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At least 397 records · Page 22

Electrochemical growth of linear conducting crystals in microgravity

Much attention has been given to the synthesis of linear conducting materials. These inorganic, organic, and polymeric materials have some very interesting electrical and optical properties, including low temperature superconductivity. Because of the anisotropic nature of these compounds, impurities and defects strongly influences the unique physical properties of such crystals. Investigations have demonstrated that electrochemical growth has provided the most reproducible and purest crystals. Space, specifically microgravity, eliminates phenomena such as buoyancy driven convection, and could permit formation of crystals many times purer than the ones grown to date. Several different linear conductors were flown on Get Away Special G-007 on board the Space Shuttle Columbia, STS 61-C, the first of a series of Project Explorer payloads. These compounds were grown by electrochemical methods, and the growth was monitored by photographs taken throughout the mission. Due to some thermal problems, no crystals of appreciable size were grown. The experimental results will be incorporated into improvements for the next 2 missions of Project Explorer. The results and conclusions of the first mission are discussed.

Cronise, Raymond J., IV↗

Studies of thermal wave phenomena on the Jovian planets

Ground based and Voyager observations of Jupiter have provided evidence that the tropospheric temperature shows global scale longitudinal variations which are often wavelike in character. Voyager data are reported to exhibit the presence of slowly moving thermal features, wherein the jovian tropospheric temperature patterns are not advected by the equatorial zonal winds, but are not found to rotate at the System III (interior) rate. Ground based data in a broad infrared band (8 to 13 micron) show a wavelike structure whose amplitude and spatial scale are similar to the reported properties of the slowly moving thermal features. This study is directed toward obtaining additional ground based data in infrared spectral bands whose contribution functions are optimized for specific atmospheric regions (tropospheric at 20 micron, and stratospheric at 7.8 micron), in order to confirm the previous results, and to identify the nature and physical significance of wavelike longitudinal temperature fluctuations on the Jovian planets. A 2-D infrared array detector and low resolution cryogenic grating spectrometer is being adapted to obtain maps in approx. 2/cm bandpasses.

Deming, Drake↗

Transient nucleate pool boiling in microgravity: Some initial results

Variable gravity provides an opportunity to test the understanding of phenomena which are considered to depend on buoyancy, such as nucleate pool boiling. The active fundamental research in nucleate boiling has sought to determine the mechanisms or physical processes responsible for its high effectiveness, manifested by the high heat flux levels possible with relatively low temperature differences. Earlier research on nucleate pool boiling at high gravity levels under steady conditions demonstrated quantitatively that the heat transfer is degraded as the buoyancy normal to the heater surfaced increases. Correspondingly, it was later shown, qualitatively for short periods of time only, that nucleate boiling heat transfer is enhanced as the buoyancy normal to the heater surface is reduced. It can be deduced that nucleate pool boiling can be sustained as a quasi-steady process provided that some means is available to remove the vapor generated from the immediate vicinity of the heater surface. One of the objectives of the research, the initial results of which are presented here, is to quantify the heat transfer associated with boiling in microgravity. Some quantitative results of nucleate pool boiling in high quality microgravity (a/g approximately 10(exp -5)) of 5s duration, obtained in an evacuated drop tower, are presented here. These experiments were conducted as precursors of longer term space experiments. A transient heating technique is used, in which the heater surface is a transparent gold film sputtered on a qua rtz substrate, simultaneously providing the mean surface temperature from resistance thermometry and viewing of the boiling process both from beneath and across the surface. The measurement of the transient mean heater surface temperature permits the computation, by numerical means, of the transient mean heat transfer coefficient. The preliminary data obtained demonstrates that a quasi-steady boiling process can occur in microgravity if the bulk liquid subcooling is sufficiently high and if the imposed heat flux is sufficiently low. This is attributed to suface tension effects at the liquid-vapor-solid junction causing rewetting to take place, sustaining the nucleate boiling. Otherwise, dryout at the heater surface will occur, as observed.

