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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 307 records · Page 17

Reversible and Selective CO 2 to HCO 2 - Electrocatalysis near the Thermodynamic Potential

Reversible catalysis is an emblem of energy-efficient chemical transformations, but can only be achieved if the changes in free energy of intermediate steps are minimized and the catalytic cycle is devoid of high transition-state barriers. Using these criteria, we show reversible CO 2 /HCO 2 - conversion catalyzed by [Pt(depe) 2 ] 2+ (depe=1,2- bis (diethylphosphino)ethane). Direct measurement of the free energies associated with each catalytic step correctly predicts a slight bias towards CO 2 reduction. We demonstrate how the experimentally measured free energy of each step directly contributes to the <50mV overpotential. We also find that for CO 2 reduction, H 2 evolution is negligible and the Faradaic efficiency for HCO 2 - production is nearly quantitative. A free-energy analysis reveals H 2 evolution is endergonic, providing a thermodynamic basis for highly selective CO 2 reduction.

10 SYNTHETIC FUELS↗

Modeling of Kink-Shaped Carbon-Nanotube Schottky Diode with Gate Bias Modulation

A model is proposed for the recent gate-voltage (V(sub G)) modulation experiment of a kink-shaped carbon nanotube (NT) Schottky diode. Since larger V(sub G) increases both the forward and the reverse turn-on voltages of the diode in the experiment, we show that: (1) the rectification must occur at the kink where the metallic and the semiconducting NTs meet, and not at the electrode contact, and (2) the semiconducting NT must be n-type. The turn-on voltages are derived analytically as a function of V(sub G) with the electrode contact contribution and a good agreement is obtained with the experimental data.

Yamada, Toshishige↗

Exploring ENSO-Induced Anomalies over North America in Historical and Future Climate Simulations That Use HadGEM2-ESM Output to Drive WRF

Projected changes to the El Niño Southern Oscillation (ENSO) climate mode have been explored using global Earth system models (ESMs). Regional expressions of such changes have yet to be fully advanced and may require the use of regional downscaling. Here, we employ regional climate modeling (RCM) using the Weather Research and Forecasting (WRF) model at convection-permitting resolution and nested in output from the HadGEM2 ESM. We quantify ENSO teleconnections to temperature and precipitation anomalies in historical and future climate scenarios over eastern North America. Two paired simulations are run, a strong El Niño (positive ENSO phase) and a weak La Niña (negative ENSO phase), for the historical and future years. The HadGEM2 direct output and HadGEM2-WRF simulation output are compared to the anomalies derived from the NOAA ENSO Climate Normals dataset. The near-surface temperature and precipitation differences by ENSO phase, as represented by the HadGEM2-WRF historical simulations, show a poor degree of association with the NOAA ENSO Climate Normals, in part because of the large biases in the HadGEM2 model. Downscaling with the WRF model does improve the agreement with the observations, and large discrepancies remain. The model chain HadGEM2-WRF reverses the sign of the ENSO phase response over eastern North America under simulations of the future climate with high greenhouse gas forcing, but due to the poor agreement with the NOAA ENSO Climate Normals it is difficult to assign confidence to this prediction.

54 ENVIRONMENTAL SCIENCES↗

Dispersive nonreciprocity between a qubit and a cavity

The dispersive interaction between a qubit and a cavity is ubiquitous in circuit and cavity quantum electrodynamics. It describes the frequency shift of one quantum mode in response to excitations in the other and, in closed systems, is necessarily bidirectional, i.e., reciprocal. Here, we present an experimental study of a nonreciprocal dispersive-type interaction between a transmon qubit and a superconducting cavity, arising from a common coupling to dissipative intermediary modes with broken time reversal symmetry. We characterize the qubit-cavity dynamics, including asymmetric frequency pulls and photon shot noise dephasing, under varying degrees of nonreciprocity by tuning the magnetic field bias of a ferrite component in situ. We introduce a general master equation model for nonreciprocal interactions in the dispersive regime, providing a compact description of the observed qubit-cavity dynamics agnostic to the intermediary system. Our result provides an example of quantum nonreciprocal phenomena beyond the typical paradigms of non-Hermitian Hamiltonians and cascaded systems.

