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At least 793 records · Page 44
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Metal–Ligand Cooperativity via Exchange Coupling Promotes Iron- Catalyzed Electrochemical CO 2 Reduction at Low Overpotentials

Biological and heterogeneous catalysts for the electrochemical CO 2 reduction reaction (CO 2 RR) often exhibit a high degree of electronic delocalization that serves to minimize overpotential and maximize selectivity over the hydrogen evolution reaction (HER). Here, we report a molecular iron(II) system that captures this design concept in a homogeneous setting through the use of a redox non-innocent terpyridine-based pentapyridine ligand (tpyPY2Me). As a result of strong metal-ligand exchange coupling between the Fe(II) center and ligand, [Fe(tpyPY2Me)] 2+ exhibits redox behavior at potentials 640 mV more positive than the isostructural [Zn(tpyPY2Me)] 2+ analog containing the redox-inactive Zn(II) ion. This shift in redox potential is attributed to the requirement for both an open-shell metal ion and a redox non-innocent ligand. The metal-ligand cooperativity in [Fe(tpyPY2Me)] 2+ drives the electrochemical reduction of CO 2 to CO at low overpotentials with high selectivity for CO 2 RR (>90%) and turnover frequencies of 100,000 s -1 with no degradation over 20 h. The decrease in the thermodynamic barrier engendered by this coupling also enables homogeneous CO 2 reduction catalysis in water without compromising selectivity or rates. Synthesis of the two-electron reduction product, [Fe(tpyPY2Me)] o , and characterization by X-ray crystallography, Mössbauer spectroscopy, X-ray absorption spectroscopy (XAS), variable temperature NMR, and density functional theory (DFT) calculations, support assignment of an open-shell singlet electronic structure that maintains a formal Fe(II) oxidation state with a doubly reduced ligand system. Furthermore, this work provides a starting point for the design of systems that exploit metal-ligand cooperativity for electrocatalysis where the electrochemical potential of redox non-innocent ligands can be tuned through secondary metal-dependent interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1975

Pyrotechnic shock measurement and data analysis requirements

A study of laboratory measurement and analysis of pyrotechnic shock prompted by a discrepancy in preliminary Mariner Jupiter/Saturn shock test data is reported. It is shown that before generating shock response plots from any recorded pyrotechnic event, a complete review of each instrumentation and analysis system must be made. In addition, the frequency response capability of the tape recorder used should be as high as possible; the discrepancies in the above data were due to inadequate frequency response in the FM tape recorders. The slew rate of all conditioning amplifiers and input converters must be high enough to prevent signal distortion at maximum input voltage; amplifier ranges should be selected so that the input pulse is approximately 50% of full scale; the Bessel response type should be chosen for digital shock analysis if antialiasing filters are employed; and transducer selection must consider maximum acceleration limit, mounted resonance frequency, flat clean mounting surfaces, base bending sensitivity, and proper torque.

Albers, L.↗
DOE OSTI2015

Cross-polarization phenomena in the NMR of fast spinning solids subject to adiabatic sweeps

Cross-polarization magic-angle spinning (CPMAS) experiments employing frequency-swept pulses are explored within the context of obtaining broadband signal enhancements for rare spin S = 1/2 nuclei at very high magnetic fields. These experiments employ adiabatic inversion pulses on the S-channel ({sup 13}C) to cover a wide frequency offset range, while simultaneously applying conventional spin-locking pulse on the I-channel ({sup 1}H). Conditions are explored where the adiabatic frequency sweep width, Δν, is changed from selectively irradiating a single magic-angle-spinning (MAS) spinning centerband or sideband, to sweeping over multiple sidebands. A number of new physical features emerge upon assessing the swept-CP method under these conditions, including multiple zero- and double-quantum CP transfers happening in unison with MAS-driven rotary resonance phenomena. These were examined using an average Hamiltonian theory specifically designed to tackle these experiments, with extensive numerical simulations, and with experiments on model compounds. Ultrawide CP profiles spanning frequency ranges of nearly 6⋅γB{sub 1}{sup s} were predicted and observed utilizing this new approach. Potential extensions and applications of this extremely broadband transfer conditions are briefly discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Rare variants contribute disproportionately to quantitative trait variation in yeast

