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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 1,639 records · Page 91
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Dispersion relation for gauge-free electromagnetic drift kinetics

Recently, a new approach to gyrokinetics, invariant under electromagnetic gauge transformations, was developed. The gyrocenter equations of motion are now expressed in terms of the perturbed fields instead of the potentials, in a form suitable for numerical simulations and analytic studies. In this paper, we verify that the long-wavelength limit, i.e., the drift-kinetic limit of the new gyrokinetic theory, is in line with existing work, providing a solid foundation for simulations. Here, we compute the dispersion relation of the new drift-kinetic theory in slab geometry and find agreement with a long-wavelength limit of the full Vlasov–Maxwell model.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

In situ thermal conductivity measurement revealing kinetics of thermochemical reactions

Utilizing thermochemical reactions for thermal energy storage and solar fuel production has been an emerging research topic. Thermal transport properties of the materials are an important parameter that can determine the kinetics and efficiency of thermochemical reactions. With the increasing number of new thermochemical materials (TCMs); however, there is a lack of reliable techniques to monitor the thermal transport property of the materials and their changes as a function of reactions in real time. In this work, we report the in situ monitoring of thermochemical reactions using modulated photothermal radiometry (MPR). The thermal conductivities of two TCMs, namely, calcium hydroxide (Ca(OH) 2 ) and Ba 0.15 Sr 0.85 FeO 3–δ (BSF1585), were measured as a function of temperature and time using the MPR technique. The measured thermal conductivities were correlated to the reaction. The work has two significant contributions to the research communities. First, it provides a non-invasive diagnostic tool for monitoring the thermal transport properties of TCMs that can potentially be a high-throughput measurement technique conducive to optimizing TCMs, reactors, and related thermal systems. Second, for TCMs that show observable changes in thermal transport properties, a correlation between the measured thermal conductivity and the conversion fraction of the reaction can be established for monitoring the reaction kinetics based on thermal characterization.

14 SOLAR ENERGY↗
DOE OSTI2023

Gas-phase microactuation using kinetically controlled surface states of ultrathin catalytic sheets

Biological systems convert chemical energy into mechanical work by using protein catalysts that assume kinetically controlled conformational states. Synthetic chemomechanical systems using chemical catalysis have been reported, but they are slow, require high temperatures to operate, or indirectly perform work by harnessing reaction products in liquids (e.g., heat or protons). Here, we introduce a bioinspired chemical strategy for gas-phase chemomechanical transduction that sequences the elementary steps of catalytic reactions on ultrathin (<10 nm) platinum sheets to generate surface stresses that directly drive microactuation (bending radii of 700 nm) at ambient conditions (T = 20 °C; P total = 1 atm). When fueled by hydrogen gas and either oxygen or ozone gas, we show how kinetically controlled surface states of the catalyst can be exploited to achieve fast actuation (600 ms/cycle) at 20 °C. Finally, we also show that the approach can integrate photochemically controlled reactions and can be used to drive the reconfiguration of microhinges and complex origami- and kirigami-based microstructures.

42 ENGINEERING↗
DOE OSTI2011

THERMOCHEMICAL AND PHOTOCHEMICAL KINETICS IN COOLER HYDROGEN-DOMINATED EXTRASOLAR PLANETS: A METHANE-POOR GJ436b?