74 ATOMIC AND MOLECULAR PHYSICS↗

Power consumption in acoustic amplifiers under conditions of maximum stable gain

Comparison is made of the power consumed and the acoustic amplification realized when a dc bias field is placed across a piezoelectric semiconductor and adjusted to amplify a microwave acoustic signal to the point where the forward gain is just equal to the reverse attenuation. This represents the maximum possible gain condition.

Johnson, V. R.↗

The Contribution of Proton-Donor pKa on Reactivity Profiles of [FeFe]-hydrogenases

The [FeFe]-hydrogenases are enzymes that catalyze the reversible activation of H 2 coupled to the reduction–oxidation of electron carriers. Members of the different taxonomic groups of [FeFe]-hydrogenases display a wide range of preference, or bias, for H 2 oxidation or H 2 production reactions, despite sharing a common catalytic cofactor, or H-cluster. Identifying the properties that control reactivity remains an active area of investigation, and models have emerged that include diversity in the catalytic site coordination environments and compositions of electron transfer chains. The kinetics of proton-coupled electron transfer at the H-cluster might be expected to be a point of control of reactivity. To test this hypothesis, systematic changes were made to the conserved cysteine residue that functions in proton exchange with the H-cluster in the three model enzymes: CaI, CpII, and CrHydA1. CaI and CpII both employ electron transfer accessory clusters but differ in bias, whereas CrHydA1 lacks accessory clusters having only the H-cluster. Changing from cysteine to either serine (more basic) or aspartate (more acidic) modifies the sidechain pKa and thus the barrier for the proton exchange step. The reaction rates for H 2 oxidation or H 2 evolution were surveyed and measured for model [FeFe]-hydrogenases, and the results show that the initial proton-transfer step in [FeFe]-hydrogenase is tightly coupled to the control of reactivity; a change from cysteine to more basic serine favored H 2 oxidation in all enzymes, whereas a change to more acidic aspartate caused a shift in preference toward H 2 evolution. Overall, the changes in reactivity profiles were profound, spanning 10 5 in ratio of the H 2 oxidation-to-H 2 evolution rates. The fact that the change in reactivity follows a common trend implies that the effect of changing the proton-transfer residue pKa may also be framed as an effect on the scaling relationship between the H-cluster di(thiolmethyl)amine (DTMA) ligand pKa and E m values of the H-cluster. Experimental observations that support this relationship, and how it relates to catalytic function in [FeFe]-hydrogenases, are discussed.

59 BASIC BIOLOGICAL SCIENCES↗

Study of Bulk and Elementary Screw Dislocation Assisted Reverse Breakdown in Low-Voltage (< 250 V) 4H-SiC p(sup +)n Junction Diodes--Part II: Dynamic Breakdown Properties: Dynamic Breakdown Properties - Part 2

This paper outlines the dynamic reverse-breakdown characteristics of low-voltage (<250 V) small-area <5 x 10(exp -4) sq cm 4H-SiC p(sup +)n diodes subjected to nonadiabatic breakdown-bias pulsewidths ranging from 0.1 to 20 microseconds. 4H-SiC diodes with and without elementary screw dislocations exhibited positive temperature coefficient of breakdown voltage and high junction failure power densities approximately five times larger than the average failure power density of reliable silicon pn rectifiers. This result indicates that highly reliable low-voltage SiC rectifiers may be attainable despite the presence of elementary screw dislocations. However, the impact of elementary screw dislocations on other more useful 4H-SiC power device structures, such as high-voltage (>1 kV) pn junction and Schottky rectifiers, and bipolar gain devices (thyristors, IGBT's, etc.) remains to be investigated.

Neudeck, Philip G.↗

Heterogenized Pyridine-Substituted Cobalt(II) Phthalocyanine Yields Reduction of CO2 by Tuning the Electron Affinity of the Co Center

Conversion of CO 2 to reduced products is a promising route to alleviate irreversible climate change. In this paper we report the synthesis of a Co-based phthalocyanine with pyridine moieties (CoPc-Pyr), which is supported on a carbon electrode and shows Faradaic efficiency ~90% for CO at 490 mV of overpotential (-0.6 V vs reversible hydrogen electrode (RHE)). In addition, its catalytic activity at -0.7 V versus RHE surpasses other Co-based molecular and metal-organic framework catalysts for CO 2 reduction at this bias. Density functional theory calculations show that pyridine moieties enhance CO 2 adsorption and electron affinity of the Co center by an inductive effect, thus lowering the overpotential necessary for CO 2 conversion. Our study shows that CoPc-Pyr reduces CO 2 at lower overpotential and with higher activity than noble metal electrodes, such as silver.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Greatly improved 3C-SiC p-n junction diodes grown by chemical vapor deposition

