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Results for “Kinetic Modelling”

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 973 records · Page 54
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Quantitative kinetic rules for plastic strain-induced α - ω phase transformation in Zr under high pressure

Plastic strain-induced phase transformations (PTs) and chemical reactions under high pressure are broadly spread in modern technologies, friction and wear, geophysics, and astrogeology. However, because of very heterogeneous fields of plastic strain $E$ p and stress σ tensors and volume fraction c of phases in a sample compressed in a diamond anvil cell (DAC) and impossibility of measurements of σ and $E$ p , there are no strict kinetic equations for them. Here, we develop a kinetic model, finite element method (FEM) approach, and combined FEM-experimental approaches to determine all fields in strongly plastically predeformed Zr compressed in DAC, and specific kinetic equation for α-ω PT consistent with experimental data for the entire sample. Since all fields in the sample are very heterogeneous, data are obtained for numerous complex 7D paths in the space of 3 components of the plastic strain tensor and 4 components of the stress tensor. Kinetic equation depends on accumulated plastic strain (instead of time) and pressure and is independent of plastic strain and deviatoric stress tensors, i.e., it can be applied for various above processes. Our results initiate kinetic studies of strain-induced PTs and provide efforts toward more comprehensive understanding of material behavior in extreme conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2022

CO 2 methanation reaction pathways over unpromoted and NaNO 3 -promoted Ru/Al 2 O 3 catalysts

Catalytic CO 2 sorbents, materials that adsorb and pre-concentrate CO 2 on the catalyst surface prior to subsequent conversion, are becoming important materials in CO 2 capture and utilization. In this work, a prototypical CO 2 methanation catalyst – Ru/Al 2 O 3 – and a related catalytic sorbent – NaNO 3 /Ru/Al 2 O 3 – are used for CO 2 methanation in flowing hydrogen in a fixed bed reactor at temperatures ranging from 220 to 280 °C. Activation energies for the NaNO 3 /Ru/Al 2 O 3 material are slightly higher than unpromoted Ru/Al 2 O 3 catalysts, and the reaction orders vary more significantly. In situ IR spectroscopy and steady-state isotopic kinetic analysis (SSITKA) using in situ IR/MS spectroscopy show that bicarbonate and linear carbonyl species are the likely reaction intermediates over unpromoted Ru/Al 2 O 3 , while bidentate carbonate, formate and linear carbonyl species are among likely reaction intermediates over NaNO 3 /Ru/Al 2 O 3 . Rate laws consistent with the obtained experimental data are proposed after kinetic modeling of multiple plausible reaction pathways. In conclusion, results suggest that the pathway over the NaNO 3 /Ru/Al 2 O 3 catalyst likely has an additional kinetically relevant irreversible step in the CO 2 methanation reaction pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

High-Pressure Turbulent Flame Speeds and Chemical Kinetics of Syngas Blends with and without Impurities

This Final Report documents the entire four years of the project, from October 1, 2013 through September 30, 2017. This project was concerned with the chemical kinetics of fuel blends with high-hydrogen content in the presence of impurities. Emphasis was also on the design and construction of a new, high-pressure turbulent flame speed facility and the use of ignition delay times and flame speeds to elucidate the diluent and impurity effects on the fuel chemistry at gas turbine engine conditions and to also validate the chemical kinetics models. The project was divided into five primary tasks: 1) Project Management and Program Planning; 2) Turbulent Flame Speed Measurements at Atmospheric Pressure; 3) Experiments and Kinetics of Syngas Blends with Impurities; 4) Design and Construction of a High-Pressure Turbulent Flame Speed Facility; and 5) High-Pressure Turbulent Flame Speed Measurements. Details on the execution and results of each of these tasks are provided in the main report.

