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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 1,243 records · Page 69
All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

Advances in Studies of Electrode Kinetics and Mass Transport in AMTEC Cells

Previous work reported from JPL has included characterization of electrode kinetics and alkali atom transport from electrodes including Mo, W, WRh x (Mn), in sodium AMTEC cells and vapor exposure cells; and Mo in potassium vapor exposure cells. These studies were generally performed in cells with small area electrodes (about 1 to 5 cm 2 ), and device geometry had little effect on transport. Alkali metal diffusion coefficients through these electrodes have been characterized, and approximate surface diffusion coefficients were derived in cases of activated transport. A basic model of electrode kinetics and transport at the alkali metal vapor/pourous metal electrode/alkali beta"-alumina solid electrolyte (BASE) three phase boundary has been proposed which accounts for electrochemical reaction rates with a collision frequency near the three phase boundary and tunneling from the porous electrode partially covered with adsorbed alkali metal atoms. The small electrode effect in AMTEC cells has been discussed in several papers, but quantitative investigations have described only the overall effect and the important contribution of electrolyte resistance. The quantitative characterization of transport losses in cells with large area electrodes has been limited to simulations of large area electrode effects, or characterization of transport losses from large area electrodes with significant longitudinal temperature gradients. This paper describes new investigations of electrochemical kinetics and transport, with four 14.4 cm 2 WPt 3.5 electrodes, including the influence of electrode size on the mass transport loss in the AMTEC cell. These electrodes exhibit very slow sintering, as well as excellent sodium transport properties, making them attractive candidates for AMTEC power conversion use. However, the facile sodium transport in WPt 3.5 electrodes makes characterization of the transport process difficult.

electrode↗
DOE OSTI2010

The response of the HMX-based material PBXN-9 to thermal insults: thermal decomposition kinetics and morphological changes

PBXN-9, an HMX-formulation, is thermally damaged and thermally decomposed in order to determine the morphological changes and decomposition kinetics that occur in the material after mild to moderate heating. The material and its constituents were decomposed using standard thermal analysis techniques (DSC and TGA) and the decomposition kinetics are reported using different kinetic models. Pressed parts and prill were thermally damaged, i.e. heated to temperatures that resulted in material changes but did not result in significant decomposition or explosion, and analyzed. In general, the thermally damaged samples showed a significant increase in porosity and decrease in density and a small amount of weight loss. These PBXN-9 samples appear to sustain more thermal damage than similar HMX-Viton A formulations and the most likely reasons are the decomposition/evaporation of a volatile plasticizer and a polymorphic transition of the HMX from {beta} to {delta} phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

A model for the adsorption kinetics of CO2 on amine-impregnated mesoporous sorbents in the presence of water

A simple model for the adsorption kinetics carbon dioxide onto an amine-impregnated mesoporous sorbent, NETL-32D, was developed. The model was developed based on the mechanistic pathways believed to be responsible for the uptake of CO2 by the sorbent, including interactions with H2O. The model consists of quasi-ideal expressions to describe the kinetics of three reactions responsible for the uptake of CO2 and H2O by the sorbent. The model was fitted to experimental data obtained from thermogravimetric analysis and found to be a reasonable representation of the observed equilibrium and kinetics. The model is able to predict the increased uptake due to the interaction between CO2 and H2O in the sorbent. The heat of reaction predicted by the model for the uptake of CO2 in dry conditions of -65 kJ/mol compares well to the value of -67 kJ/mol obtained via calorimetry for similar sorbents.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2011

Effect of Oxygen Gas Pressure on the Kinetics of Alumina Film Growth During the Oxidation of Al(111) at Room Temperature

