Results for “Conditional rate functions” — Page 31

NASA NTRS1999

SiC and Si3N4 Recession Due to SiO2 Scale Volatility Under Combustor Conditions

SiC and Si3N4 materials were tested under various turbine engine combustion environments, chosen to represent either conventional fuel-lean or fuel-rich mixtures proposed for high speed aircraft. Representative CVD, sintered, and composite materials were evaluated in both furnace and high pressure burner rig exposure. While protective SiO2 scales form in all cases, evidence is presented to support paralinear growth kinetics, i.e. parabolic growth moderated simultaneously by linear volatilization. The volatility rate is dependent on temperature, moisture content, system pressure, and gas velocity. The burner tests were used to map SiO2 volatility (and SiC recession) over a range of temperature, pressure, and velocity. The functional dependency of material recession (volatility) that emerged followed the form: exp(-QIRT) * P(exp x) * v(exp y). These empirical relations were compared to rates predicted from the thermodynamics of volatile SiO and SiO(sub x)H(sub Y) reaction products and a kinetic model of diffusion through a moving, boundary layer. For typical combustion conditions, recession of 0.2 to 2 micron/h is predicted at 1200- 1400C, far in excess of acceptable long term limits.

Smialek, James L.↗

NASA NTRS1999

SiC and Si3N4 Recession Due to SiO2 Scale Volatility Under Combustor Conditions

Silicon carbide (SiC) and Si3N4 materials were tested in various turbine engine combustion environments chosen to represent either conventional fuel-lean or fuel-rich mixtures proposed for high-speed aircraft. Representative chemical vapor-deposited (CVD), sintered, and composite materials were evaluated by furnace and high-pressure burner rig exposures. Although protective SiO2 scales formed in all cases, the evidence presented supports a model based on paralinear growth kinetics (i.e., parabolic growth moderated simultaneously by linear volatilization). The volatility rate is dependent on temperature, moisture content, system pressure, and gas velocity. The burner tests were thus used to map SiO2 volatility (and SiC recession) over a range of temperatures, pressures, and velocities. The functional dependency of material recession (volatility) that emerged followed the form A[exp(-Q / RT)](P(sup x)v(sup y). These empirical relations were compared with rates predicted from the thermodynamics of volatile SiO and SiOxHy reaction products and a kinetic model of diffusion through a moving boundary layer. For typical combustion conditions, recession of 0.2 to 2 micrometers/hr is predicted at 1200 to 1400 C, far in excess of acceptable long-term limits.

Smialek, James L.↗

NASA NTRS2016

Environmentally Friendly Coating Technology for Autonomous Corrosion Control

This work concerns the development of environmentally friendly encapsulation technology, specifically designed to incorporate corrosion indicators, inhibitors, and self-healing agents into a coating, in such a way that the delivery of the indicators and inhibitors is triggered by the corrosion process, and the delivery of self-healing agents is triggered by mechanical damage to the coating. Encapsulation of the active corrosion control ingredients allows the incorporation of desired autonomous corrosion control functions such as: early corrosion detection, hidden corrosion detection, corrosion inhibition, and self-healing of mechanical damage into a coating. The technology offers the versatility needed to include one or several corrosion control functions into the same coating.The development of the encapsulation technology has progressed from the initial proof-of-concept work, in which a corrosion indicator was encapsulated into an oil-core (hydrophobic) microcapsule and shown to be delivered autonomously, under simulated corrosion conditions, to a sophisticated portfolio of micro carriers (organic, inorganic, and hybrid) that can be used to deliver a wide range of active corrosion ingredients at a rate that can be adjusted to offer immediate as well as long-term corrosion control. The micro carriers have been incorporated into different coating formulas to test and optimize the autonomous corrosion detection, inhibition, and self-healing functions of the coatings. This paper provides an overview of progress made to date and highlights recent technical developments, such as improved corrosion detection sensitivity, inhibitor test results in various types of coatings, and highly effective self-healing coatings based on green chemistry.

