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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 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Wave-Particle Interactions As a Driving Mechanism for the Solar Wind

Our research has been focusing on a highly experimentally relevant issue: intermittency of the fluctuating fields in outflowing plasmas. We have contributed to both the theoretical and experimental research of the topic. In particular, we have developed a theoretical model and data analyzing programs to examine the issue of intermittency in space plasma outflows, including the solar wind. As fluctuating electric fields in the solar wind are likely to provide a heating and acceleration mechanism for the ions, our studies of the intermittency in turbulence in space plasma outflows help us toward achieving the goal of comparing major physical mechanisms that contribute to the driving of the fast solar wind. Our new theoretical model extends the utilities of our global hybrid model, which has allowed us to follow the kinetic evolution of the particle distributions along an inhomogeneous field line while the particles are subjected to various physical mechanisms. The physical effects that were considered in the global hybrid model included wave-particle interactions, an ambipolar electric field that was consistent with the particle distributions themselves, and Coulomb collisions. With an earlier version of the global hybrid model, we examined the overall impact on the solar wind flow due to the combination of these physical effects. In particular, we studied the combined effects of two major mechanisms that had been proposed as the drivers of the fast solar wind: (1) velocity filtration effect due to suprathermal electrons; (2) ion cyclotron resonance. Since the approval of this research grant, we have updated the model such that the effects due to these two driving mechanisms can be examined separately, thereby allowing us to compare their contributions to the acceleration of the solar wind. In the next section, we shall demonstrate that the velocity filtration effect is rather insignificant in comparison with that due to ion cyclotron resonance.

Wagner, William J.↗
NASA NTRS2008

Observational and Theoretical Challenges to Wave or Turbulence Accelerations of the Fast Solar Wind

We use both observations and theoretical considerations to show that hydromagnetic waves or turbulence cannot produce the acceleration of the fast solar wind and the related heating of the open solar corona. Waves do exist as shown by Hinode and other observations, and can play a role in the differential heating and acceleration of minor ions but their amplitudes are not sufficient to power the wind, as demonstrated by extrapolation of magnetic spectra from Helios and Ulysses observations. Dissipation mechanisms invoked to circumvent this conclusion cannot be effective for a variety of reasons. In particular, turbulence does not play a strong role in the corona as shown by both eclipse observations of coronal striations and theoretical considerations of line-tying to a nonturbulent photosphere, nonlocality of interactions, and the nature of kinetic dissipation. In the absence of wave heating and acceleration, the chromosphere and transition region become the natural source of open coronal energization. We suggest a variant of the velocity filtration approach in which the emergence and complex churning of the magnetic flux in the chromosphere and transition region continuously and ubiquitously produces the nonthermal distributions required. These particles are then released by magnetic carpet reconnection at a wide range of scales and produce the wind as described in kinetic approaches. Since the carpet reconnection is not the main source of the energization of the plasma, there is no expectation of an observable release of energy in nanoflares.

Roberts, D. Aaron↗
DOE OSTI2020

Fundamental Studies of Oxidation Reactions on Model Catalysts. Final report

This report covers the reporting period from 08/15/2003 to 08/31/2019. The research activities were focused on the oxidation of methane, nitric oxide, and propylene in addition to contributions on the kinetics, synthesis, theory and characterization of various catalytic systems. As described in the report, we were able to formulate hypotheses, construct specialized equipment and carry out experimental and theoretical work to test the hypotheses. Major advances were accomplished in the fundamental understanding of these systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Carbon Dioxide Insertion into Rhenium Hydrides as a Probe for the Impact of Solvent on Linear Free Energy Relationships between Thermodynamic and Kinetic Hydricity