We introduce a thermochemical kinetics and photochemical model. We use high-temperature bidirectional reaction rates for important H, C, O, and N reactions (most importantly for CH{sub 4} to CO interconversion), allowing us to attain thermochemical equilibrium, deep in an atmosphere, purely kinetically. This allows the chemical modeling of an entire atmosphere, from deep-atmosphere thermochemical equilibrium to the photochemically dominated regime. We use our model to explore the atmospheric chemistry of cooler (T{sub eff} < 10{sup 3} K) extrasolar giant planets. In particular, we choose to model the nearby hot-Neptune GJ436b, the only planet in this temperature regime for which spectroscopic measurements and estimates of chemical abundances now exist. Recent Spitzer measurements with retrieval have shown that methane is driven strongly out of equilibrium and is deeply depleted on the day side of GJ436b, whereas quenched carbon monoxide is abundant. This is surprising because GJ436b is cooler than many of the heavily irradiated hot Jovians and thermally favorable for CH{sub 4}, and thus requires an efficient mechanism for destroying it. We include realistic estimates of ultraviolet flux from the parent dM star GJ436, to bound the direct photolysis and photosensitized depletion of CH{sub 4}. While our models indicate fairly rich disequilibrium conditions are likely in cooler exoplanets over a range of planetary metallicities, we are unable to generate the conditions for substantial CH{sub 4} destruction. One possibility is an anomalous source of abundant H atoms between 0.01 and 1 bars (which attack CH{sub 4}), but we cannot as yet identify an efficient means to produce these hot atoms.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Relativistic Guiding-Center Motion: Action Principle, Kinetic Theory and Hydrodynamics

We treat the guiding-center dynamics in a varying external Maxwell field using a relativistically covariant action principle which reproduces the known Vandervoort expression for the drift velocity and extends it to curved spacetime. We derive the corresponding kinetic theory and ideal hydrodynamic theory. In contrast to conventional five-equation hydrodynamics, the guiding-center hydrodynamics needs only three equations due to a constraint on the motion across magnetic field. Furthermore, we argue that such a hydrodynamics is applicable to strongly coupled plasmas where kinetic theory fails.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2011

Kinetic Isotope Effects for the Reactions of Muonic Helium and Muonium with H2

The neutral muonic helium atom may be regarded as the heaviest isotope of the hydrogen atom, with a mass of ~4.1 amu (4.1H), because the negative muon screens one proton charge. We report the reaction rate of 4.1H with 1H2 to produce 4.1H1H + 1H at 295 to 500 K. The experimental rate constants are compared with the predictions of accurate quantum mechanical dynamics calculations carried out on an accurate Born-Huang potential energy surface and with previously measured rate constants of 0.11H (where 0.11H is shorthand for muonium). Kinetic isotope effects can be compared for the unprecedentedly large mass ratio of 36. The agreement with accurate quantum dynamics is quantitative at 500 K, and variational transition state theory is used to interpret the extremely low (large inverse) kinetic isotope effects in the 10-4 to 10-2 range.

08 HYDROGEN↗
DOE OSTI2023

A Theoretical Study of NH 2 Radical Reactions with Propane and Its Kinetic Implications in NH 3 -Propane Blends’ Oxidation

The reaction of NH 2 radicals with C 3 H 8 is crucial for understanding the combustion behavior of NH 3 /C 3 H 8 blends. In this study, we investigated the temperature dependence of the rate coefficients for the hydrogen abstraction reactions of C 3 H 8 by NH 2 radicals using high-level theoretical approaches. The potential energy surface was constructed at the CCSD(T)/cc-pV(T, Q)//M06-2X/aug-cc-pVTZ level of theory, and the rate coefficients were computed using conventional transition state theory, incorporating the corrections for quantum tunneling and hindered internal rotors (HIR). The computed rate coefficients showed a strong curvature in the Arrhenius behavior, capturing the experimental literature data well at low temperatures. However, at T > 1500 K, the theory severely overpredicted the experimental data. The available theoretical studies did not align with the experiment at high temperatures, and the possible reasons for this discrepancy are discussed. At 300 K, the reaction of NH 2 with C 3 H 8 predominantly occurs at the secondary C-H site, which accounts for approximately 95% of the total reaction flux. However, the hydrogen abstraction reaction at the primary C-H site becomes the dominant reaction above 1700 K. A composite kinetic model was built, which incorporated the computed rate coefficients for NH 2 + C 3 H 8 reactions. The importance of NH 2 + C 3 H 8 reactions in predicting the combustion behavior of NH 3 /C 3 H 8 blends was demonstrated by kinetic modeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2010

Oxy-combustion of pulverized coal : modeling of char-combustion kinetics.