Merte, Herman, Jr.↗

Effects of Ambient Inert Gas Properties on Cool-Flame Combustion of Normal-Alkane Droplets in Microgravity

Cool-flame-supported quasi-steady droplet combustion was first observed during droplet combustion experiments conducted onboard the International Space Station (ISS) in the Combustion Integrated Rack (CIR) with n-alkane fuels. These cool flames, not visible to the naked eye, result from the existence of the negative-temperature-coefficient (NTC) region during the combustion n-alkane fuels when the chemical-kinetic pathways experience a transition from the low-temperature chemistry to the normal, high-temperature-controlled chemistry. In this study, we present results for the cool-flame-supported droplet burning rates and extinction diameters for n-alkane fuels (n-heptane, n-octane, n-decane, and n-dodecane) in inert-diluent-substituted ambient environments. In these ISS experiments, some of the nitrogen in the ambient gas mixture is replaced by an inert gas, namely, carbon dioxide, helium, or xenon. Different diluents were observed to exert remarkably different influences on the cool-flame combustion of fuel droplets. The results show that the cool-flame extinction diameter is drastically increased with helium dilution compared to N2, CO2 or Xe, and Xe dilution leads to longer burning with a smaller extinction diameter. Unlike hot flames, the cool-flame burning rates are controlled by the cool-flame temperature established in the NTC region by the chemical kinetics, rather than by equilibrium thermodynamics, and the thermo-physical properties of the ambient gases, which control the heat feed back to the liquid droplet. The cool-flame extinction is triggered by the instability that occurs at the low-temperature end of the NTC region, below which cool diffusion flames become statically unstable. A quasi-steady theoretical model, presented earlier, which involves a six-step reduced-chemistry mechanism, valid around the lower end of the NTC region, is shown to explain the observed experimental trends qualitatively.

microgravity↗

X-Ray Spectroscopy Using Low Temperature Detectors

After several decades of development, a significant amount of the effort in low temperature detectors (LTDs) is concentrated on deploying real-world experiments. This has resulted from a great deal of basic detector physics performed by several generations of students, post-docs, and researchers. One of the most fruitful applications of LTDs is in non-dispersive x-ray spectroscopy. LTD x-ray spectrometers are broadband, efficient, moderately high-resolution, and can handle moderately high count rates. However, they require significantly more power, mass, and infrastructure compared to traditional solid state x-ray spectrometers, and cannot achieve, at least at low energies, the resolving powers achieved with dispersive spectrometers. In several fields, however, LTDs have or will make a significant contribution. In this review, we will discuss x-ray spectroscopy in general, the fields of science where LTDs are making a significant impact, and some of the current and near-term LTD spectrometers.

Porter, Frederick↗

Climatic Implications of the Observed Temperature Dependence of the Liquid Water Path of Low Clouds

The uncertainty in the global climate sensitivity to an equilibrium doubling of carbon dioxide is often stated to be 1.5-4.5 K, largely due to uncertainties in cloud feedbacks. The lower end of this range is based on the assumption or prediction in some GCMs that cloud liquid water behaves adiabatically, thus implying that cloud optical thickness will increase in a warming climate if the physical thickness of clouds is invariant. Satellite observations of low-level cloud optical thickness and liquid water path have challenged this assumption, however, at low and middle latitudes. We attempt to explain the satellite results using four years of surface remote sensing data from the Atmospheric Radiation Measurements (ARM) Cloud And Radiation Testbed (CART) site in the Southern Great Plains. We find that low cloud liquid water path is insensitive to temperature in winter but strongly decreases with temperature in summer. The latter occurs because surface relative humidity decreases with warming, causing cloud base to rise and clouds to geometrically thin. Meanwhile, inferred liquid water contents hardly vary with temperature, suggesting entrainment depletion. Physically, the temperature dependence appears to represent a transition from higher probabilities of stratified boundary layers at cold temperatures to a higher incidence of convective boundary layers at warm temperatures. The combination of our results and the earlier satellite findings imply that the minimum climate sensitivity should be revised upward from 1.5 K.