The kinetics of CO 2 insertion into electronically different Re( R bpy)(CO) 3 H ( R bpy = 4,4'-R-2,2'- bipyridine; R = OMe, t Bu, Me, H, Br, COOMe, CF 3 ) complexes to form Re( R bpy)(CO) 3 {OC(H)O} compounds were determined in acetone, dimethylacetamide (DMAc), dimethylformamide (DMF), dimethylsulfoxide (DMSO), and 3-methoxypropionitrile (3-MPN) and compared with previous data in acetonitrile (MeCN). The rates of CO 2 insertion for any one complex of the type Re(Rbpy)(CO) 3 H in different solvents correlates with the Dimroth-Reichardt (E T (30)) solvent parameter. Hammett plots in each solvent indicate that insertion reactions are faster for bpy ligands with electron-donating groups. There is, however, no correlation between the slope of the Hammett plot in different solvents and any common solvent parameter. Similarly, the enthalpies and entropies of activation and kinetic isotope effects associated with CO 2 insertion into Re(bpy)(CO) 3 H in different solvents do not correlate with any common solvent parameters. Theoretical calculations were used to determine the relative thermodynamic hydricities of Re( R bpy)(CO) 3 H type complexes in MeCN, acetone, DMF, and DMSO and in each solvent complexes with more electron-donating substituents on the bpy ligand are stronger hydride donors. Linear Free Energy Relationships (LFERs) between calculated thermodynamic and experimental kinetic hydricity, as measured through CO 2 insertion reactions, were observed in MeCN, acetone, DMF, and DMSO. Furthermore, the slopes of the LFERs correlate with the dielectric constant of the solvent. Overall, this work provides fundamental information about the thermodynamics and kinetics of hydride transfer reactions in different solvents, which is valuable for catalyst design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

The kinetics of static recovery by dislocation climb

Abstract The initial microstructure of a wide range of structural materials is conditioned by thermo-mechanical treatments such as hot-working, tempering, or solution annealing. At the elevated temperatures associated with these treatments the dislocation microstructure evolves, usually decreasing in density through a process known as static recovery. Despite its technological relevance, static recovery is not fully characterized from a theoretical standpoint, with even the controlling mechanisms subject to debate. In this study, a climb-enabled discrete dislocation dynamics (DDD) capability is leveraged to explore the kinetics of static recovery in pure Fe when controlled by dislocation climb. Quantitative data from these simulations is used to develop a revised static recovery law, and provides the parameters appropriate for predictive microstructure models in Fe. This law differs from previous analytical derivations invoking climb of dislocations, following the logarithmic trends typical of experimental observations where prior work did not. Direct comparison between the recovery law derived from DDD to experimental recovery data in alpha Fe shows strong agreement across a range of temperatures, and suggests that climb is the controlling mechanism for static recovery in pure metals.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Mechanism and kinetics of light alkane dehydrogenation and cracking over isolated Ga species in Ga/H-MFI

The objective of this study is to examine the mechanisms and kinetics of C2H6 dehydrogenation and n-C4H10 dehydrogenation and cracking over isolated Ga species in Ga/HMFI and to compare these results to those reported previously for C3H8 dehydrogenation and cracking. C2H6 dehydrogenation is found to be catalyzed by both [GaH]2+ and [GaH2]+ cations at similar turnover frequencies. Rate measurements over Ga/H-MFI containing predominantly [GaH2]+ cations reveal that C2H6 dehydrogenation rates exhibit a Langmuir.Hinshelwood dependence on C2H6 partial pressure at elevated temperatures (>730 K), consistent with the involvement of chemisorbed [C2H5.GaH]+ species. The reaction kinetics suggest that C2H6 dehydrogenation proceeds via heterolytic C-H cleavage of adsorbed C2H6 by [GaH2]+ cations to form H2 and [C2H5-GaH]+ species, which further decompose via β-hydride elimination to form C2H4. By contrast, C4H10 dehydrogenation and both terminal and central cracking are catalyzed exclusively by [GaH]2+ cations. All three reactions exhibit a Langmuir-Hinshelwood dependence on C4H10 partial pressure and are inhibited by H2. Ratios of dehydrogenation to cracking (total) and terminal to central cracking are approximately independent of C4H10 partial pressure consistent with the involvement of a common C4H10-derived surface intermediate. The observed reaction kinetics are consistent with an alkyl-mediated mechanism occurring over [GaH]2+, analogous to that reported previously for C3H8 dehydrogenation/cracking over Ga/H-MFI (Phadke, N. M.; et al. J. Am. Chem. Soc. 2019, 141, 1614-1627). The mechanism proceeds via facile, heterolytic dissociation of adsorbed C4H10 to form [C4H9-GaH]+-H+ cation pairs via methyl C-H-activated pathways. Dehydrogenation then proceeds via β-hydride elimination, respectively, forming butene, while terminal and central cracking proceed via C-H-activated H+ attack. Methylene activation was also considered but found to occur at a significantly lower rate. Theoretical analysis of the proposed reaction pathways leads to apparent activation enthalpies in good agreement with values extracted from the measured kinetics, thereby supporting the proposed pathways and the roles of [GaH]2+ and [GaH2]+ cations in the dehydrogenation and cracking of light alkanes on Ga/H-MFI.