In this study, char combustion of pulverized coal under oxy-fuel combustion conditions was investigated on the basis of experimentally observed temperature-size characteristics and corresponding predictions of numerical simulations. Using a combustion-driven entrained flow reactor equipped with an optical particle-sizing pyrometer, combustion characteristics (particle temperatures and apparent size) of pulverized coal char particles was determined for combustion in both reduced oxygen and oxygen-enriched atmospheres with either a N{sub 2} or CO{sub 2} bath gas. The two coals investigated were a low-sulfur, high-volatile bituminous coal (Utah Skyline) and a low-sulfur subbituminous coal (North Antelope), both size-classified to 75-106 {micro}m. A particular focus of this study lies in the analysis of the predictive modeling capabilities of simplified models that capture char combustion characteristics but exhibit the lowest possible complexity and thus facilitate incorporation in existing computational fluid dynamics (CFD) simulation codes. For this purpose, char consumption characteristics were calculated for char particles in the size range 10-200 {micro}m using (1) single-film, apparent kinetic models with a chemically 'frozen' boundary layer, and (2) a reacting porous particle model with detailed gas-phase kinetics and three separate heterogeneous reaction mechanisms of char-oxidation and gasification. A comparison of model results with experimental data suggests that single-film models with reaction orders between 0.5 and 1 with respect to the surface oxygen partial pressure may be capable of adequately predicting the temperature-size characteristics of char consumption, provided heterogeneous (steam and CO{sub 2}) gasification reactions are accounted for.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2011

COMSOL-based Nuclear Reactor Kinetics Studies at the HFIR

The computational ability to accurately predict the dynamic behavior of a nuclear reactor core in response to reactivity-induced perturbations is an important subject in reactor physics. Space-time and point kinetics methodologies were developed for the purpose of studying the transient-induced behavior of the High Flux Isotope Reactor s (HFIR) compact core. The space-time simulations employed the three-energy-group neutron diffusion equations, and transients initiated by control cylinder and hydraulic tube rabbit ejections were studied. The work presented here is the first step towards creating a comprehensive multiphysics methodology for studying the dynamic behavior of the HFIR core during reactivity perturbations. The results of these studies show that point kinetics is adequate for small perturbations in which the power distribution is assumed to be time-independent, but space-time methods must be utilized to determine localized effects.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2012

On fast reactor kinetics studies

The results and the program of fast reactor core time and space kinetics experiments performed and planned to be performed at the IPPE critical facility is presented. The TIMER code was taken as computation support of the experimental work, which allows transient equations to be solved in 3-D geometry with multi-group diffusion approximation. The number of delayed neutron groups varies from 6 to 8. The code implements the solution of both transient neutron transfer problems: a direct one, where neutron flux density and its derivatives, such as reactor power, etc, are determined at each time step, and an inverse one for the point kinetics equation form, where such a parameter as reactivity is determined with a well-known reactor power time variation function. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2017

Reactivity Worth Measurement of Control Rods of CFBR-II with Inverse Kinetics Method

CFBR-II is a Godiva type metal HEU fast burst reactor. Reactivity adjustment of the reactor depends on three metal HEU rods (CPI, CP2 and CP3), which have positive reactivity worth. Reactivity effectiveness curves of the three rods are important to safe operation and control of CFBR-I. To measure the reactivity, two different techniques were used: the asymptotic period method (APM) and the inverse kinetic method(IKM). The APM is the most common used method on fast burst reactor, which measured the asymptotic power period then determined reactivity with the in-hour equation. This method only works for positive periods (super criticality state). The IKM can measured continuously reactivity changes by analyzing the variation of reactor power level with the inverse kinetic equation, which works for both subcritical and super critical state. We will mainly discuss how to measure reactivity effectiveness curves of control rods by the IKM.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Operando Neutron Imaging of Lithium Flux and Gradient Cathode Design for Enhanced Kinetics in High‐Loading All‐Solid‐State Li─S Batteries