We have studied the effect of oxygen pressure on the self-limiting oxidation of an Al(111) surface at room temperature for oxygen pressures from 1 x 10{sup -8} to 5 Torr. Using x-ray photoelectron spectroscopy measurements, we monitor the oxidation kinetics and the oxide film thickness for different oxidation times and pressures. After a rapid initial growth stage, the oxide film reaches a saturated thickness, which depends on the oxygen pressure. The kinetic potential, oxide growth rate, oxide film limiting thickness, and the density of oxygen anions on the oxide surface are determined by the measured oxidation kinetics. These quantities show a Langmuir isotherm dependence on the oxygen gas pressure.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Fuel Properties and Kinetics

The Co-Optimization of Fuels and Engines (CoOptima) program is focused on a two-pronged approach to develop new, lower net-carbon fuels and advanced engine technologies in tandem. This effort brings nine national labs and several university and industry partners together to simultaneously identify new fuel candidates and to further engine technology development in the light-, medium-, and heavy-duty vehicle sectors with a focus on fuel economy and emission reduction. The fuel properties and kinetics project is aimed at achieving a better understanding of fuel property kinetics and how they impact engine performance such that more efficient and lower emitting engines can be made a reality. Several promising biofuel candidates were identified through tiered screening approaches and were evaluated utilizing unique bench-scale measurement techniques. Kinetic models were developed to describe autoignition and soot pre-cursor formation mechanisms to identify the most promising candidates that advanced various combustion strategies.

ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2012

Comparison of direct and quasi-static methods for neutron kinetic calculations with the EDF R and D COCAGNE code

Quasi-Static (QS) methods are quite popular in the reactor physics community and they exhibit two main advantages. First, these methods overcome both the limits of the Point Kinetic (PK) approach and the issues of the computational effort related to the direct discretization of the time-dependent neutron transport equation. Second, QS methods can be implemented in such a way that they can be easily coupled to very different external spatial solvers. In this paper, the results of the coupling between the QS methods developed by Politecnico di Torino and the EDF R and D core code COCAGNE are presented. The goal of these activities is to evaluate the performances of QS methods (in term of computational cost and precision) with respect to the direct kinetic solver (e.g. {theta}-scheme) already available in COCAGNE. Additionally, they allow to perform an extensive cross-validation of different kinetic models (QS and direct methods). (authors)

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2012

Comparison of gasification kinetics parameters of different types of nuclear graphite

A chemical-reaction kinetics model of nuclear graphite gasification has recently been developed and successfully validated with gasification rate measurements for nuclear graphite grades of IG-110, IG-430, NBG-18 and NBG-25. The model employs 4 elementary chemical reactions with applicable parameters, including the values and Gaussian-like distributions of the specific activation energies, the pre-exponential coefficients for adsorption of oxygen and desorption of CO and CO{sub 2} gases, and the surface area of free active sites. These parameters are determined from the reported measurements of the total gasification and transient weight loss using a multi-parameter optimization algorithm. The determined chemical kinetics parameters for IG-100 and NB-25 are nearly the same, but slightly different from those for NBG-18 and IG-430. The initial specific area of free active sites is inversely proportional to the square root of the mass or volume of the graphite specimens used in experiments. The recommended chemical kinetics parameters in this paper for these grades of nuclear graphite should be applicable to future safety analysis of high-temperature gas cooled reactors in the unlikely event of a massive air ingress accident. (authors)

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2013

Performance of non-conventional factorization approaches for neutron kinetics

The use of factorization techniques provides a interesting option for the simulation of the time-dependent behavior of nuclear systems with a reduced computational effort. While point kinetics neglects all spatial and spectral effects, quasi-statics and multipoint kinetics allow to produce results with a higher accuracy for transients involving relevant modifications of the neutron distribution. However, in some conditions these methods can not work efficiently. In this paper, we discuss some possible alternative formulations for the factorization process for neutron kinetics, leading to mathematical models of reduced complications that can allow an accurate simulation of transients involving spatial and spectral effects. The performance of these innovative approaches are compared to standard techniques for some test cases, showing the benefits and shortcomings of the method proposed. (authors)