This paper reports the fabrication and initial electrical characterization of greatly improved 3C-SiC (beta-SiC) p-n junction diodes. These diodes, which were grown on commercially available 6H-SiC substrates by chemical vapor deposition, demonstrate rectification to -200 V at room temperature, representing a fourfold improvement in reported 3C-SiC diode blocking voltage. The reverse leakage currents and saturation current densities measured on these diodes also show significant improvement compared to previously reported 3C-SiC p-n junction diodes. When placed under sufficient forward bias, the diodes emit significantly bright green-yellow light. These results should lead to substantial advancements in 3C-SiC transistor performance.

Neudeck, Philip G.↗

Reversible and Selective CO 2 to HCO 2 − Electrocatalysis near the Thermodynamic Potential

Abstract Reversible catalysis is a hallmark of energy‐efficient chemical transformations, but can only be achieved if the changes in free energy of intermediate steps are minimized and the catalytic cycle is devoid of high transition‐state barriers. Using these criteria, we demonstrate reversible CO 2 /HCO 2 − conversion catalyzed by [Pt(depe) 2 ] 2+ (depe=1,2‐ bis (diethylphosphino)ethane). Direct measurement of the free energies associated with each catalytic step correctly predicts a slight bias towards CO 2 reduction. We demonstrate how the experimentally measured free energy of each step directly contributes to the <50 mV overpotential. We also find that for CO 2 reduction, H 2 evolution is negligible and the Faradaic efficiency for HCO 2 − production is nearly quantitative. A free‐energy analysis reveals H 2 evolution is endergonic, providing a thermodynamic basis for highly selective CO 2 reduction.

Cunningham, Drew W.↗

Direct observation of nanoscale dynamics of ferroelectric degradation

Failure of polarization reversal, i.e., ferroelectric degradation, induced by cyclic electric loadings in ferroelectric materials, has been a long-standing challenge that negatively impacts the application of ferroelectrics in devices where reliability is critical. It is generally believed that space charges or injected charges dominate the ferroelectric degradation. However, the physics behind the phenomenon remains unclear. Here, using in-situ biasing transmission electron microscopy, we discover change of charge distribution in thin ferroelectrics during cyclic electric loadings. Charge accumulation at domain walls is the main reason of the formation of c domains, which are less responsive to the applied electric field. The rapid growth of the frozen c domains leads to the ferroelectric degradation. This finding gives insights into the nature of ferroelectric degradation in nanodevices, and reveals the role of the injected charges in polarization reversal.

42 ENGINEERING↗

Generalized Lapse Rate Formulas for Use in Entraining CAPE Calculations

Abstract Common assumptions in temperature lapse rate formulas for lifted air parcels include neglecting mixing, hydrostatic balance, the removal of all condensate once it forms (pseudoadiabatic), and/or the retention of all condensate within the parcel (adiabatic). These formulas are commonly derived from the conservation of entropy, which leads to errors when nonequilibrium mixed-phase condensate is present. To evaluate these assumptions, a new general lapse rate formula is derived from an expression for energy conservation, rather than entropy conservation. This new formula incorporates mixing of the parcel with its surroundings, relaxes the hydrostatic assumption, allows for nonequilibrium mixed-phase condensate, and can be formulated for pseudoadiabatic or adiabatic ascent. The new formula is shown to exactly conserve entropy for reversible ascent. Predictions by the new formula are compared to that of older and less general formulas. The errors in previous formulas arise from the assumption of hydrostatic balance, which results in considerable warm biases due to the neglect of the energy sink from buoyancy. Predictions of ascent with entrainment using the new formula are then compared to parcel properties along trajectories in large eddy simulations. Simulated parcel properties are better predicted by the formula using a diluted analogy to adiabatic ascent, wherein condensate is diluted at the same rate as other parcel properties, than by the diluted analogy to pseudoadiabatic ascent, wherein all condensate is removed. These results suggest that CAPE should be computed with adiabatic, rather than pseudoadiabatic, parcel ascent.