Coatings↗

NASA NTRS2016

Corrosion-Activated Micro-Containers for Environmentally Friendly Corrosion Protective Coatings

This work concerns the development of environmentally friendly encapsulation technology, specifically designed to incorporate corrosion indicators, inhibitors, and self-healing agents into a coating, in such a way that the delivery of the indicators and inhibitors is triggered by the corrosion process, and the delivery of self-healing agents is triggered by mechanical damage to the coating. Encapsulation of the active corrosion control ingredients allows the incorporation of desired autonomous corrosion control functions such as: early corrosion detection, hidden corrosion detection, corrosion inhibition, and self-healing of mechanical damage into a coating. The technology offers the versatility needed to include one or several corrosion control functions into the same coating.The development of the encapsulation technology has progressed from the initial proof-of-concept work, in which a corrosion indicator was encapsulated into an oil-core (hydrophobic) microcapsule and shown to be delivered autonomously, under simulated corrosion conditions, to a sophisticated portfolio of micro carriers (organic, inorganic, and hybrid) that can be used to deliver a wide range of active corrosion ingredients at a rate that can be adjusted to offer immediate as well as long-term corrosion control. The micro carriers have been incorporated into different coating formulas to test and optimize the autonomous corrosion detection, inhibition, and self-healing functions of the coatings. This paper provides an overview of progress made to date and highlights recent technical developments, such as improved corrosion detection sensitivity, inhibitor test results in various types of coatings, and highly effective self-healing coatings based on green chemistry. The NASA Kennedy Space Centers Corrosion Technology Lab at the Kennedy Space Center in Florida, U.S.A. has been developing multifunctional smart coatings based on the microencapsulation of environmentally friendly corrosion indicators, inhibitors and self-healing agents. This allows the incorporation of autonomous corrosion control functionalities, such as corrosion detection and inhibition as well as the self-healing of mechanical damage, into coatings. This paper presents technical details on the characterization of inhibitor-containing particles and their corrosion inhibitive effects using electrochemical and mass loss methods.Three organic environmentally friendly corrosion inhibitors were encapsulated in organic microparticles that are compatible with desired coatings. The release of the inhibitors from the microparticles in basic solution was studied. Fast release, for immediate corrosion protection, as well as long-term release for continued protection, was observed.The inhibition efficacy of the inhibitors, incorporated directly and in microparticles, on carbon steel was evaluated. Polarization curves and mass loss measurements showed that, in the case of 2MBT, its corrosion inhibition effectiveness was greater when it was delivered from microparticles.

Corrosion Control↗

DOE OSTI2024

Emergence of catalytic function in prebiotic information-coding polymers

Life as we know it relies on the interplay between catalytic activity and information processing carried out by biological polymers. Here we present a plausible pathway by which a pool of prebiotic information-coding oligomers could acquire an early catalytic function, namely sequence-specific cleavage activity. Starting with a system capable of non-enzymatic templated replication, we demonstrate that even non-catalyzed spontaneous cleavage would promote proliferation by generating short fragments that act as primers. Furthermore, we show that catalytic cleavage function can naturally emerge and proliferate in this system. Specifically, a cooperative catalytic network with four subpopulations of oligomers is selected by the evolution in competition with chains lacking catalytic activity. The cooperative system emerges through the functional differentiation of oligomers into catalysts and their substrates. The model is inspired by the structure of the hammerhead RNA enzyme as well as other DNA- and RNA-based enzymes with cleavage activity that readily emerge through natural or artificial selection. We identify the conditions necessary for the emergence of the cooperative catalytic network. In particular, we show that it requires the catalytic rate enhancement over the spontaneous cleavage rate to be at least 10 2 –10 3 , a factor consistent with the existing experiments. The evolutionary pressure leads to a further increase in catalytic efficiency. The presented mechanism provides an escape route from a relatively simple pairwise replication of oligomers toward a more complex behavior involving catalytic function. This provides a bridge between the information-first origin of life scenarios and the paradigm of autocatalytic sets and hypercycles, albeit based on cleavage rather than synthesis of reactants.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2024