How variants with different frequencies contribute to trait variation is a central question in genetics. We use a unique model system to disentangle the contributions of common and rare variants to quantitative traits. We generated ~14,000 progeny from crosses among 16 diverse yeast strains and identified thousands of quantitative trait loci (QTLs) for 38 traits. We combined our results with sequencing data for 1011 yeast isolates to show that rare variants make a disproportionate contribution to trait variation. Evolutionary analyses revealed that this contribution is driven by rare variants that arose recently, and that negative selection has shaped the relationship between variant frequency and effect size. We leveraged the structure of the crosses to resolve hundreds of QTLs to single genes. These results refine our understanding of trait variation at the population level and suggest that studies of rare variants are a fertile ground for discovery of genetic effects.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1991

Solution to the indexing problem of frequency domain simulation experiments

A frequency domain simulation experiment is one in which selected system parameters are oscillated sinusoidally to induce oscillations in one or more system statistics of interest. A spectral (Fourier) analysis of these induced oscillations is then performed. To perform this spectral analysis, all oscillation frequencies must be referenced to a common, independent variable - an oscillation index. In a discrete-event simulation, the global simulation clock is the most natural choice for the oscillation index. However, past efforts to reference all frequencies to the simulation clock generally yielded unsatisfactory results. The reason for these unsatisfactory results is explained in this paper and a new methodology which uses the simulation clock as the oscillation index is presented. Techniques for implementing this new methodology are demonstrated by performing a frequency domain simulation experiment for a network of queues.

Mitra, Mousumi↗
NASA NTRS2015

Trend Estimates of AERONET-Observed and Model-Simulated AOTs Between 1993 and 2013

Recently, temporal changes in Aerosol Optical Thickness (AOT) have been investigated based on model simulations, satellite and ground-based observations. Most AOT trend studies used monthly or annual arithmetic means that discard details of the generally right-skewed AOT distributions. Potentially, such results can be biased by extreme values (including outliers). This study additionally uses percentiles (i.e., the lowest 5%, 25%, 50%, 75% and 95% of the monthly cumulative distributions fitted to Aerosol Robotic Network (AERONET)-observed and ECHAM/MESSy Atmospheric Chemistry (EMAC)-model simulated AOTs) that are less affected by outliers caused by measurement error, cloud contamination and occasional extreme aerosol events. Since the limited statistical representativeness of monthly percentiles and means can lead to bias, this study adopts the number of observations as a weighting factor, which improves the statistical robustness of trend estimates. By analyzing the aerosol composition of AERONET-observed and EMAC-simulated AOTs in selected regions of interest, we distinguish the dominant aerosol types and investigate the causes of regional AOT trends. The simulated and observed trends are generally consistent with a high correlation coefficient (R = 0.89) and small bias (slope+/-2(sigma) = 0.75 +/- 0.19). A significant decrease in EMAC-decomposed AOTs by water-soluble compounds and black carbon is found over the USA and the EU due to environmental regulation. In particular, a clear reversal in the AERONET AOT trend percentiles is found over the USA, probably related to the AOT diurnal cycle and the frequency of wildfires. In most of the selected regions of interest, EMAC-simulated trends are mainly attributed to the significant changes of the dominant aerosols; e.g., significant decrease in sea salt and water soluble compounds over Central America, increase in dust over Northern Africa and Middle East, and decrease in black carbon and organic carbon over Australia.

