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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Theoretically Informed Kinetics (ThInK): Establishing a modern C 0 -C 3 mechanism for combustion modeling

In contrast to the adage “Models are to be used, not believed”, combustion kinetics models have been intended to be predictive in nature. Theoretical chemical kinetics is now understood to provide a firm foundation for the reaction parameters, thereby facilitating predictive simulations of chemical reactivity, even in regimes that are poorly characterized by chemical kinetic and/or combustion experiments. In this study, we describe a theory-informed kinetics model (ThInK) for small molecule combustion chemistry (H 2 and C 1 – C 3 species) that is based on the prodigious use of theoretical predictions for reaction rate coefficients, thermochemistry, and transport parameters. The distinct features of this kinetics model, which was developed over the course of several decades, are illustrated through simulations of flame propagation and auto-ignition.

Energy transfer↗
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↗
NASA NTRS1994

What can we learn from relaxation measurements of a laser-perturbed atmosphere? A modeling study

The chemical kinetic aspects of a transient increase in OH and HO2 by several orders of magnitude are explored in three model tropospheres. This chemical kinetic modeling effort was undertaken to support the operation of a pump-and-probe LIDAR instrument. A powerful excimer laser pulse perturbs the troposphere after which its relaxation back to steady state is examined by remote sensing, for example by DIAL or LIF. Instead of probing ambient levels of key free radicals, a study of the relaxation kinetics in real time enables chemical mechanistic studies in situ.

Clericetti, Agostino↗
DOE OSTI2024

Probing O 2 -dependence of cyclopentyl reactions via isomer-resolved speciation

Modeling chemical kinetics relevant to low-temperature combustion requires complete description of reactions involving critical species such as hydroperoxyalkyl radicals, Q̇OOH, which undergo competing unimolecular reactions and bimolecular reactions with O 2 . The balance of flux across the two pathways affects rates of chain-branching and depends on temperature, pressure, and oxygen concentration. Accordingly, the influence of [O 2 ] on product formation from alkyl + O 2 reactions and the subsequent fate of Q̇OOH and related products is central to the development of an accurate chemical kinetics mechanism. Furthermore, chemical reactions consuming Q̇OOH-mediated species are often simplified to such a degree that mechanism truncation error (uncertainty derived from incomplete reaction networks) becomes significant.

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

Theoretical and kinetic modeling study of H 2 S pyrolysis

Hydrogen sulfide pyrolysis was investigated theoretically and through chemical kinetic modeling. Reactions on the SHH potential energy surface, primarily S + H 2 (+Ar) ⇌ H 2 S (+ Ar) (R1) and S + H 2 ⇌ SH + H (R6b) were characterized by ab initio calculations. Results for k 1 were in good agreement with experiment, but deviated strongly below 2000 K from values previously used in modeling. Collider efficiencies for H 2 S, S 2 , and N 2 compared to Ar were calculated for R1. Hydrogen sulfide decomposition experiments reported in literature were re-examined in terms of an updated detailed chemical kinetic model. Concentration profiles for the atomic S at high temperature in shock tubes supported the present value of k 1 and served to constrain the rate constants for reaction of S with SH and H 2 S. To explain results from batch and flow reactors, conducted at high H 2 S concentrations in the 900–1400 K range, a very fast rate constant was required for HSS + H ⇌ SH + SH. Under dilute conditions, the gas-phase chemistry was too slow to compete and the decomposition of H 2 S was controlled by loss on the reactor surface.

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

Magnetic resonance insights into the heterogeneous, fractal-like kinetics of chemically recyclable polymers

Moving toward a circular plastics economy is a vital aspect of global resource management. Chemical recycling of plastics ensures that high-value monomers can be recovered from depolymerized plastic waste, thus enabling circular manufacturing. However, to increase chemical recycling throughput in materials recovery facilities, the present understanding of polymer transport, diffusion, swelling, and heterogeneous deconstruction kinetics must be systematized to allow industrial-scale process design, spanning molecular to macroscopic regimes. To develop a framework for designing depolymerization processes, we examined acidolysis of circular polydiketoenamine elastomers. We used magnetic resonance to monitor spatially resolved observables in situ and then evaluated these data with a fractal method that treats nonlinear depolymerization kinetics. This approach delineated the roles played by network architecture and reaction medium on depolymerization outcomes, yielding parameters that facilitate comparisons between bulk processes. These streamlined methods to investigate polymer hydrolysis kinetics portend a general strategy for implementing chemical recycling on an industrial scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