DelGenio, Anthony↗

Co-existence of atomically dispersed Ru and Ce 3+ sites is responsible for excellent low temperature N 2 O reduction activity of Ru/CeO 2

Nitrous oxide N 2 O reduction is a big challenge due to high global warming potential of N 2 O. (~300 times higher compared with CO 2 ). The best known catalysts, such as Rh/ceria, require relatively high temperatures for N 2 O decomposition. Herein, we report that Ru/ceria catalysts with low Ru loading of ~0.25 wt% efficiently catalyze low temperature N 2 O reduction by CO starting at 100 °C (full N 2 O conversion below 200 °C) under industrially relevant flow rates and gas concentrations. Further, this remarkable performance stems from maintaining isolated Ru cations even on reduced ceria surface and, simultaneously, the propensity of Ru to affect ceria surface to form labile surface oxygen thereby creating large number of oxygen vacancies (Ce +3 cations) in the presence of CO. In contrast, for Rh/CeO 2 catalysts with equivalent metal loading, the activity is much lower because atomically dispersed Rh sinters into metallic clusters at the onset reaction temperature (~200 °C): these clusters are much less effective than isolated single Ru ions, with lower Ce +3 concentration maintained on reduced Rh/CeO 2 catalyst. Our study highlights the benefits of gaining molecular-level insight into the dynamic nature of catalytically active sites under reaction conditions for preparing catalysts containing low loading of precious metals with unsurpassed low temperature activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

How magnetic field can transform a superconductor into a Bose metal

Abstract We discuss whether a simple theory of superconducting stripes coupled by Josephson tunneling can describe a metallic transport, once the coherent tunneling of pairs is suppressed by the magnetic field. For a clean system, the conclusion we reached is negative: the excitation spectrum of preformed pairs consists of Landau levels, and once the magnetic field exceeds a critical value, the transport becomes insulating. As a speculation, we suggest that a Bose metal can exist in disordered systems provided that the disorder is strong enough to localize some pairs. Then the coupling between propagating and localized pairs broadens the Landau levels, resulting in a metallic conductivity. Our model respects the particle–hole symmetry, which leads to a zero Hall response. And intriguingly, the resulting anomalous metallic state has no Drude peak and the spectral weight of the cyclotron resonance vanishes at low temperatures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Collapse of the waiting time effect in a spin glass

Waiting time measurements are reported here for a bulk polycrystalline sample of the spin glass Cu 0.95 Mn 0.05 . We observe a suppression of aging as the glass temperature is approached from below. These results are interpreted in terms of a spin-glass correlation length approaching and reaching crystallite sizes. They provide a direct experimental connection between the correlation length scale and relaxation times in the spin-glass state. In particular, these measurements track the value of the dynamic critical exponent as the system transitions from the critical temperature regime to its low-temperature, quasistatic nonequilibrium phase.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Distinguishing the gapped and Weyl semimetal scenario in ZrTe 5 : insights from an effective two-band model

In this work, we study the static and dynamic transport properties of a low-energy two-band model proposed previously in Martino et al. [PRL 122, 217402 (2019)], with an anisotropic in-plane linear momentum dependence and a parabolic out-of-plane dispersion. The model is extended to include a negative band gap, which leads to the emergence of a Weyl semimetal (WSM) state, as opposed to the gapped semimetal (GSM) state when the band gap is positive. Furthermore, we calculate and compare the zero- and finite-frequency transport properties of the GSM and WSM cases. The DC properties that are calculated for the GSM and WSM cases are Drude spectral weight, mobility, and resistivity. We determine their dependence on the Fermi energy and crystal direction. The in- and out-of-plane optical conductivities are calculated in the limit of the vanishing interband relaxation rate for both semimetals. The main common features are an ω 1/2 in-plane and ω 3/2 out-of-plane frequency dependence of the optical conductivity. We seek particular features related to the charge transport that could unambiguously point to one ground state over the other, based on the comparison with the experiment. Differences between the WSM and GSM are in principle possible only at extremely low carrier concentrations and at low temperatures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ignition Delays of Alkyl Thiophosphites with White and Red Fuming Nitric Acids Within Temperature Range 80 to -105 F

Ignition delays of alkyl thiophosphites were obtained in a modified open-cup apparatus and a small-scale rocket engine apparatus. At -40 F, mixed alkyl thiophosphites gave short delays with white fuming nitric acid containing 2 percent water and red fuming nitric acids of widely varying compositions. At -40 F and higher, triethyl trithiophosphite blended with as much as 40 percent n-heptane gave satisfactory self-igniting properties at temperatures as low as -76 F.