AERONET↗
DOE OSTI2019

Tool for Searching USEPA’s TMDL Reports Repository to Analyze TMDL Modeling State of the Practice

We report that total maximum daily load (TMDL) reports archived in the USEPA database can provide useful guidance for the development of new TMDLs and watershed management plans by aiding the selection process for the most appropriate modeling tool. The database contains more than 70,000 individual documents; therefore, a rapid screening tool is needed to elicit information about previous modeling studies that might help guide stakeholders and regulators in dealing with the TMDL application at hand, save time, and lead to a more cost-effective regulatory outcome. The paper introduces a smart web-based software tool for TMDL report selection based on different water management criteria. The tool uses an automated search method based on frequency of common water body impairments and models to categorize and select TMDL reports. Additionally, this tool provides better insight on the relationship between the modeling tools used and the impairments they address. This tool has proven useful in reviewing the state of integrated modeling (IM), applications of remote sensing (RS), application of basic versus mechanistic modeling, margin of safety (MOS) assessment, and the state of practice regarding relationships among impairments, models, and regions where TMDLs for various pollutants are being developed. Despite limitations on direct access to all TMDLs developed and reported to the EPA by the user, the tool can be improved over time to derive a better understanding of the relationships between these impairments, data, and the TMDL development process. Finally, although the MOS is not directly quantified in the current version of the TRS tool, this feature may be incorporated in future updates.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1990

On-line in-situ control of the resin transfer molding process

Resin transfer molding of three-dimensionally stitched fabrics promises to be a cost effective process for obtaining composite parts of exceptional strength. The technique eliminates many problems involving prepreg preparation, storage and layup. It replaces, on the other hand, the single step cure process with a two-stage impregnation and cure process. Of particular importance therefore is selecting and controlling the viscosity during impregnation and cure. The use of in-situ frequency-dependent electromagnetic sensors and the Loos-Springer model for selecting and controllng the processing properties of the resin transfer molding resin during impregnation and cure are discussed.

Kranbuehl, D.↗
DOE OSTI2014

Anisotropic lattice thermal expansion of PbFeBO{sub 4}: A study by X-ray and neutron diffraction, Raman spectroscopy and DFT calculations

Highlights: • Mullite-type PbFeBO{sub 4} shows uni-axial negative coefficient of thermal expansion. • Anisotropic thermal expansion of the metric parameters was modeled using modified Grüneisen approximation. • The model includes harmonic, quasi-harmonic and intrinsic anharmonic contributions to the internal energy. • DFT calculation, temperature- and pressure-dependent Raman spectra help understand the phonon decay and associated anharmonicity. - Abstract: The lattice thermal expansion of mullite-type PbFeBO{sub 4} is presented in this study. The thermal expansion coefficients of the metric parameters were obtained from composite data collected from temperature-dependent neutron and X-ray powder diffraction between 10 K and 700 K. The volume thermal expansion was modeled using extended Grüneisen first-order approximation to the zero-pressure equation of state. The additive frame of the model includes harmonic, quasi-harmonic and intrinsic anharmonic potentials to describe the change of the internal energy as a function of temperature. The unit-cell volume at zero-pressure and 0 K was optimized during the DFT simulations. Harmonic frequencies of the optical Raman modes at the Γ-point of the Brillouin zone at 0 K were also calculated by DFT, which help to assign and crosscheck the experimental frequencies. The low-temperature Raman spectra showed significant anomaly in the antiferromagnetic regions, leading to softening or hardening of some phonons. Selected modes were analyzed using a modified Klemens model. The shift of the frequencies and the broadening of the line-widths helped to understand the anharmonic vibrational behaviors of the PbO{sub 4}, FeO{sub 6} and BO{sub 3} polyhedra as a function of temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Mode-Selective Vibrational Energy Transfer Dynamics in 1,3,5-Trinitroperhydro-1,3,5-triazine (RDX) Thin Films

The coupling of inter- and intramolecular vibrations plays a critical role in initiating chemistry during the shock-to-detonation transition in energetic materials. In this work, we report on the subpicosecond to subnanosecond vibrational energy transfer (VET) dynamics of the solid energetic material 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) by using broadband, ultrafast infrared transient absorption spectroscopy. Experiments reveal VET occurring on three distinct time scales: subpicosecond, 5 ps, and 200 ps. The ultrafast appearance of signal at all probed modes in the mid-infrared suggests strong anharmonic coupling of all vibrations in the solid, whereas the long-lived evolution demonstrates that VET is incomplete, and thus thermal equilibrium is not attained, even on the 100 ps time scale. Density functional theory and classical molecular dynamics simulations provide valuable insights into the experimental observations, revealing compression-insensitive time scales for the initial VET dynamics of high-frequency vibrations and drastically extended relaxation times for low-frequency phonon modes under lattice compression. Mode selectivity of the longest dynamics suggests coupling of the N–N and axial NO2 stretching modes with the long-lived, excited phonon bath.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2014