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2016

Derivation of the Point-Kinetics Parameters for the Coupled Reactors

The design of coupled reactors, which provide two distinct spectral zones (fast and thermal), has recently drawn attention because it can provide configurations that could not be met in current thermal neutron test reactors and thus allows versatile irradiation tasks. A coupled reactor core is characterized by the neutron multiplicity of each zone as well as by the coupling between the two zones. It is desired to evaluate the integral point kinetics parameters that characterize the neutron physics of the coupled system. This summary provides a derivation of the equations for evaluating these point kinetics parameters. Following the strong and the weak form of the multigroup diffusion equation, the weak forms for the partial forward and adjoint solutions, each for a particular active region of the reactor core, are derived. These partial solutions are then used to collapse the weak form into the coupled-reactor point kinetics equations with the approximation of equilibrium. It is noted that these parameters are not meant for transient analysis because of the equilibrium approximation. They are rather used for characterizing the coupled system. The derived reactivity equations are then compared with those in Ref. 1. The equations are implemented in Rattlesnake, the INL MOOSE-based radiation transport application for multi-physics simulations. Numerical results are presented for a simple two-group problem. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
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 OSTI2019

Mass Transfer and Reaction Kinetic Enhanced Electrode for High‐Performance Aqueous Flow Batteries

Abstract A scalable and efficient process to modify electrodes with enhanced mass transfer and reaction kinetics is critical for redox flow batteries (RFBs). For the first time, this work introduces electrochemical exfoliation as a surface modification method of graphite felt (GF) to enhance the mass transfer and reaction kinetics in RFBs. Anion intercalation and subsequent gas evolutions at room temperature for one minute expand the graphite layers that increase the electrode surface area. Meanwhile, sufficient oxygen functional groups are introduced to the electrode, resulting in enhanced reaction kinetics and improved hydrophilicity. Further, spin‐polarized density functional theory is employed to reveal the role of oxygen functional groups in accelerating the vanadium redox reaction. Benefitting from sufficient oxygen groups, larger surface area, and superior wettability, the as‐prepared exfoliated GF (E‐GF) shows exceptional electrocatalytic activity with minimized overpotential, higher volumetric capacity, and improved energy efficiency. The redox flow battery assembled with the E‐GF electrode delivers voltage and energy efficiencies of 89.72% and 86.41% at the current density of 100 mA cm −2 , respectively. Remarkably, compared to the traditional GF treatment method, the elimination of the high temperature and long‐time treatment processes make this approach much more energy and time efficient, scalable, and affordable for large‐scale manufacturing.

Mukhopadhyay, Alolika↗
DOE OSTI2022

Investigating Particle Size‐Dependent Redox Kinetics and Charge Distribution in Disordered Rocksalt Cathodes

Abstract Understanding how various redox activities evolve and distribute in disordered rocksalt oxides (DRX) can advance insights into manipulating materials properties for achieving stable, high‐energy batteries. Herein, the authors present how the reaction kinetics and spatial distribution of redox activities are governed by the particle size of DRX materials. The size‐dependent electrochemical performance is attributed to the distinct cationic and anionic reaction kinetics at different sizes, which can be tailored to achieve optimal capacity and stability. Overall, the local charged domains in DRX particles display random heterogeneity caused by the isotropic delithiation pathways. Owing to the kinetic limitation, the micron‐sized particles exhibit a holistic “core‐shell” charge distribution, whereas sub‐micron particles show more uniform redox reactions throughout the particles and ensembles. Sub‐micron DRX particles exhibit increasing anionic redox activities yet inferior cycling stability. In summary, engineering particle size can effectively modulate how cationic and anionic redox activities evolve and distribute in DRX materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

3D‐Printed Structure Boosts the Kinetics and Intrinsic Capacitance of Pseudocapacitive Graphene Aerogels