FUELS - PROPERTIES PHYSICAL AND CHEMICAL↗

Three-dimensional modelling of a self-sustained atmospheric pressure glow discharge

The atmospheric pressure glow discharge (APGD) is a relatively simple and versatile plasma source used in diverse applications. Stable APGD operation at high currents, generally a challenge due to instabilities leading to glow-to-arc transition, has been demonstrated using actively-controlled cathodic cooling. This article presents the computational modelling and simulation of a self-sustained direct-current APGD in helium within a 10 mm pin-to-plate inter-electrode gap for currents ranging from 4 to 40 mA. The APGD model is comprised of the conservation equations for total mass, chemical species, momentum, thermal energy of heavy-species and of free electrons, and electric charge. The model equations are discretized using a nonlinear variational multi-scale finite element method that has demonstrated superior accuracy in other plasma flow problems, on a temporal and three-dimensional computational domain suitable to unveil the potential occurrence of instabilities. Modelling results show good agreement with experimental measurements of voltage drop and the same trend but higher values of temperature. The higher temperatures obtained by the simulations appear to be due to the absence of a near-cathode heat dissipation model. Here, the results also reveal that the distribution of electron density and of the ratio of atomic helium ions to total ions transitions from monotonically increasing away from the cathode to presenting a minimum near the centre of the gap with increasing current.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Low temperature catalytic conversion of CH 4 , CO 2 , and C 2 H 4 to value-added C 3 oxygenates and olefins via C 1 -C 2 coupling on Pd-Au/CeO 2

The catalytic conversion of CH 4 and CO 2 in the presence of more reactive co-reactants C 2 H 4 and O 2 on Pd-Au/CeO 2 is achieved at 200 °C and elevated pressures. Propene and acetone were produced from the catalyzed reaction of CH 4 +C 2 H 4 +O 2 ; addition of CO 2 to the reactant stream produced methyl acetate (MAc) but it significantly reduced the C-selectivities of propene and acetone. DRIFTS experiments confirmed the formation of methoxy species from CH 4 +CO 2 at 200 °C, which is an intermediate in the formation of MAc. Here, control experiments with blanks, and with CeO 2 did not show any propene, acetone, or MAc products. The complete oxidation of C 2 H 4 was avoided; the catalyst is stable, and reactant conversions and product yields were sustained for the observed 1200 min time-on-stream, indicating that there is little or no carbon deposition and sintering. This direct coupling of CH 4 and C 2 H 4 intermediates to higher carbon-number products at 200 °C is significant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fluoroester Co-Solvents for Low-Temperature Li+ Cells

Electrolytes comprising LiPF6 dissolved in alkyl carbonate/fluoroester mixtures have been found to afford improved low-temperature performance and greater high-temperature resilience in rechargeable lithium-ion electrochemical cells. These and other electrolytes comprising lithium salts dissolved mixtures of esters have been studied in continuing research directed toward extending the lower limit of operating temperatures of such cells. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. The purpose of the present focus on high-temperature resilience in addition to low-temperature performance is to address issues posed by the flammability of the esters and, at temperatures near the upper end (about 55 C) of their intended operating temperature range, by their high chemical reactivity. As used here, high-temperature resilience signifies, loosely, a desired combination of low flammability of an electrolyte mixture and the ability of a cell that contains the mixture to sustain a relatively small loss of reversible charge/discharge capacity during storage in the fully charged condition at high temperature. The selection of fluoroesters for study as candidate electrolyte solvent components to increase high-temperature resilience was prompted in part by the observation that like other halogenated compounds, fluoroesters have low flammability. The fluoroesters investigated in this study include trifluoroethyl butyrate (TFEB), ethyl trifluoroacetate (ETFA), trifluoroethyl acetate (TFEA), and methyl pentafluoropropionate (MPFP). Solvent mixtures were prepared by mixing these fluoroesters with two other esters: ethylene carbonate (EC) and ethyl methyl carbonate (EMC).