Emergence of catalytic function in prebiotic information-coding polymers

Life as we know it relies on the interplay between catalytic activity and information processing carried out by biological polymers. Here we present a plausible pathway by which a pool of prebiotic information-coding oligomers could acquire an early catalytic function, namely sequence-specific cleavage activity. Starting with a system capable of non-enzymatic templated replication, we demonstrate that even non-catalyzed spontaneous cleavage would promote proliferation by generating short fragments that act as primers. Furthermore, we show that catalytic cleavage function can naturally emerge and proliferate in this system. Specifically, a cooperative catalytic network with four subpopulations of oligomers is selected by the evolution in competition with chains lacking catalytic activity. The cooperative system emerges through the functional differentiation of oligomers into catalysts and their substrates. The model is inspired by the structure of the hammerhead RNA enzyme as well as other DNA- and RNA-based enzymes with cleavage activity that readily emerge through natural or artificial selection. We identify the conditions necessary for the emergence of the cooperative catalytic network. In particular, we show that it requires the catalytic rate enhancement over the spontaneous cleavage rate to be at least 10 2 –10 3 , a factor consistent with the existing experiments. The evolutionary pressure leads to a further increase in catalytic efficiency. The presented mechanism provides an escape route from a relatively simple pairwise replication of oligomers toward a more complex behavior involving catalytic function. This provides a bridge between the information-first origin of life scenarios and the paradigm of autocatalytic sets and hypercycles, albeit based on cleavage rather than synthesis of reactants.

Tkachenko, Alexei V. (ORCID:000000031291243X)↗

DOE OSTI2019

A sparse Gaussian sigmoid basis function approximation of hyperspectral data for detection of solids

We define a new characterization of emissivity and reflectance curves for compositional exploitation of hyperspectral data. Here, our method decomposes each spectrum into a sparse set of Gaussian sigmoid components using penalized regression. Detection is based on the combination of Gaussian sigmoid components unique to a target material. Focusing on the presence of spectral upslopes and downslopes rather than spectral correlations makes detection more robust to both target variation and spectral variability from atmosphere and background encountered during the collection process. We present simulation studies that demonstrate the potential to reduce false positive rates without compromising sensitivity. Characterization of long–wave infrared (LWIR) experimental data validates our method using minerals of different particle sizes, measurement angles, and collection conditions.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2021

Thin Water Films Enable Low-Temperature Magnesite Growth Under Conditions Relevant to Geologic Carbon Sequestration

Injecting supercritical CO2 (scCO2) into basalt formations for long-term storage is a promising strategy for mitigating CO2 emissions. Mineral carbonation can result in permanent entrapment of CO2; however, carbonation kinetics in thin H2O films in humidified scCO2 is not well understood. We investigated forsterite (Mg2SiO4) carbonation to magnesite (MgCO3) via amorphous magnesium carbonate (AMC; MgCO3·xH2O, 0.5 < x < 1), with the goal to establish the fundamental controls on magnesite growth rates at low H2O activity and temperature. Experiments were conducted at 25, 40, and 50 °C in 90 bar CO2 with a H2O film thickness on forsterite that averaged 1.78 ± 0.05 monolayers. In situ infrared spectroscopy was used to monitor forsterite dissolution and the growth of AMC, magnesite, and amorphous SiO2 as a function of time. Geochemical kinetic modeling showed that magnesite was supersaturated by two to three orders of magnitude and grew according to a zero-order rate law. The results indicate that the main drivers for magnesite growth are sustained high supersaturation coupled with low H2O activity, a combination of thermodynamic conditions not attainable in bulk aqueous solution. This improved understanding of reaction kinetics can inform subsurface reactive transport models for better predictions of CO2 fate and transport.

Kerisit, Sebastien N.↗

NASA NTRS2012

Optical Diagnostic Characterization of High-Power Hall Thruster Wear and Operation

Optical emission spectroscopy is employed to correlate BN insulator erosion with high-power Hall thruster operation. Specifically, actinometry leveraging excited xenon states is used to normalize the emission spectra of ground state boron as a function of thruster operating condition. Trends in the strength of the boron signal are correlated with thruster power, discharge voltage, and discharge current. In addition, the technique is demonstrated on metallic coupons embedded in the walls of the HiVHAc EM thruster. The OES technique captured the overall trend in the erosion of the coupons which boosts credibility in the method since there are no data to which to calibrate the erosion rates of high-power Hall thrusters. The boron signals are shown to trend linearly with discharge voltage for a fixed discharge current as expected. However, the boron signals of the higher-power NASA 300M and NASA 457Mv2 trend with discharge current and show an unexpectedly weak to inverse dependence on discharge voltage. Electron temperatures measured optically in the near-field plume of the thruster agree well with Langmuir probe data. However, the optical technique used to determine Te showed unacceptable sensitivity to the emission intensities. Near-field, single-frequency imaging of the xenon neutrals is also presented as a function of operating condition for the NASA 457 Mv2.