All-solid-state Li–sulfur batteries (ASSLSBs) are considered promising candidates for next-generation energy storage owing to their inherent safety, high energy density, and abundant sulfur resources. However, slow redox kinetics greatly limit sulfur utilization during solid-solid sulfur reactions, leading to significant challenges to achieve efficient performance in high-mass-loading ASSLSBs. Here, operando neutron image is employed to directly visualize, for the first time, that sluggish Li + transport kinetics and the uneven distribution of Li + during cathodic reactions are critical factors limiting sulfur conversion. To address this issue, gradient cathode architectures comprising three and five layers are designed, in which catholyte concentrations are strategically varied to optimize Li-ion flux and enhance ionic conductivity of the whole composite cathode electrode. Operando neutron imaging distinctly visualizes and confirms that three-layer gradient approach significantly enhances Li-ion mobility, resulting in more uniform redox reactions and greatly improved sulfur utilization compared to traditional non-gradient structures. Consequently, the three-layer gradient cathode achieves superior rate performance and reduced electrode polarization at high sulfur mass loadings of 4.5 and 6.0 mg cm −2 . Furthermore, the applicability and scalability of this design are demonstrated in a five-layer gradient cathode architecture, achieving an impressive discharge specific capacity increase from 656 mAh g −1 (three-layer gradient) to 1232 mAh g −1 at 1/20 C for ultra-high sulfur loading of 7.5 mg cm −2 . In conclusion, this innovative gradient cathode design offers substantial advancements in understanding and overcoming Li-ion transport limitations, paving the way toward practical, high-energy-density ASSLSBs.

25 ENERGY STORAGE↗
DOE OSTI2019

In Situ Optical Absorption Studies of Point Defect Kinetics and Thermodynamics in Oxide Thin Films

The authors discuss the use of in situ optical absorption to probe point defect equilibria and kinetics in oxides, with particular attention to thin films and high-temperature measurements evaluating changes in oxygen content. The introduction notes the effect of point defects on oxide behavior, including differences in thin films versus bulk materials, and describes methods to evaluate point defect equilibria and kinetics; advantages of optical absorption among these methods are highlighted. Section 2 provides an overview of how optical absorption and point defect concentrations are related, including various possible structural and electronic origins of defect-mediated absorption changes corresponding to oxygen content changes. Section 3 traces the development of historical understanding of optical absorption in nonstoichiometric oxides and emergence of thin film applications and measurement approaches that resulted. Section 4 details the procedure for determining surface exchange coefficients from optical transmission relaxation measurements and provides specific examples of how this approach uniquely has enabled new insights into thin film surface exchange behavior with and without current collectors. Section 5 provides examples of optically derived diffusivity measurements and comparisons of bulk and thin film defect equilibria. Section 7 outlines potential opportunities and future developments in this area, and Section 7 concludes the manuscript.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Enantioselective Kinetic Resolution/Desymmetrization of Para</em-Quinols: A Case Study in Boronic-Acid-Directed Phosphoric Acid Catalysis

A chiral phosphoric acid-catalyzed kinetic resolution and desymmetrization of para-quinols operating via oxa-Michael addition was developed and subsequently subjected to mechanistic study. Good to excellent s-factors/enantioselectivities were obtained over a broad range of substrates. Kinetic studies were performed, and DFT studies favor a hydrogen bonding activation mode. The mechanistic studies provide insights to previously reported chiral anion phase transfer reactions involving chiral phosphate catalysts in combination with boronic acids.

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

Toward Higher Voltage Solid-State Batteries by Metastability and Kinetic Stability Design

The energy density of battery systems is limited largely by the electrochemical window of the electrolyte. Here, the combined thermodynamic and kinetic effects of mechanically induced metastability are shown to greatly widen the operational voltage window of solid-state batteries based on ceramic-sulfide electrolytes. Solid electrolyte voltage stability up to 10 V is achieved with minimal degradation, far beyond the capability of organic liquid electrolytes. Furthermore, combined experiment, ab initio computation, and theoretical modeling identify the nature of mechanically constrained Li 10 GeP 2 S 12 decomposition both within the bulk and at interfaces with cathode materials at very high voltages. Previously unclear kinetic processes are identified that, when properly implemented, can potentially allow solid-state full cells with remarkably high operational voltages.