08 HYDROGEN↗
DOE OSTI2017

Role of Hydrogen Bonding in Photoinduced Electron-Proton Transfer from Phenols to a Polypyridine Ru Complex with a Proton-Accepting Ligand

Electron-proton transfer, EPT, from phenols to a triplet MLCT-excited Ru polypyridine complex containing an uncoordinated nitrogen site, 1(T), can be described by a kinetic model that accounts for the H-bonding of 1(T) to phenol, 1(T) to solvent, and phenol to solvent. The latter plays a major role in the kinetic solvent effect and commonly precludes simultaneous determination of the EPT rate constant and 1(T)-phenol H-bonding constant. A number of these quantities previously reported for similar systems are shown to be in error due to an inconsistent data analysis. In conclusion, control experiments replacing either 1(T) by its structural isomer with a sterically screened nitrogen site or phenol by its H-bonding surrogate, trifluoroethanol, and the observation of negative activation enthalpies for the overall reactions between 1(T) and phenols lend support to the proposed model and provide evidence for the formation of a precursor H-bonded complex between the reactants, which is a prerequisite for EPT.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Reduced entropic model for studies of multidimensional nonlocal transport in high-energy-density plasmas

Hydrodynamic simulations of high-energy-density plasmas require a detailed description of energy fluxes. For low and intermediate atomic number materials, the leading mechanism is the electron transport, which may be a nonlocal phenomenon requiring a kinetic modeling. In this paper, we present and test the results of a nonlocal model based on the first angular moments of a simplified Fokker-Planck equation. This multidimensional model is closed thanks to an entropic relation (the Boltzman H-theorem). It provides a better description of the electron distribution function, thus enabling studies of small scale kinetic effects within the hydrodynamic framework. Examples of instabilities of electron plasma and ion-acoustic waves, driven by the heat flux, are presented and compared with the classical formula.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2019

The kinetic study of excited singlet oxygen atom O( 1 D) reactions with acetylene

Understanding the multi-channel dynamics of O( 1 D) reactions with unsaturated hydrocarbon molecules in low temperature reaction kinetics is critically important in stratospheric chemistry, plasma chemistry, plasma assisted fuel reforming, materials synthesis, and plasma assisted combustion. A photolysis flow reactor coupled with highly selective mid-infrared Faraday Rotation Spectroscopy (FRS) and direct ultraviolet-infrared (UV-IR) absorption spectroscopy (DAS) techniques was developed for the first time to study the multi-channel dynamics of excited singlet oxygen atom O( 1 D) reactions with C 2 H 2 and the kinetics of subsequent reactions. Time-resolved species concentrations of OH, HO 2 and H 2 O were obtained and used to develop a validated kinetic model of O(1D) reactions with C 2 H 2 . The branching ratios of O( 1 D) reaction with C 2 H 2 and subsequent HO 2 kinetics were also quantified. It is found that, contrary to O( 1 D) reactions with saturated alkanes, OH formation via direct H abstraction by O( 1 D) is negligible. The results revealed that two chain-branching and propagation reactions via direct O( 1 D) insertion are the major pathways for radical production. The present study clearly demonstrated the advantage of radical detection and kinetic studies using FRS in the effective suppression of absorption interference from non-paramagnetic hydrocarbons.

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

High-pressure ignition delay time measurements of a four-component gasoline surrogate and its high-level blends with ethanol and methyl acetate

Ignition delay times of a gasoline surrogate (iso-octane/toluene/n-heptane/1-hexene at 55/25/15/5% by liquid volume, developed in McCormick et al. 2017) with high-level bioblendstock-gasoline surrogate blends (50% and 85% biofuel by liquid volume of each ethanol and methyl acetate) were collected behind reflected shock waves. Post-reflected-shock temperatures ranged from 968 to 1361 K at pressures of about 4, 10, 25, and 50 atm. Data were collected for real fuel–air mixtures at fuel lean and stoichiometric conditions (φ = 0.5, 1.0) with focus on the more-practical, fuel-lean conditions. Ignition delay times were measured from OH* chemiluminescence around 307 nm using an endwall diagnostic. The RON and MON of the surrogate were 90.3 and 84.7, respectively. Ethanol was chosen due to its wide use in flex-fuel vehicles and availability, while also providing an increased octane rating. Methyl acetate was chosen for its especially high octane rating to investigate the effect of an extreme case. To validate the gasoline surrogate, the data are compared to real gasoline (RD387) and several gasoline surrogate experiments from the literature. Using the wide range of pressures studied, the gasoline surrogate’s pressure dependence was quantified to account for test-to-test variations using regression analysis. Similarly, a global correlation for gasoline and its surrogates was developed using all available data from the literature. Two modern chemical kinetics models targeting gasoline and its surrogates are compared to the ignition delay time measurements. These new high-pressure, high-bioblendstock concentration tests provide required chemical kinetic data for optimizing fuel and engine design.