Abstract The performance of pseudocapacitive electrodes at fast charging rates are typically limited by the slow kinetics of Faradaic reactions and sluggish ion diffusion in the bulk structure. This is particularly problematic for thick electrodes and electrodes highly loaded with active materials. Here, a surface‐functionalized 3D‐printed graphene aerogel (SF‐3D GA) is presented that achieves not only a benchmark areal capacitance of 2195 mF cm −2 at a high current density of 100 mA cm −2 but also an ultrahigh intrinsic capacitance of 309.1 µF cm −2 even at a high mass loading of 12.8 mg cm −2 . Importantly, the kinetic analysis reveals that the capacitance of SF‐3D GA electrode is primarily (93.3%) contributed from fast kinetic processes. This is because the 3D‐printed electrode has an open structure that ensures excellent coverage of functional groups on carbon surface and facilitates the ion accessibility of these surface functional groups even at high current densities and large mass loading/electrode thickness. An asymmetric device assembled with SF‐3D GA as anode and 3D‐printed GA decorated with MnO 2 as cathode achieves a remarkable energy density of 0.65 mWh cm −2 at an ultrahigh power density of 164.5 mW cm −2 , outperforming carbon‐based supercapacitors operated at the same power density.

asymmetric supercapacitors↗
DOE OSTI2020

The Role of Demixing and Crystallization Kinetics on the Stability of Non‐Fullerene Organic Solar Cells

Abstract With power conversion efficiency now over 17%, a long operational lifetime is essential for the successful application of organic solar cells. However, most non‐fullerene acceptors can crystallize and destroy devices, yet the fundamental underlying thermodynamic and kinetic aspects of acceptor crystallization have received limited attention. Here, room‐temperature (RT) diffusion coefficients of 3.4 × 10 −23 and 2.0 × 10 −22 are measured for ITIC‐2Cl and ITIC‐2F, two state‐of‐the‐art non‐fullerene acceptors. The low coefficients are enough to provide for kinetic stabilization of the morphology against demixing at RT. Additionally profound differences in crystallization characteristics are discovered between ITIC‐2F and ITIC‐2Cl. The differences as observed by secondary‐ion mass spectrometry, differential scanning calorimetry (DSC), grazing‐incidence wide‐angle X‐ray scattering, and microscopy can be related directly to device degradation and are attributed to the significantly different nucleation and growth rates, with a difference in the growth rate of a factor of 12 at RT. ITIC‐4F and ITIC‐4Cl exhibit similar characteristics. The results reveal the importance of diffusion coefficients and melting enthalpies in controlling the growth rates, and that differences in halogenation can drastically change crystallization kinetics and device stability. It is furthermore delineated how low nucleation density and large growth rates can be inferred from DSC and microscopy experiments which could be used to guide molecular design for stability.

Hu, Huawei↗
DOE OSTI2022

Unraveling Thermodynamic and Kinetic Contributions to the Stability of Doped Nanocrystalline Alloys using Nanometallic Multilayers

Abstract Targeted doping of grain boundaries is widely pursued as a pathway for combating thermal instabilities in nanocrystalline metals. However, certain dopants predicted to produce grain‐boundary‐segregated nanocrystalline configurations instead form small nanoprecipitates at elevated temperatures that act to kinetically inhibit grain growth. Here, thermodynamic modeling is implemented to select the Mo–Au system for exploring the interplay between thermodynamic and kinetic contributions to nanostructure stability. Using nanoscale multilayers and in situ transmission electron microscopy thermal aging, evolving segregation states and the corresponding phase transitions are mapped with temperature. The microstructure is shown to evolve through a transformation at lower homologous temperatures (<600 °C) where solute atoms cluster and segregate to the grain boundaries, consistent with predictions from thermodynamic models. An increase in temperature to 800 °C is accompanied by coarsening of the grain structure via grain boundary migration but with multiple pinning events uncovered between migrating segments of the grain boundary and local solute clustering. Direct comparison between the thermodynamic predictions and experimental observations of microstructure evolution thus demonstrates a transition from thermodynamically preferred to kinetically inhibited nanocrystalline stability and provides a general framework for decoupling contributions to complex stability transitions while simultaneously targeting a dominant thermal stability regime.