Smart, Marshall↗

Effect of nitric oxide and exhaust gases on gasoline surrogate autoignition: iso-octane experiments and modeling

Exhaust gas recirculation (EGR) is widely used in advanced internal combustion engines to reduce engine emissions as well as control combustion phasing. Among various species present in EGR gases, CO 2 and H 2 O are two major components that can thermally and chemically affect fuel autoignition. It is of fundamental interest to isolate the thermal and chemical effects of CO 2 and H 2 O on fuel autoignition, especially as such an effort has not been reported in the literature. Moreover, nitric oxide (NO) is known to exhibit strong chemical effects on fuel autoignition, which in turn affects engine combustion phasing. The effects of ultra-low NO addition (< 100 ppm) on fuel autoignition at low temperatures are also not well understood. Recognizing these problems, autoignition experiments of iso-octane (a major gasoline surrogate component) in air are performed in this study using a rapid compression machine at varying compressed pressures, equivalence ratios, dilution levels with an EGR gas analogue (consisting of CO 2 , H 2 O, O 2 , and N 2 ) and N 2 only, and varying amounts of NO addition. Furthermore, the thermal and chemical effects of the EGR gas analogue are isolated and evaluated by comparing the ignition delay time datasets of EGR and N2-only diluted cases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrous Nickel–Iron Turnbull’s Blue as a High-Rate and Low-Temperature Proton Electrode

Proton batteries are emerging as a promising solution for energy storage; however, their development has been hindered by the lack of suitable cathode materials. Herein, a hydrous Turnbull’s blue analogue (TBA) of Ni[Fe(CN) 6 ] 2/3 ·4H 2 O has been investigated as a viable proton cathode. Particularly, it shows an extremely high rate performance up to 6000 C (390 A g –1 ) at room temperature and delivers good capacity values at a low temperature of -40 °C in an aqueous electrolyte. The excellent rate capability is also amenable to high mass loadings of 10 mg cm –2 . Such fast and low-temperature rate behavior likely stems from the fast proton conduction that is afforded by the Grotthuss mechanism inside the TBA structure. Furthermore, advanced characterization, including in operando synchrotron X-ray diffraction (XRD), and X-ray absorption near-edge structure (XANES) were employed to understand the changes of crystal structures and the oxidation-states of metal elements of the electrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low-pressure inductively coupled plasmas in hydrogen: impact of gas heating on the spatial distribution of atomic hydrogen and vibrationally excited states

Non-equilibrium inductively coupled plasmas (ICPs) operating in hydrogen are of significant interest for applications including large-area materials processing. Increasing control of spatial gas heating, which drives the formation of neutral species density gradients and the rate of gas-temperature-dependent reactions, is critical. In this study, we use 2D fluid-kinetic simulations with the Hybrid Plasma Equipment Model to investigate the spatially resolved production of atomic hydrogen in a low-pressure planar ICP operating in pure hydrogen (10–20 Pa or 0.075–0.15 Torr, 300 W). The reaction set incorporates self-consistent calculation of the spatially resolved gas temperature and 14 vibrationally excited states. We find that the formation of neutral-gas density gradients, which result from spatially non-uniform electrical power deposition at constant pressure, can drive significant variations in the vibrational distribution function and density of atomic hydrogen when gas heating is spatially resolved. This highlights the significance of spatial gas heating on the production of reactive species in relatively high-power-density plasma processing sources.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

A Review of Single Source Precursors for the Deposition of Ternary Chalcopyrite Materials

The development of thin-film solar cells on flexible, lightweight, space-qualified durable substrates (i.e. Kapton) provides an attractive solution to fabricating solar arrays with high specific power, (W/kg). The syntheses and thermal modulation of ternary single source precursors, based on the [{LR}2Cu(SR')2In(SR')2] architecture in good yields are described. Thermogravimetric analyses (TGA) and Low temperature Differential Scanning Caloriometry, (DSC) demonstrate that controlled manipulation of the steric and electronic properties of either the group five-donor and/or chalcogenide moiety permits directed adjustment of the thermal stability and physical properties of the precursors. TGA-Evolved Gas Analysis, confirms that single precursors decompose by the initial extrusion of the sulphide moiety, followed by the loss of the neutral donor group, (L) to release the ternary chalcopyrite matrix. X-ray diffraction studies, EDS and SEM on the non-volatile pyrolized material demonstrate that these derivatives afford single-phase CuInS2/CuInSe2 materials at low temperature. Thin-film fabrication studies demonstrate that these single source precursors can be used in a spray chemical vapor deposition process, for depositing CuInS2 onto flexible polymer substrates at temperatures less than 400 C.

Banger, K. K.↗