Williams, George J., Jr.↗

DOE OSTI2019

Creep Resistance of Bulk Copper-Niobium Composites: an Inverse Effect of Multilayer Length Scale

We present that metallic multilayer systems show promising performance in extreme environments, with high stability of bi-metal interfaces down to nanometer length scales. The creep behavior of bulk, accumulative roll bonded (ARB) Copper-Niobium (Cu-Nb) composites has been studied at 400 °C as a function of layer thickness, ranging from 2μm to 65μm. Similar to single phase metallic systems, three regimes are observed during creep: transient, steady-state and tertiary. The mechanism controlling minimum creep rate for all conditions tested has a strong dependence on stress, consistent with dislocation-dominated creep. Additionally, unlike the conventional effect of grain size on creep resistance, this study reveals that decreasing length scale increases creep resistance.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Final Report: In-Situ TEM Observations of Degradation Mechanisms in Next-Generation High-Energy Density Lithium-Ion Battery Systems

This project originally sought to characterize nanoscale processes associated with the degradation of next-generation high energy density lithium-ion battery electrodes via in-situ transmission electron microscopy (TEM). The research also focused on developing the experimental techniques necessary for investigating electrochemical systems by in-situ transmission electron microscopy and providing a framework for understanding and quantifying electron beam effects that influence experimental results. In line with these goals, this project demonstrated and published the first in-situ TEM cycling of a Li-ion battery electrode in commercially relevant non-aqueous electrolyte: a technique subsequently adopted by a number of researchers in the field. Experiments performed on Sn anodes, demonstrated porosity evolution during Li dealloying as a mechanism for strain accommodation during the first cycle, and observed partially reversible crystalline to amorphous phase transitions associated with Li insertion and extraction in subsequent cycles. Complementary study of in-situ dealloying in a simple model, Au-Cu, was also performed. We also published the earliest quantitative measurements of electron beam effects in aqueous and non-aqueous liquids. Specifically, we utilized a model system to quantify the fraction of incident electron beam that contributed to charge transfer mediated reactions in non-aqueous liquid, since such liquids are primarily dose sensitive. We also quantified the evolution of model aqueous chemistries as a function of dose rate and chemical potential to better understand the reaction mechanisms active in liquids exposed to electron beams. The original project goals included the use of controlled environments to simulate different battery operational conditions. To aid such experiments, we developed new experimental apparatuses and techniques to perform in-situ liquid cell TEM under controlled temperature, including heating and cooling. We demonstrated this capability in aqueous systems; specifically understanding phase selection and solid-liquid interface interactions with particles during water crystallization and hydrothermal precipitation kinetics of ZnO. We also published the first demonstration of in-situ TEM based high-field (plasma) experiments and in-situ TEM of aqueous photochemistry, which demonstrated an previously unrecognized early growth mode transition during Au sputtering and delocalization of gas bubble nucleation during water splitting, respectively. In addition to the scientific results, this portion of the project greatly expanded the range of systems that can be characterized in realistic environments at the nanoscale via in-situ TEM. Unfortunately, commercial battery electrolytes are quite sensitive to electron dose. This limits the time of acquisition and/or the spatial resolution of the experiments. The same problem has been encountered in all subsequent publications in the field. The major problem, relative to the project original goals, is that long term cycling is challenging to characterize and the desired high resolution or analytical capabilities are limited. In line with our original goals to characterize battery reaction and degradation mechanisms under controlled electrochemical cycling, we developed a completely new type of Li-ion electrochemical cell that has been useful for both structural and analytical characterization. To date, we have demonstrated this platform for in-situ cycling of Li-ion batteries during scanning electron microscopy (SEM), Auger electron spectroscopy (AES), and x-ray photoelectron spectroscopy (XPS). In-situ AES has been found to be a quite powerful tool to characterize the chemical evolution of Li-ion batteries cycled in-situ and much of our effort in the final project period has focused on charactering Li-ion cathodes using the technique. We utilized in-situ SEM to propose a new mechanism for Li whisker/dendrite formation and show the importance of diffusion mediated stress relaxation in fracture of Sn anode particles. A combination of in-situ XPS and AES was used to clarify the CuO anode reaction mechanism. In the final project period, we have gained new insights into surface reactions occurring on cathodes at high voltage using in-situ AES. Specifically, we have discovered that many of the SEI formation reactions typically attributed to electrolyte decomposition are actually more fundamental to the electrode material surface thermodynamics in the presence of an arbitrary carbon source. These insights greatly affect how we understand and control surface degradation induced capacity fade at cathodes. Finally, we have made some effort to apply this novel in-situ platform to TEM characterization and believe this is a fruitful avenue for future research.