Phadke, NM↗
DOE OSTI2021

Kinetic, metabolic, and statistical analytics: addressing metabolic transport limitations among organelles and microbial communities

Microbial organisms engage in a variety of metabolic interactions. A crucial part of these interactions is the exchange of molecules between different organelles, cells, and the environment. The main forces mediating this metabolic exchange are transporters. This transport can be difficult to measure experimentally because several transport mechanisms remain opaque. However, theoretical calculations about the inputs and outputs of cells via metabolic exchanges have enabled the successful inference of the workings of intra-organismal and inter-organismal systems. Kinetic, metabolic, and statistical modeling approaches in combination with omics data are enhancing our knowledge and understanding about metabolic exchange and mass resource allocation. Furthermore, this model-driven analytics approach can guide effective experimental design and yield new insights into biological function and control.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Carbon dioxide capture with aqueous amino acids: Mechanistic study of amino acid regeneration by guanidine crystallization and process intensification

CO 2 capture from powerplant-generated flue gas via a phase-changing process involving absorption with aqueous amino acids (e.g., glycine or sarcosine) and bicarbonate crystallization with bis-iminoguanidines (e.g., glyoxal-bis-iminoguanidine or GBIG) is investigated in this paper. This process is of high interest due to its potential to decrease the energy penalty for CO 2 capture by significantly reducing the solvent regeneration energy typically associated with aqueous amine solvents. A critical step in the proposed CO 2 capture mechanism is the regeneration of the amino acid by removal of protons and bicarbonate ions from solution through crystallization of GBIGH 2 2+ bicarbonate salt. Here, we investigated the thermodynamics and kinetics of glycine regeneration by crystallization of GBIGH 2 2+ (HCO 3 – ) 2 (H 2 O) 2 . A theoretical model was developed and compared to experimental data to simulate and predict the glycine regeneration and determine its reaction mechanism. This combined experimental and theoretical study led to the conclusion that, while the GBIGH 2 2+ bicarbonate crystallization step provides most of the thermodynamic driving force for the glycine regeneration, the rate-limiting step is the protonation of GBIG prior to crystallization. The CO 2 loading and amino acid regeneration steps were combined into a single, intensified process using a bubble column reactor. The CO 2 loading capacity of GBIG was experimentally determined to be roughly 1.36 mol CO 2 per mol GBIG. These results provide the fundamental basis for developing an effective carbon capture technology with phase-changing amino acid/guanidine absorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Ethylene oxidation on unpromoted silver catalysts: Reaction pathway and selectivity analysis using DFT calculations

Chemical conversions in catalytic partial oxidation processes of light hydrocarbons are responsible for the production of numerous industrial chemicals, plastics, and intermediates. These processes are relatively expensive to perform, and are typically operated at high thermodynamic inefficiency, so the development of novel, highly efficient catalysts would prove to be very cost effective. Herein, our study focused on surface catalytic mechanisms of the ethylene oxide (EO) formation process. Periodic plane-wave Density Functional Theory (DFT) methods were used to analyze related reaction mechanisms on the Ag(111) surface facet with low coverage. Energetic changes of related species and pathways were calculated. Key surface species are identified to suggest the factors for the observed selectivity during EO formation. Our results are consistent with previous kinetic modeling efforts in the literature which did not employ DFT analysis. Lastly, our study demonstrates how fundamental theoretical investigations and multi-scale modeling techniques are currently impacting the advancement of rational catalyst design and microkinetic modeling techniques in the light hydrocarbon processing industry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Semiconducting High-Entropy Chalcogenide Alloys with Ambi-ionic Entropy Stabilization and Ambipolar Doping