25 ENERGY STORAGE↗
DOE OSTI2019

Reduction Kinetics of Perovskite Oxides for Selective Hydrogen Combustion in the Context of Olefin Production

Chemical looping represents a novel approach for generating light olefins in which thermal cracking or catalytic dehydrogenation is coupled with selective hydrogen combustion (SHC) by a metal oxide redox catalyst, which enables autothermal operation, increased per-pass conversion, and greater-than-equilibrium yields. Recent studies indicate that Na 2 WO 4 -promoted perovskite oxides are effective redox catalysts with high olefin selectivity. Herein, kinetic parameters, rates, and reaction models for the reduction of unpromoted and Na 2 WO 4 -promoted CaMnO 3 redox catalysts by H 2 , C 2 H 4 , and C 2 H 6 , is reported. Reduction rates of CaMnO 3 under ethylene and ethane are significantly lower than under H 2 . Additionally, model fitting of reduction kinetics show good agreement with reaction order–controlled models for CaMnO 3 reduction and predict greater oxygen site dependence and higher activation energy for CaMnO 3 reduction by C 2 H 4 as compared with H 2 . Avrami–Erofe'ev nucleation and growth models provide the best fit to the reduction of Na 2 WO 4 /CaMnO 3 in H 2 and in C 2 H 4 . After Na 2 WO 4 promotion, the reduction rate of CaMnO 3 is three orders of magnitude lower in ethylene in comparison to hydrogen, consistent with its superior selectivity to hydrogen combustion. The models developed can be applied toward reactor design and optimization in the context of enhanced olefin production via SHC under a cyclic redox scheme.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Contrasting Chemical Kinetic Parameters for Near In‐Service‐Temperature Aging and High‐Temperature Thermal Decomposition of Triaminotrinitrobenzene Formulations

Triaminotrinitrobenzene-based high explosives such as LX-17 offer high energy density and exceptional safety, yet their long-term aging behavior at low temperatures remains poorly understood. In this study, several legacy and new production lots of LX-17 were subjected to accelerated aging experiments below 100°C, during which the formation rate of the initial degradation product, monofurazan (F1), was monitored. Kinetic analysis was performed using a sample-age-aware computational approach, yielding activation energy estimates of 82–91 kJ mol −1 for the low-temperature initiation step—markedly lower than the ∼200 kJ mol −1 associated with high-temperature thermal decomposition. Extrapolation from established cookoff models supports the conclusion that the dominant degradation mechanism at low temperatures differs from that at high temperatures. In conclusion, our results provide a unified kinetic framework that bridges the gap between in-service conditions and high-temperature damage.

Chemistry - Chemical explosives↗
DOE OSTI2019

Kinetic Simulations of Cu Doping in Chlorinated CdSeTe PV Absorbers

This paper reports on 1D kinetic modeling of p-type doping formation in Cu-doped chlorinated CdSeTe photovoltaic (PV) absorbers with graded Se profiles. Following the recent progress in kinetic simulations of the defect chemistry in stoichiometric CdTe films, this work extends simulation capabilities to a domain of semiconductor alloy films with graded stoichiometries. The defect formation energies and ionization levels, as well as the diffusion and reaction barriers used in the reaction-diffusion equations are calculated from the first principles. A new formalism is employed to account for the uncertainty of the defect formation energies in semiconductor alloys caused by unknown local surrounding. Finally, the developed methodology is used to model a practical fabrication process of p-type doping formation in graded CdSeTe absorbers and to study the effect of alloy stoichiometry on the doping activation.

14 SOLAR ENERGY↗