Design Concepts for a Small Space-Based GEO Relay Satellite for Missions Between Low Earth and near Earth Orbits

The main purpose of the Small Space-Based Geosynchronous Earth orbiting (GEO) satellite is to provide a space link to the user mission spacecraft for relaying data through ground networks to user Mission Control Centers. The Small Space Based Satellite (SSBS) will provide services comparable to those of a NASA Tracking Data Relay Satellite (TDRS) for the same type of links. The SSBS services will keep the user burden the same or lower than for TDRS and will support the same or higher data rates than those currently supported by TDRS. At present, TDRSS provides links and coverage below GEO; however, SSBS links and coverage capability to above GEO missions are being considered for the future, especially for Human Space Flight Missions (HSF). There is also a rising need for the capability to support high data rate links (exceeding 1 Gbps) for imaging applications. The communication payload on the SSBS will provide S/Ka-band single access links to the mission and a Ku-band link to the ground, with an optical communication payload as an option. To design the communication payload, various link budgets were analyzed and many possible operational scenarios examined. To reduce user burden, using a larger-sized antenna than is currently in use by TDRS was considered. Because of the SSBS design size, it was found that a SpaceX Falcon 9 rocket could deliver three SSBSs to GEO. This will greatly reduce the launch costs per satellite. Using electric propulsion was also evaluated versus using chemical propulsion; the power system size and time to orbit for various power systems were also considered. This paper will describe how the SSBS will meet future service requirements, concept of operations, and the design to meet NASA users' needs for below and above GEO missions. These users' needs not only address the observational mission requirements but also possible HSF missions to the year 2030. We will provide the trade-off analysis of the communication payload design in terms of the number of links looking above and below GEO; the detailed design of a GEO SSBS spacecraft bus and its accommodation of the communication payload, and a summary of the trade study that resulted in the selection of the Falcon 9 launch vehicle to deploy the SSBS and its impact on cost reductions per satellite. ======================================================================== Several initiatives have taken place within NASA1 and international space agencies2 to create a human exploration strategy for expanding human presence into the solar system; these initiatives have been driven by multiple factors to benefit Earth. Of the many elements in the strategy one stands out: to send robotic and human missions to destinations beyond Low Earth Orbit (LEO), including cis-lunar space, Near-Earth Asteroids (NEAs), the Moon, and Mars and its moons.3, 4 The time frame for human exploration to various destinations, based on the public information available,1,4 is shown in Figure 1. Advance planning is needed to define how future space communications services will be provided in the new budget environment to meet future space communications needs. The spacecraft for these missions can be dispersed anywhere from below LEO to beyond GEO, and to various destinations within the solar system. NASA's Space Communications and Navigation (SCaN) program office provides communication and tracking services to space missions during launch, in-orbit testing, and operation phases. Currently, SCaN's space networking relay satellites mainly provide services to users below GEO, at Near Earth Orbit (NEO), below LEO, and in deep space. The potential exists for using a space-based relay satellite, located in the vicinity of various solar system destinations, to provide communication space links to missions both below and above its orbit. Such relays can meet the needs of human exploration missions for maximum connectivity to Earth locations and for reduced latency. In the past, several studies assessed the ability of satellite-based relays working above GEO in conjunction with Earth ground stations. Many of these focused on the trade between space relay and direct-to-Earth station links5,6,7. Several others focused on top-level architecture based on relays at various destinations8,9,10,11,12. Much has changed in terms of microwave and optical technology since the publication of the referenced papers; Ka-band communication systems are being deployed, optical communication is being demonstrated, and spacecraft buses are becoming increasingly more functional and operational. A design concept study was undertaken to access the potential for deploying a Small Space-Based Satellite (SSBS) relay capable of serving missions between LEO and NEO. The needs of future human exploration missions were analyzed, and a notional relay-based architecture concept was generated as shown in Fig. 1. Relay satellites in Earth through cis-Lunar orbits are normally located in stable orbits requiring low fuel consumption. Relay satellites for Mars orbit are normally selected based on the mission requirement and projected fuel consumption. Relay satellites have extreme commonalities of functions between them, differing only in the redundancy and frequencies used; therefore, the relay satellite in GEO was selected for further analysis since it will be the first step in achieving a relay-based architecture for human exploration missions (see Fig.Figure 2). The mission design methodology developed by the Collaborative Modeling for Parametric Assessment of Space Systems (COMPASS) team13 was used to produce the satellite relay design and to perform various design trades. At the start of the activity, the team was provided with the detailed concept of the notional architecture and the system and communication payload drivers.