25 ENERGY STORAGE↗

DOE OSTI2026

Robust Measurement of Stellar Streams around the Milky Way: Correcting Spatially Variable Observational Selection Effects in Optical Imaging Surveys

Observations of density variations in stellar streams are a promising probe of low-mass dark matter substructure in the Milky Way. However, survey systematics such as variations in seeing and sky brightness can also induce artificial fluctuations in the observed densities of known stellar streams. These variations arise because survey conditions affect both object detection and star–galaxy misclassification rates. To mitigate these effects, we use Balrog synthetic source injections in the Dark Energy Survey (DES) Y3 data to calculate detection rate variations and classification rates as functions of survey properties. We show that these rates are nearly separable with respect to survey properties and can be estimated with sufficient statistics from the synthetic catalogs. Applying these corrections reduces the standard deviation of relative detection rates across the DES footprint by a factor of 5, and our corrections significantly change the inferred linear density of the Phoenix stream when including faint objects. Additionally, for artificial streams with DES-like survey properties we are able to recover density power spectra with reduced bias. We also find that uncorrected power-spectrum results for Legacy Survey of Space and Time (LSST)-like data can be around 5 times more biased, highlighting the need for such corrections in future ground-based surveys.

79 ASTRONOMY AND ASTROPHYSICS↗

NASA NTRS1972

Millimeter wave propagation measurements using the ATS 5 satellite

The ATS 5 millimeter wave propagation experiment determines long- and short-term attenuation statistics of operational millimeter wavelength earthspace links as functions of defined meteorological conditions. A preliminary analysis of results with 15 GHz downlink and 32 GHz uplink frequency bands indicates that both frequency bands exhibit an excellent potential for utilization in reliable high data rate earth-space communications systems.

Ippolito, L. J.↗

NASA NTRS1987

A kinetic study of hydrous alteration of amorphous MgSiO smokes - Implications for cometary particles and chondrite matrix

Measurements of the rate of hydrous alteration of amorphous Mg-SiO smokes are reported as a function of temperature, as inferred by observing changes in the infrared spectra of these materials. It is shown that under the conditions reported for the nucleus of Comet Halley, based on measurements made by the Vega and Giotto missions, amorphous, anhydrous Mg-SiO smokes would become hydrated within several weeks in the dusty regolith observed on the surface. However, if such grains were released in 'jets' or from loose ice fragments, then previously amorphous grains would retain their anhydrous nature. Similarly, brief periods of aqueous activity on meteorite parent bodies would convert amorphous, fine-grained material to hydrated phyllosilicates much more rapidly than coarse mineral grains. A kinetic model might therefore be developed to explain the observed textural relationships in the matrices of carbonaceous chondrites such as Mokoia, where amorphous phyllosilicates are intimately associated with coarse anhydrous grains.