Surrogate Fuel Chemistry from ReaxFF Molecular Dynamics

Reactive molecular dynamics with ReaxFF simulations are used to study the chemistry of four component jet fuel mixtures of n-dodecane, iso-octane, n-propylbenzene, and mesitylene. ReaxFF does not require knowledge of the chemistry a priori providing insight into reactions otherwise not seen in established chemical kinetic mechanisms. The results show that a difference in the local chemical environment can change the fuel decomposition pathways across the surrogate mixtures where the same fuel species are used. These simulations highlight the need to consider cross-chemical interactions in chemical kinetic mechanism development and the importance of resonance stabilized polyaromatic hydrocarbon reactions for soot growth and formation. A method for predicting the threshold sooting index from the carbon species formed at the end of the simulations is established. The results of the simulations are consistent with measurements of the threshold sooting index with the predicted values within 20% of the measured data

Surrogate Fuels↗
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 OSTI2023

Catalyst: Fast and flexible modeling of reaction networks

We introduce Catalyst.jl, a flexible and feature-filled Julia library for modeling and high-performance simulation of chemical reaction networks (CRNs). Catalyst supports simulating stochastic chemical kinetics (jump process), chemical Langevin equation (stochastic differential equation), and reaction rate equation (ordinary differential equation) representations for CRNs. Through comprehensive benchmarks, we demonstrate that Catalyst simulation runtimes are often one to two orders of magnitude faster than other popular tools. More broadly, Catalyst acts as both a domain-specific language and an intermediate representation for symbolically encoding CRN models as Julia-native objects. This enables a pipeline of symbolically specifying, analyzing, and modifying CRNs; converting Catalyst models to symbolic representations of concrete mathematical models; and generating compiled code for numerical solvers. Leveraging ModelingToolkit.jl and Symbolics.jl, Catalyst models can be analyzed, simplified, and compiled into optimized representations for use in numerical solvers. Finally, we demonstrate Catalyst’s broad extensibility and composability by highlighting how it can compose with a variety of Julia libraries, and how existing open-source biological modeling projects have extended its intermediate representation.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1982

Heterogeneous atmospheric chemistry

The present conference on heterogeneous atmospheric chemistry considers such topics concerning clusters, particles and microparticles as common problems in nucleation and growth, chemical kinetics, and catalysis, chemical reactions with aerosols, electron beam studies of natural and anthropogenic microparticles, and structural studies employing molecular beam techniques, as well as such gas-solid interaction topics as photoassisted reactions, catalyzed photolysis, and heterogeneous catalysis. Also discussed are sulfur dioxide absorption, oxidation, and oxidation inhibition in falling drops, sulfur dioxide/water equilibria, the evidence for heterogeneous catalysis in the atmosphere, the importance of heterogeneous processes to tropospheric chemistry, soot-catalyzed atmospheric reactions, and the concentrations and mechanisms of formation of sulfate in the atmospheric boundary layer.

Schryer, D. R.↗
NASA NTRS1990

Kinetics and thermochemistry of polyatomic free radicals: New results and new understandings

An experimental facility for the study of the chemical kinetics of polyatomic free radicals is described which consists of a heatable tubular reactor coupled to a photoionization mass spectrometer. Its use in different kinds of chemical kinetic studies is also discussed. Examples presented include studies of the C2H3 + O2, C2H3 + HC1, CH3 + O, and CH3 + CH3 reactions. The heat of formation of C2H3 was obtained from the results of the study of the C2H3 + HC1 reaction.