42 ENGINEERING↗
DOE OSTI2026

Pressure-dependent kinetics of cyclopentene consumption

Recent experiments have uncovered deficiencies in the ability of current kinetic models for cyclopentane combustion to predict species profiles as a function of O2 concentration. One likely source of these discrepancies flows from the limited availability of relevant kinetic data for key functionalized intermediates, requiring the use of distant analogies to estimate their rates. This work fills this gap for cyclopentene, the most prominent C5 intermediate in low-temperature cyclopentane combustion. Ab initio transition-state-theory based master equation methods are used to calculate pressure-dependent rate constants across four potential energy surfaces (C5H8 + OH, C5H8 + HO2, C5H7, and C5H7 + O2). Potential energy surfaces are characterized at the CCSD(T)-F12/cc-pVDZ-F12//revDSD-PBEP86-D3BJ/def2-TZVPP level of theory. Pressure-dependent rate constants and branching fractions are determined via 1D master equation calculations. The results are used to analyze the competition for radicals between cyclopentene and cyclopentane in the intermediate temperature region, and to identify the dominant pathways flowing from these initiation channels. On the OH initiation surface, we find good agreement with recently published experimental rate constants at high temperature, and we elucidate the complex temperature dependence below 800 K, where 𝜋𝜋 addition becomes prominent. On the HO2 initiation surface, we find an interesting alternative route to bicyclic ether formation via well-skipping over the HO2 adduct well. On the cyclopentenyl radical surface, the major product is cyclopentadiene plus H. On the cyclopentenyl + O2 surface, we find that resonance stabilization largely prevents the allylic radical from undergoing oxidation, whereas the alkylic radical has a somewhat elevated propensity for oxidation pathways relative to cyclopentyl.

ab initio calculations↗
DOE OSTI2022

Large thermal hysteresis in a single-phase NiTiNb shape memory alloy

Large thermal hysteresis ($T$ hys ) is favorable in shape memory alloys (SMAs) because it renders wide service and storage temperature range of the SMA-made parts. In this letter, we show that large intrinsic $T$ hys up to 100 K is achieved in a low Nb content (2 at.%), β-Nb-free and single-phase NiTiNb SMA fabricated by casting, forging, wire-drawing and annealing. Such a large $T$ hys is comparable to that of the widely used dual-phase NiTiNb SMAs in which high Nb content and β-Nb are required. By exploiting the grain-size-dependence of $T$ hys in our single-phase NiTiNb SMA and that in an equiatomic NiTi SMA, we attribute the large $T$ hys to the enhanced kinetic resistance of transformation by the small grains. In conclusion, the connection between the $T$ hys and the kinetic resistance is demonstrated by a modified dislocation-based kinetic model.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Resolving Dynamics in the Ensemble: Finding Paths through Intermediate States and Disordered Protein Structures

Proteins have been found to inhabit a diverse set of three-dimensional structures. The dynamics that govern protein interconversion between structures happen over a wide range of time scales-picoseconds to seconds. Our understanding of protein functions and dynamics is largely reliant upon our ability to elucidate physically populated structures. From an experimental structural characterization perspective, we are often limited to measuring the ensemble-averaged structure both in the steady-state and time-resolved regimes. Generating kinetic models and understanding protein structure–function relationships require atomistic knowledge of the populated states in the ensemble. Here, we present ensemble refinement methodologies that integrate time-resolved experimental signals with molecular dynamics models. We first discuss integration of experimental structural restraints to molecular models in disordered protein systems that adhere to the principle of maximum entropy for creating a complete set of ensemble structures. We then propose strategies to find kinetic pathways between the refined structures, using time-resolved inputs to guide molecular dynamics trajectories and the use of inference to generate tailored stimuli to prepare a desired ensemble of protein states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Ultrafast Spectroscopic Investigation of Energy Transfer in Site-Directed Mutants of the Fenna–Matthews–Olson (FMO) Antenna Complex from Chlorobaculum tepidum

