl phosphate (DBP) at air-aqueous interfaces to simulate liquid-liquid systems relevant to the Plutonium Uranium Redox Extraction (PUREX) Process. The objective of this work is to establish qualitative relationships between changes in the bulk aqueous phase concentrations of DBP and its concentration and structure at air-liquid interface as probed with VSFG. Nitric acid concentration and solution ionic strength were varied to examine their effect on the interfacial DBP.. Introduction of DBP into neat water resulted in reduction of the VSFG spectral intensity in the dangling O-H region (3680 – 3800 cm -1 ) but large increase in the H-bonded O-H stretch frequency region (3000 – 3500 cm-1) and the appearance of the CH 3 symmetric stretch and CH 3 Fermi resonance peaks at ~ 2880 and 2945 cm -1 , respectively, indicating DBP at the air-water interface. The intensity of the C-H strecth peaks increased as DBP concentration increased from 0.24 to 32 mM, accompanied by a decreasing surface tension values. At fixed DBP concentration, the addition of either or both of HNO 3 and NaNO 3 to an ionic strength of 1 M or 3 M led to significant reduction of the O-H VSFG peaks and enhancement of the C-H peaks. The origins of these experimental observations are attributed to both the increased HDBP molecules partitioning and adsorption to the interface and the protonation of the interfacial DBP- molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