Relay Satellites↗
DOE OSTI2016

The Measurand: The Problem of Frequency

The conceptual entity that metrologists term the measurand is a model selected to represent the physical entity being measured. In a world of digital measurements, it should be defined first mathematically, and only then put into words. Human linguistic processes lack the precision required when all we do is use labels. In this paper, reactive power and frequency are used as examples. The act of measurement finds the values of the coef-ficients of the model. In other words, it solves an equation. In a digital instrument, information about the quality of the fit between the physical entity being measured and the conceptual model is often available. In essence the instrument can comment on the selection of the model. This comment should be reported as part of the statement of the result of the measurement, along with the declared value and the uncertainty.

frequency↗
NASA NTRS1986

Turbulent Boundary Layers in Oscillating Flows. Part 1: an Experimental and Computational Study

An experimental-computational study of the behavior of turbulent boundary layers for oscillating air flows over a plane surface with a small favorable mean pressure gradient is described. Experimental studies were conducted for boundary layers generated on the test section wall of a facility that produces a flow with a mean free stream velocity and a superposed nearly-pure sinusoidal component over a wide range of frequency. Flow at a nominal mean free stream velocity of 50 m/s were studied at atmospheric pressure and temperature at selected axial positions over a 2 m test length for frequencies ranging from 4 to 29 Hz. Quantitative experimental results are presented for unsteady velocity profiles and longitudinal turbulence levels obtained from hot wire anemometer measurements at three axial positions. Mean velocity profiles for oscillating flows were found to exhibit only small deviations from corresponding steady flow profiles, while amplitudes and phase relationships exhibited a strong dependence on axial position and frequency. Since sinusoidal flows could be generated over a wide range of frequency, studies at fixed values of reduced frequency at different axial positions were studied. Results show that there is some utility in the use of reduced frequency to correlate unsteady velocity results. The turbulence level u' sub rms was observed to vary essentially sinusoidally around values close to those measured in steady flow. However, the amplitude of oscillation and phase relations for turbulence level were found to be strongly frequency dependent. Numerical predictions were obtained using an unsteady boundary layer computational code and the Cebeci-Smith and Glushko turbulence models. Predicted quantities related to unsteady velocity profiles exhibit fair agreement with experiment when the Cebeci-Smith turbulence model is used.

Cook, W. J.↗
DOE OSTI2023

Frequency combs in optically injected terahertz ring quantum cascade lasers

Quantum cascade lasers (QCLs) have emerged as promising candidates for generating chip-scale frequency combs in mid-infrared and terahertz wavelengths. In this work, we demonstrate frequency comb formation in ring terahertz QCLs using the injection of light from a distributed feedback (DFB) laser. The DFB design frequency is chosen to match the modes of the ring cavity (near 3.3 THz), and light from the DFB is injected into the ring QCL via a bus waveguide. By controlling the power and frequency of the optical injection, we show that combs can be selectively formed and controlled in the ring cavity. Numerical modeling suggests that this comb is primarily frequency-modulated in character, with the injection serving to trigger comb formation. We also show that the ring can be used as a filter to control the output of the DFB QCL, potentially being of interest in terahertz photonic integrated circuits. Our work demonstrates that waveguide couplers are a compelling approach for injecting and extracting radiation from ring terahertz combs and offer exciting possibilities for the generation of new comb states in terahertz, such as frequency-modulated waves, solitons, and more.