Ultrafast transient absorption (TA) and time-resolved fluorescence (TRF) spectroscopic studies were performed on several mutants of the bacteriochlorophyll (BChl) a-containing Fenna–Matthews–Olson (FMO) complex from the green sulfur bacterium Chlorobaculum tepidum. These mutants were generated to perturb a particular BChl a site and determine its effects on the optical spectroscopic properties of the pigment–protein complex. Measurements conducted at 77 K under both oxidizing and reducing conditions revealed changes in the dynamics of the various spectral components as compared to the data set from wild-type FMO. TRF results show that under reducing conditions all FMO samples decay with a similar lifetime in the ~2 ns range. The oxidized samples revealed varying fluorescence lifetimes of the terminal BChl a emitter, considerably shorter than those recorded for the reduced samples, indicating that the quenching mechanism in wild-type FMO is still present in the mutants. Global fitting of TA data yielded similar overall results, and in addition, the lifetimes of early decaying components were determined. Target analyses of TA data for select FMO samples generated kinetic models that better simulate the TA data. Here, a comparison of the lifetime of excitonic components for all samples reveals that the mutations affect mainly the early kinetic components, but not that of the lowest energy exciton, which reflects the flexibility of energy transfer in FMO.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Stiff neural ordinary differential equations

Neural Ordinary Differential Equations (ODEs) are a promising approach to learn dynamical models from time-series data in science and engineering applications. This work aims at learning neural ODEs for stiff systems, which are usually raised from chemical kinetic modeling in chemical and biological systems. We first show the challenges of learning neural ODEs in the classical stiff ODE systems of Robertson’s problem and propose techniques to mitigate the challenges associated with scale separations in stiff systems. We then present successful demonstrations in stiff systems of Robertson’s problem and an air pollution problem. The demonstrations show that the usage of deep networks with rectified activations, proper scaling of the network outputs as well as loss functions, and stabilized gradient calculations are the key techniques enabling the learning of stiff neural ODEs. The success of learning stiff neural ODEs opens up possibilities of using neural ODEs in applications with widely varying time-scales, such as chemical dynamics in energy conversion, environmental engineering, and life sciences.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2016

Femtosecond, two-photon-absorption, laser-induced-fluorescence (fs-TALIF) imaging of atomic hydrogen and oxygen in non-equilibrium plasmas

Here, Femtosecond, two-photon-absorption laser-induced fluorescence (fs-TALIF) is employed to measure space- and time-resolved distributions of atomic hydrogen and oxygen in moderate-pressure, non-equilibrium, nanosecond-duration pulsed-discharge plasmas. Temporally and spatially resolved hydrogen and oxygen TALIF images are obtained over a range of low-temperature plasmas in mixtures of helium and argon at 100 Torr total pressure. The high-peak-intensity, low-average-energy fs pulses combined with the increased spectral bandwidth compared to traditional ns-duration laser pulses provide a large number of photon pairs that are responsible for the two-photon excitation, which results in an enhanced TALIF signal. Krypton and xenon TALIF are used for quantitative calibration of the hydrogen and oxygen concentrations, respectively, with similar excitation schemes being employed. This enables 2D collection of atomic-hydrogen and -oxygen TALIF signals with absolute number densities ranging from 2 × 10 12 cm -3 to 6 × 10 15 cm -3 and 1×10 13 cm -3 to 3 × 10 16 cm -3 , respectively. These 2D images are the first application of TALIF imaging in moderate-pressure plasma discharges. 1D self-consistent modeling predictions show agreement with experimental results within the estimated experimental error of 25%. The present results can be used to further the development of higher fidelity kinetic models while quantifying plasma-source characteristics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Possible acceleration of cosmic rays in a rotating system: Uehling-Uhlenbeck model