Nelson, Robert↗

NASA NTRS1987

Scattering parameters for aspherical hydrometeors at microwave frequencies

Scattering parameters for ensembles of aspherical ice and liquid hydrometeors were calculated at Psi = 50 deg for frequencies of 37.0, 50.3, and 85.6 GHz. Hydrometeors were assumed to be oblate spheroids whose semiminor axes were aligned at Psi = 0 deg. The angle of 50 deg is determined by the viewing angle of recent satellite-borne radiometers. Backscattering phase functions and extinction coefficients at Psi = 0 deg were also computed at 18.0, 37.0, and 85.6 GHz to provide information for future nadir scanning radars. The hydrometeors were assumed to be characterized by Marshall-Palmer (1948) size distributions. The extended boundary condition method was used to calculate the extinction and backscattering coefficients as well as the albedo for single scattering and the asymmetry factor of the phase function. Results are fitted to simple functions of the rainfall rate. Some comparisons intended to illustrate the differences and similarities of these results with those obtained from equal volume spheres are also presented.

Kummerow, C.↗

NASA NTRS1989

Electrochemical Studies Of Aluminum Coated With Primer

Technical paper describes experiments using ac-impedance method of analyzing corrosion of metal surfaces and breakdown of protective coatings. Alternating-current-impedance scans provide more detailed information, indicating changes in corrosion rates, progressive deterioration of coatings, changes in metal surfaces, and reaction mechanisms. Changes in conditions of coatings detected by ac method before dc methods show increase in metal-corrosion current. Measurements of impedance as function of frequency provides sufficient data to enable resistances and capacitances to be determined by performing least-squares fit. Knowledge of dependence of these values on time leads to more detailed understanding of corrosion process.

Danford, Merlin D.↗

NASA NTRS1993

Check valve with poppet damping mechanism

An inline check valve for a flow line is presented where the valve element is guided for inline travel forward and rearward of a valve sealing member and is spring biased to a closed sealing condition. One of the guides for the valve element includes a dashpot bore and plunger member to control the rate of travel of the valve element in either direction as well as provided a guiding function. The dashpot is not anchored to the valve body so that the valve can be functional even if the plunger member becomes jammed in the dashpot.

Morris, Brian G.↗

NASA NTRS2002

Convection and Easterly Wave Structure Observed in the Eastern Pacific Warm-Pool during EPIC-2001

During September-October 2001, the East Pacific Investigation of Climate Processes in the Coupled Ocean-Atmosphere System (EPIC-2001) ITCZ field campaign focused on studies of deep convection in the warm-pool region of the East Pacific. In addition to the TAO mooring array, observational platforms deployed during the field phase included the NOAA ship RN Ronald H. Brown, the NSF ship RN Horizon, and the NOAA P-3 and NCAR C-130 aircraft. This study combines C-band Doppler radar, rawinsonde, and surface heat flux data collected aboard the RN Brown to describe ITCZ convective structure and rainfall statistics in the eastern Pacific as a function of 3-5 day easterly wave phase. Three distinct easterly wave passages occurred during EPIC-2001. Wind and thermodynamic data reveal that the wave trough axes exhibited positively correlated U and V winds and a slight westward phase tilt with height. A relatively strong (weak) northeasterly deep tropospheric shear followed the trough (ridge) axis. Temperature and humidity perturbations exhibited mid-to upper level cooling (warming) and drying (moistening) in the northerly (trough and southerly) phase. At low levels warming (cooling) occurred in the northerly (southerly) phase with little change in the relative humidity, though mixed layer mixing ratios were larger during the northerly phase. When composited, radar, sounding, lightning and surface heat flux observations suggest the following systematic behavior as a function of wave phase: approximately zero to one quarter wavelength ahead of (behind) the wave trough in northerly (southerly) flow, larger (smaller) CAPE, lower (higher) CIN, weaker (stronger) tropospheric shear, higher (lower) conditional mean rain rates, higher (lower) lightning flash densities, and more (less) robust convective vertical structure occurred. Latent and sensible heat fluxes reached a minimum in the northerly phase and then increased through the trough, reaching a peak during the ridge phase (leading the peak in CAPE). From a radar echo coverage perspective, larger areas of light rain and slightly larger (10%) area averaged rain rates occurred in the vicinity of, and just behind, the trough axes in southerly flow. Importantly, the transition in convective structure observed across the trough axis when considered with the relatively small change in area mean rain rates suggests the presence of a transition in the vertical structure of diabatic heating across the easterly waves examined. The inferred transition in heating structure is supported by radar diagnosed divergence profiles that exhibit convective (stratiform) characteristics ahead of (behind) the trough.

Peterson, Walter A.↗