54 ENVIRONMENTAL SCIENCES↗

Cascading Tesla Oscillating Flow Diode for Stirling Engine Gas Bearings

Replacing the mechanical check-valve in a Stirling engine with a micromachined, non-moving-part flow diode eliminates moving parts and reduces the risk of microparticle clogging. At very small scales, helium gas has sufficient mass momentum that it can act as a flow controller in a similar way as a transistor can redirect electrical signals with a smaller bias signal. The innovation here forces helium gas to flow in predominantly one direction by offering a clear, straight-path microchannel in one direction of flow, but then through a sophisticated geometry, the reversed flow is forced through a tortuous path. This redirection is achieved by using microfluid channel flow to force the much larger main flow into this tortuous path. While microdiodes have been developed in the past, this innovation cascades Tesla diodes to create a much higher pressure in the gas bearing supply plenum. In addition, the special shape of the leaves captures loose particles that would otherwise clog the microchannel of the gas bearing pads.

Dyson, Rodger↗

Dynamic Characterization of Galfenol (Fe81.6Ga18.4)

Galfenol has the potential to transform the smart materials industry by allowing for the development of multifunctional, load-bearing devices. One of the primary technical challenges faced by this development is the very limited experimental data on Galfenol's frequency-dependent response to dynamic stress, which is critically important for the design of such devices. This report details a novel and precise characterization of the constitutive behavior of polycrystalline Galfenol (Fe81.6Ga18.4) under quasi-static (1 Hz) and dynamic (4 to 1000 Hz) stress loadings. Mechanical loads are applied using a high-frequency load frame. Quasi-static minor and major hysteresis loop measurements of magnetic flux density and strain are presented for constant electromagnet currents (0 to 1.1 A) and constant magnetic fields 0 to 14 kA/m (0 to 180 Oe). The dynamic stress amplitude for minor and major loops is 2.88 and 31.4 MPa (418 and 4550 psi), respectively. Quasi-static material properties closely match published values for similar Galfenol materials. Quasi-static actuation responses are also measured and compared to quasi-static sensing responses; the high degree of reversibility seen in the comparison is consistent with published measurements and modeling results. Dynamic major and minor loops are measured for dynamic stresses up to 31 MPa (4496 psi) and 1 kHz, and the bias condition resulting in maximum, quasi-static sensitivity. Eddy current effects are quantified by considering solid and laminated Galfenol rods. Three key sources of error in the dynamic measurements are accounted for: (1) electromagnetic noise in strain signals due to Galfenol's magnetic response, (2) error in load signals due to the inertial force of fixturing, and (3) phase misalignment between signals due to conditioning electronics. For dynamic characterization, strain error is kept below 1.2 percent of full scale by wiring two collocated gauges in series (noise cancellation) and through leadwire weaving. Inertial force error is kept below 0.41 percent by measuring the dynamic force in the specimen using a nearly collocated piezoelectric load washer. The phase response of all conditioning electronics is explicitly measured and corrected for. In general, as frequency is increased, the sensing response becomes more linear because of an increase in eddy currents. As frequency increases above approximately 100 Hz, the elbow in the strain-versus-stress response disappears as the active (soft) regime stiffens toward the passive (hard) regime. Under constant-field conditions, the loss factors of the solid rod peak between 200 and 600 Hz, rather than exhibiting a monotonic increase. Compared to the solid rod, the laminated rod exhibits much slower increases in hysteresis with frequency, and its quasi-static behavior extends to higher frequencies. The elastic modulus of the laminated rod decreases between 100 and 300 Hz; this trend is currently unexplained.