We illustrate the possible acceleration of cosmic rays passing through a kind of amplification channel (via diffusion modes of propagating plane-wave fronts) induced by a rotating system. Our analysis is mainly based on the quantum discrete kinetic model (considering a discrete Uehling-Uhlenbeck collision term), which has been used to study the propagation of plane (e.g., acoustic) waves in a system of rotating gases.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Wire directed energy deposition of steel-aluminum structures using cold metal transfer process

In this study, a sharp transition from 316L stainless steel to 4043 aluminum alloy was fabricated using wire directed energy deposition (DED) via the cold metal transfer (CMT) process. The CMT process with its inherently low heat input, led to a significant reduction in intermetallic thickness at the bi-metallic interface compared to blown powder DED technique reported in the literature resulting in superior properties when compared to those of dissimilar steel-aluminum welds. Thermo-kinetic modeling confirmed that the intermetallic formation is through a classical nucleation and growth mechanism, and the fraction and thickness can be controlled by adjusting CMT process parameters to kinetically arrest or minimize the intermetallic formation. These findings underscore the efficacy of CMT-based wire DED for fabrication of steel-aluminum bi-metallic structures.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Effect of the abolition of intersubunit salt bridges on allosteric protein structural dynamics

A salt bridge, one of the representative structural factors established by non-covalent interactions, plays a crucial role in stabilizing the structure and regulating the protein function, but its role in dynamic processes has been elusive. Here, to scrutinize the structural and functional roles of the salt bridge in the process of performing the protein function, we investigated the effects of salt bridges on the allosteric structural transition of homodimeric hemoglobin (HbI) by applying time-resolved X-ray solution scattering (TRXSS) to the K30D mutant, in which the interfacial salt bridges of the wild type (WT) are abolished. The TRXSS data of K30D are consistent with the kinetic model that requires one monomer intermediate in addition to three structurally distinct dimer intermediates (I 1 , I 2 , and I 3 ) observed in WT and other mutants. The kinetic and structural analyses show that K30D has an accelerated biphasic transition from I 2 to I 3 by more than nine times compared to WT and lacks significant structural changes in the transition from R-like I 2 to T-like I 3 observed in WT, unveiling that the loss of the salt bridges interrupts the R–T allosteric transition of HbI. Besides, the correlation between the bimolecular CO recombination rates in K30D, WT, and other mutants reveals that the bimolecular CO recombination is abnormally decelerated in K30D, indicating that the salt bridges also affect the cooperative ligand binding in HbI. These comparisons of the structural dynamics and kinetics of K30D and WT show that the interfacial salt bridges not only assist the physical connection of two subunits but also play a critical role in the global structural signal transduction of one subunit to the other subunit via a series of well-organized structural transitions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Temperature and density dependence of Kr L-shell spectrum in hot dense plasmas

Kr L-shell spectroscopy modeling results are discussed in this paper, focusing on the n = 4 to n = 2 line transitions of Be- and Li-like Kr ions. Collisional radiative atomic kinetic and Stark-broadened spectral line shape calculations show electron temperature Te and density ne sensitivity in the spectrum. The combination of the Te dependence due to the relative intensity of Be-like to Li-like line emissions in the range from 1.5 to 3 keV and the ne sensitivity from the Stark broadening effect on the line shapes in the range from 5×1023 to 2×1024/ cc results in a spectrum that can be employed to diagnose Te and ne. Two different collisional radiative atomic kinetic models i.e., Prismspect [J. J. MacFarlane, et al., Int. Fusion Sci. Appl. Conf. Proc. 457 (2003)] and ABAKO [Florido, et al., PRE, 80, 056402 (2009)] produce similar results in level populations and spectra. In x-ray spectroscopy of implosion cores, this Kr L-shell spectrum may prove useful in an intermediate Te range in which Ar is too ionized for its K-shell to be of diagnostic value and Kr is not ionized enough for its K-shell emission to be useful.

Physics↗