Entropy stabilization is a novel materials-design paradigm to realize new compounds with widely tunable properties. However, almost all entropy-stabilized materials so far are either conducting metals or insulating ceramics, with a clear dearth in the semiconducting regime. Here, a new class of the multi-cationic and -anionic entropy-stabilized chalcogenide alloys based on the (Ge,Sn,Pb)(S,Se,Te) formula are synthesized and characterized experimentally. The con-figurational entropy from the disorder of both the anion and the cation sublattices reaches a record value of ~2.2 R mol -1 for the equimolar composition and stabilizes the single-phase solid solution. Theoretical calculations and experiments both show that the synthesized alloys are thermodynamically stable at the growth temperature and kinetically metastable at room temperature, segregating by spinodal decomposition at moderate temperatures. In conclusion, doping and electronic transport measurements verify that the synthesized materials are ambipolarly dopable semiconductors, which paves the way for the wider adoption of entropy-stabilized chalcogenide alloys in functional applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Re-Examination of the N 2 O + O Reaction

The reaction of N 2 O with O is a key step in consumption of nitrous oxide in thermal processes. It has two product channels, NO + NO (R2) and N 2 + O 2 (R3). The rate constant for R2 has been measured both in the forward and the reverse direction at elevated temperature and is well established. However, the rate constant for the N 2 + O 2 channel (R3) has been difficult to quantify and has significant error limits. Here, the direct reaction on the triplet surface has a barrier of around 40 kcal mol –1 , and it is too slow for the N 2 + O 2 channel to have any practical significance. Recently, Pham and Lin (2022) suggested an alternative low activation energy reaction path that involves intersystem crossing and reaction on the singlet surface. In the present work, we re-examined a wide range of experiments relevant for the N 2 O + O reaction through kinetic modeling, paying attention to the impact of artifacts such as impurities and surface reactions. Experimental results from shock tubes and batch reactors on the final NO yield in N 2 O decomposition, covering temperatures of 973–2200 K and pressures of 0.013–11.5 atm, support k 3 ~ 0, consistent with the high activation energy for reaction on the triplet surface and a low probability of ISC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Hidden figures of photo-charging: a thermo-electrochemical approach for a solar-rechargeable redox flow cell system

Achieving high current densities without thermal performance degradation at high temperatures is one of the main challenges for enhancing the competitiveness of photo-electrochemical energy storage systems. We describe a system that overcomes this challenge by incorporating an integrated photoelectrode with a redox flow cell, which functions as a coolant for the excess heat from the photo-absorber. We perform quantitative analyses to theoretically validate and highlight the merit of the system. Practical operation parameters, including daily temperature and redox reaction kinetics, are modeled with respect to heat and charge transfer mechanisms. Our analyses show a profound impact on the resulting solar-to-chemical efficiencies and stored power, which are 21.8% higher than that of a conventional photovoltaic-assisted energy storage system. This paves the way for reassessing the merit of photovoltaic-integrated systems, which have hitherto been underrated as renewable energy storage systems.

25 ENERGY STORAGE↗
DOE OSTI2020

Energetics and mechanisms for the acetonyl radical + O 2 reaction: An important system for atmospheric and combustion chemistry