Dynamic sensing↗

Laser velocimetry applied to transonic and supersonic aerodynamics

As a further demonstration of the capabilities of laser velocity in compressible aerodynamics, measurements obtained in a Mach 2.9 separated turbulent boundary layer and in the transonic flow past a two-dimensional airfoil section are presented and compared to data realized by conventional techniques. In the separated-flow study, the comparisons were made against pitot-static pressure data. Agreement in mean velocities was realized where the pressure measurements could be considered reliable; however, in regions of instantaneous reverse velocities, the laser results were found to be consistent with the physics of the flow whereas the pressure data were not. The laser data obtained in regions of extremely high turbulence suggest that velocity biasing does not occur if the particle occurrence rate is low relative to the turbulent fluctuation rate. Streamwise turbulence intensities are also presented. In the transonic airfoil study, velocity measurements obtained immediately outside the upper surface boundary layer of a 6-inch chord MACA 64A010 airfoil are compared to edge velocities inferred from surface pressure measurements. For free-stream Mach numbers of 0.6 and 0.8, the agreement in results was very good. Dual scatter optical arrangements in conjunction with a single particle, counter-type signal processor were employed in these investigations. Half-micron-diameter polystyrene spheres and naturally occurring condensed oil vapor acted as light scatterers in the two respective flows. Bragg-cell frequency shifting was utilized in the separated flow study.

Johnson, D. A.↗

Status of TRMM Monthly Estimates of Tropical Precipitation

Nearly three years of Tropical Rainfall Measuring Mission Satellite (TRMM Satellite) monthly estimates of tropical surface rainfall are analyzed to document and understand the differences among the TRMM-based estimates and how these differences relate to the pre-TRMM estimates and current operational analyses. Variation among the TRMM estimates is shown to be considerably smaller than among a pre-TRMM collection of passive microwave-based products. Use of both passive and active microwave techniques in TRMM should lead to increased confidence in converged estimates. Current TRMM estimates are shown to have a range of about 20% for the tropical ocean as a whole, with variations in heavily raining ocean areas of the ITCZ and SPCZ having differences over 30%. In mid-latitude ocean areas the differences are smaller. Over land there is a distinct difference between the tropics and mid-latitude with a reversal between some of the products as to which tends to be relatively high or low. Comparisons of TRMM estimates with ocean atoll and land gauge information point to products that might have significant regional biases. The radar-based product is significantly low biased compared with atoll raingauge data, while the passive microwave product is significantly high compared to raingauge data in the deep tropics. The evolution of rainfall patterns during the recent change from intense El Nino to a long period of La Nina and then a gradual return to near neutral conditions is described using TRMM. The time history of integrated rainfall over the tropical oceans (and land) during this period differs among the passive and active microwave TRMM estimates.

Adler, Robert F.↗

Quantifying shifts in natural selection on codon usage between protein regions: a population genetics approach

Codon usage bias (CUB), the non-uniform usage of synonymous codons, occurs across all domains of life. Adaptive CUB is hypothesized to result from various selective pressures, including selection for efficient ribosome elongation, accurate translation, mRNA secondary structure, and/or protein folding. Given the critical link between protein folding and protein function, numerous studies have analyzed the relationship between codon usage and protein structure. The results from these studies have often been contradictory, likely reflecting the differing methods used for measuring codon usage and the failure to appropriately control for confounding factors, such as differences in amino acid usage between protein structures and changes in the frequency of different structures with gene expression. Here we take an explicit population genetics approach to quantify codon-specific shifts in natural selection related to protein structure in S. cerevisiae and E. coli. Unlike other metrics of codon usage, our approach explicitly separates the effects of natural selection, scaled by gene expression, and mutation bias while naturally accounting for a region’s amino acid usage. Bayesian model comparisons suggest selection on codon usage varies only slightly between helix, sheet, and coil secondary structures and, similarly, between structured and intrinsically-disordered regions. Similarly, in contrast to previous findings, we find selection on codon usage only varies slightly at the termini of helices in E. coli. Using simulated data, we show this previous work indicating “non-optimal” codons are enriched at the beginning of helices in S. cerevisiae was due to failure to control for various confounding factors (e.g. amino acid biases, gene expression, etc.), and rather than selection to modulate cotranslational folding. Our results reveal a weak relationship between codon usage and protein structure, indicating that differences in selection on codon usage between structures are slight. In addition to the magnitude of differences in selection between protein structures being slight, the observed shifts appear to be idiosyncratic and largely codon-specific rather than systematic reversals in the nature of selection. Overall, our work demonstrates the statistical power and benefits of studying selective shifts on codon usage or other genomic features from an explicitly evolutionary approach. Limitations of this approach and future potential research avenues are discussed.

59 BASIC BIOLOGICAL SCIENCES↗