25 ENERGY STORAGE↗
DOE OSTI2022

Proton-Mediated and Ir-Catalyzed Iron/Iron-Oxide Redox Kinetics for Enhanced Rechargeability and Durability of Solid Oxide Iron–Air Battery

Long duration energy storage (LDES) is an economically attractive approach to accelerating clean renewable energy deployment. The newly emerged solid oxide iron–air battery (SOIAB) is intrinsically suited for LDES applications due to its excellent low-rate performance (high-capacity with high efficiency) and use of low-cost and sustainable materials. However, rechargeability and durability of SOIAB are critically limited by the slow kinetics in iron/iron-oxide redox couples. Here the use of combined proton-conducting BaZr 0.4 Ce 0.4 Y 0.1 Yb 0.1 O 3 (BZC4YYb) and reduction-promoting catalyst Ir to address the kinetic issues, is reported. It is shown that, benefiting from the facilitated H + diffusion and boosted FeOx-reduction kinetics, the battery operated under 550 °C, 50% Fe-utilization and 0.2 C, exhibits a discharge specific energy density of 601.9 Wh kg –1 -Fe with a round-trip efficiency (RTE) of 82.9% for 250 h of a cycle duration of 2.5 h. Under 500 °C, 50% Fe-utilization and 0.2 C, the same battery exhibits 520 Wh kg –1 -Fe discharge energy density with an RTE of 61.8% for 500 h. This level of energy storage performance promises that SOIAB is a strong candidate for LDES applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Engineering Thermally Resilient and Kinetically Active Reversible Protonic Ceramic Cells via Interfacial Design

Achieving concurrent fast electrode kinetics and long-term thermo-mechanical durability remains a critical challenge for reversible protonic ceramic electrochemical cells (R-PCECs). Herein, we report an interfacial engineering strategy that integrates a perovs.kite-type PrBaRu0.1Co1.9O5+δ (PBRC) nanoparticle layer onto a PrBa0.5Sr0.5Co1.5Fe0.5O5+δ (PBSCF) substrate (PBRC-PBSCF), together with a modified pellet-assisted sintering approach to fabricate dense BaZr0.4Ce0.4Y0.1Yb0.1O3-δ (BZCYYb4411) electrolytes. The in situ reconstructed heterointerface enhances oxygen reduction/evolution reaction (ORR/OER) kinetics, promotes H2O adsorption/dissociation, and improves steam tolerance, as verified by electrochemical measurements and interfacial microstructural analyses. Density functional theory reveals that Ru-induced electronic modulation at the PBRC-PBSCF interface lowers the energy of oxygen vacancy formation and optimizes the position of the O 2p band center, thereby accelerating oxygen redox kinetics and stabilizing the interface. The resulting R-PCECs deliver an excellent peak power density of 1.112 W cm−2 and an electrolysis current density of −1.257 A cm−2 at 1.3 V in 3% H2O wet air at 600°C, with a reasonable faradaic efficiency. Furthermore, the cells demonstrate excellent stability, sustaining 100 h of thermal cycling (400–600°C, 200°C h−1) in both fuel cell and electrolysis modes, with 600 h of stability in electrolysis mode (600°C, −0.5 to −2 A cm−2).

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2018

Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts

Abstract Catalytic cycles are typically depicted as possessing time‐invariant steps with fixed rates. Yet the true behavior of individual catalysts with respect to time is unknown, hidden by the ensemble averaging inherent to bulk measurements. Evidence is presented for variable chemical kinetics at individual catalysts, with a focus on ring‐opening metathesis polymerization catalyzed by the second‐generation Grubbs’ ruthenium catalyst. Fluorescence microscopy is used to probe the chemical kinetics of the reaction because the technique possesses sufficient sensitivity for the detection of single chemical reactions. Insertion reactions in submicron regions likely occur at groups of many (not single) catalysts, yet not so many that their unique kinetic behavior is ensemble averaged.

Easter, Quinn T.↗