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

Regional Inertia Estimation Using Actual Event Measurements: Florida Case

As inverter-based resources’ integration in power grids increases, their uneven distribution across the electrical network leads to the formation of local regions that are weakly coupled to the larger interconnection. This signifies the necessity of regional frequency dynamics investigation and analyzing various inertia metrics. This paper presents a practical methodology for estimating regional rate-of-change of frequency (RoCoF) using actual event recordings, which is then used to evaluate regional inertia. Florida (FL) is selected as the region of interest due to its distinct regional frequency dynamics and the rising levels of solar generation. We identify and analyze confirmed events from 2017 to 2024 that occurred in FL. The results indicate that FL contributes about 14% to the total inertia of the US Eastern Interconnection, which approximately matches its share of generation capacity. Results also highlight seasonal fluctuations in energy generation, which play a significant role in influencing inertia and thus the RoCoF levels. This emphasizes the importance of estimating regional inertia to enhance grid operations for a future that focuses on distributed generation.

Dulal, Saurav [University of Tennessee, Knoxville ↗
NASA NTRS1993

Program Determines Minimum-State Approximations To Unsteady Aerodynamic Forces

MIST implements minimum-state method for determining rational approximations of matrix of aerodynamic force coefficients. Accepts complex tabular data representing generalized unsteady aerodynamic forces over set of reduced frequencies. Determines approximations to tabular data in Laplace domain by use of rational functions. Provides capability to select coefficients of denominator in rational approximations, to constrain approximation selectably without increasing size of problem, and determines and emphasizes criticial frequency ranges in determining approximations. Written in ANSI FORTRAN 77.

Karpel, Mordechay↗
NASA NTRS2015

Inflight Characterization of the Cassini Spacecraft Propellant Slosh and Structural Frequencies

While there has been extensive theoretical and analytical research regarding the characterization of spacecraft propellant slosh and structural frequencies, there have been limited studies to compare the analytical predictions with measured flight data. This paper uses flight telemetry from the Cassini spacecraft to get estimates of high-g propellant slosh frequencies and the magnetometer boom frequency characteristics, and compares these values with those predicted by theoretical works. Most Cassini attitude control data are available at a telemetry frequency of 0.5 Hz. Moreover, liquid sloshing is attenuated by propellant management device and attitude controllers. Identification of slosh and structural frequency are made on a best-effort basis. This paper reviews the analytical approaches that were used to predict the Cassini propellant slosh frequencies. The predicted frequencies are then compared with those estimated using telemetry from selected Cassini burns where propellant sloshing was observed (such as the Saturn Orbit Insertion burn). Determination of the magnetometer boom structural frequency is also discussed.

Lee, Allan Y.↗
DOE OSTI2023

Safety Benefits Assessment for Accident Tolerant Fuels in Consideration of Steam Generator Tube Degradation Using Dynamic Event Tree Analysis

Accident tolerant fuel (ATF) is expected to delay or prevent core damage by providing additional coping time under accidents involving loss of core cooling. The effect of extended coping time may vary depending on the plant response to accidents. Age-related component degradation that deteriorates plant performance over time could have an impact on the actual advantages of ATF. The potential safety benefits of two near-term ATF candidates, including Cr-coated Zr cladding and FeCrAl cladding, are assessed for a 2-in. loss-of-coolant accident with failed high-pressure safety injection using the dynamic event tree (DET) approach considering possible stress corrosion cracking of steam generator (SG) tubing under aging. The DET approach allows likelihood quantification of accident sequences leading to core damage, including stochastic variation of system response and human actions during accident mitigation. The safety benefits of the selected ATF claddings in terms of additional coping time and the core damage frequency reduction rate under specified accident situations were quantitatively estimated. The results show that the deployment of the two selected ATF claddings is expected to lead to longer coping times and lower core damage frequency due to the wider safety margin to peak cladding temperature they provide. The safety advantages would be greater as SG tube degradation proceeds. Thus, the two ATF candidates would lead to less severe consequences in terms of likelihood of core damage and susceptibility to the SG tube degradation than UO 2 -Zr fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