The acetonyl radical (•CH 2 COCH 3 ) is relevant to atmospheric and combustion chemistry due to its prevalence in many important reaction mechanisms. One such reaction mechanism is the decomposition of Criegee intermediates in the atmosphere that can produce acetonyl radical and OH. In order to understand the fate of the acetonyl radical in these environments and to create more accurate kinetics models, we have examined the reaction system of the acetonyl radical with O 2 using highly reliable theoretical methods. Structures were optimized using coupled cluster theory with singles, doubles, and perturbative triples [CCSD(T)] with an atomic natural orbital (ANO0) basis set. Energetics were computed to chemical accuracy using the focal point approach involving perturbative treatment of quadruple excitations [CCSDT(Q)] and basis sets as large as cc-pV5Z. The addition of O 2 to the acetonyl radical produces the acetonylperoxy radical, and multireference computations on this reaction suggest it to be barrierless. Additionally, no submerged pathways were found for the unimolecular isomerization of the acetonylperoxy radical. Besides dissociation to reactants, the lowest energy pathway available for the acetonylperoxy radical is a 1-5 H shift from the methyl group to the peroxy group through a transition state that is 3.3 kcal mol -1 higher in energy than acetonyl radical + O 2 . The ultimate products from this pathway are the enol tautomer of the acetonyl radical along with O 2 . Multiple pathways that lead to OH formation are considered; however, all of these pathways are predicted to be energetically inaccessible, except at high temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Two-dimensional quantum gas with real time control of complete Hamiltonian (Final Report)

We developed a novel quantum platform with the complete capability to control individual atoms and their mutual interactions in real time. Ultracold atoms are employed since they have the lowest temperature and decoherence. This system is the ultimate dream of quantum physicists where the Hamiltonian of every single atom, including its kinetic energy, potential energy, and interactions, can be independently programmed in real time. We also initiated a new theoretical collaboration to explore its full potential.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1980

Microscale instabilities in stream interaction regions

A theoretical investigation of the microstructure of solar wind stream interaction regions is presented. The role of several electrostatic kinetic instabilities is discussed which may be important within the stream interface and the compression region. Inside of 1 AU the interface is likely to be stable against the electrostatic streaming instabilities considered. Between 1 and 2 AU it is argued that the interface will excite the magnetized ion-ion instability. The compression region is also found to be unstable beyond 1 AU, where the modified two-stream instability, beam-cyclotron instability, and ion-acoustic instability will be important in determining the structure of the compressive pulses as they evolve into forward and reverse shocks. It is concluded that the modified two-stream instability and beam-cyclotron instability predominately play a role in heating the electrons to the threshold for the ion-acoustic instability.

Eviatar, A.↗
NASA NTRS1985

Thermalization of neutral-beam-injected ions by lower hybrid waves in Jupiter's magnetosphere

A theoretical analysis of lower-hybrid wave generation by a ring distribution of superthermal ions is presented. A kinetic instability of waves traveling across the magnetic field occurs when fast neutrals escaping from the Io plasma torus are reionized and accelerated to corotation speed in Jupiter's magnetosphere. Instability is possible for modest threshold values of V/a0 = 3 - 7 where V is the pickup gyrospeed and a0 is the background-ion thermal speed. Consequent effects include the relaxation of the pickup-ion distribution and the acceleration of superthermal electrons.

Barbosa, D. D.↗
NASA NTRS1990

Stability of sub-Alfvenic plasma expansions

A theoretical treatment of the linear stability of sub-Alfvenic plasma expansion is developed. The theory is fully kinetic and includes finite-beta effects, collisional effects, and neutral gas flow. A variety of results are obtained, and are applied to the the AMPTE magnetotail release, the NRL laser experiment, and the upcoming CRRES GTO releases.

Huba, J. D.↗
NASA NTRS1990

Oxidation kinetics of model compounds of metabolic waste in supercritical water

In this NASA-funded study, the oxidation kinetics of methanol and ammonia in supercritical water have been experimentally determined in an isothermal plug flow reactor. Theoretical studies have also been carried out to characterize key reaction pathways. Methanol oxidation rates were found to be proportional to the first power of methanol concentration and independent of oxygen concentration and were highly activated with an activation energy of approximately 98 kcal/mole over the temperature range 480 to 540 C at 246 bar. The oxidation of ammonia was found to be catalytic with an activation energy of 38 kcal/mole over temperatures ranging from 640 to 700 C. An elementary reaction model for methanol oxidation was applied after correction for the effect of high pressure on the rate constants. The conversion of methanol predicted by the model was in good agreement with experimental data.

Webley, Paul A.↗