Gutman, David↗
NASA NTRS2010

Modeling of Alkane Oxidation Using Constituents and Species

It is currently not possible to perform simulations of turbulent reactive flows due in particular to complex chemistry, which may contain thousands of reactions and hundreds of species. This complex chemistry results in additional differential equations, making the numerical solution of the equation set computationally prohibitive. Reducing the chemical kinetics mathematical description is one of several important goals in turbulent reactive flow modeling. A chemical kinetics reduction model is proposed for alkane oxidation in air that is based on a parallel methodology to that used in turbulence modeling in the context of the Large Eddy Simulation. The objective of kinetic modeling is to predict the heat release and temperature evolution. This kinetic mechanism is valid over a pressure range from atmospheric to 60 bar, temperatures from 600 K to 2,500 K, and equivalence ratios from 0.125 to 8. This range encompasses diesel, HCCI, and gas-turbine engines, including cold ignition. A computationally efficient kinetic reduction has been proposed for alkanes that has been illustrated for n-heptane using the LLNL heptane mechanism. This model is consistent with turbulence modeling in that scales were first categorized into either those modeled or those computed as progress variables. Species were identified as being either light or heavy. The heavy species were decomposed into defined 13 constituents, and their total molar density was shown to evolve in a quasi-steady manner. The light species behave either in a quasi-steady or unsteady manner. The modeled scales are the total constituent molar density, Nc, and the molar density of the quasi-steady light species. The progress variables are the total constituent molar density rate evolution and the molar densities of the unsteady light species. The unsteady equations for the light species contain contributions of the type gain/loss rates from the heavy species that are modeled consistent with the developed mathematical forms for the total constituent molar density rate evolution; indeed, examination of these gain/loss rates shows that they also have a good quasi-steady behavior with a functional form resembling that of the constituent rate. This finding highlights the fact that the fitting technique provides a methodology that can be repeatedly used to obtain an accurate representation of full or skeletal kinetic models. Assuming success with the modified reduced model, the advantage of the modeling approach is clear. Because this model is based on the Nc rate rather than on that of individual heavy species, even if the number of species increases with increased carbon number in the alkane group, providing that the quasi-steady rate aspect persists, then extension of this model to higher alkanes should be conceptually straightforward, although it remains to be seen if the functional fits would remain valid or would require reconstruction.

Bellan, Jasette↗
NASA NTRS2003

Reduced Equations for Calculating the Combustion Rates of Jet-A and Methane Fuel

Simplified kinetic schemes for Jet-A and methane fuels were developed to be used in numerical combustion codes, such as the National Combustor Code (NCC) that is being developed at Glenn. These kinetic schemes presented here result in a correlation that gives the chemical kinetic time as a function of initial overall cell fuel/air ratio, pressure, and temperature. The correlations would then be used with the turbulent mixing times to determine the limiting properties and progress of the reaction. A similar correlation was also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium concentration of carbon monoxide as a function of fuel air ratio, pressure, and temperature. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates and the values obtained from the equilibrium correlations were then used to calculate the necessary chemical kinetic times. Chemical kinetic time equations for fuel, carbon monoxide, and NOx were obtained for both Jet-A fuel and methane.

Molnar, Melissa↗
DOE OSTI2025

Impact of gasoline composition on the effects of nitric oxide on autoignition and knock in a DISI engine

Modern spark-ignition engines use exhaust gas recirculation (EGR) to dilute the charge and suppress knock, enabling the use of higher compression ratios and/or more optimum combustion phasing for higher efficiency. The effectiveness of EGR is affected by the composition of the fuel and its chemical-kinetic interactions with combustion products. Among those, nitric oxide (NO) has been shown to strongly affect autoignition reactivity. However, the impact of fuel composition of the effect of NO on reactivity is not well-understood. Here, in this study, engine experiments were conducted to assess the impact of NO seeded to the intake on knock-limited operation of two gasoline fuels (high cycloalkane content, or HCA, and high olefin content, or HO). Results showed that compositionally-different fuels responded differently to NO. HCA, which was less knock-limited than HO for NO < 200 ppm, became more knock-limited for NO > 200 ppm. Moreover, it was found that differences in knock between fuels were caused by differences in autoignition chemistry and not in the sequential autoignition process of the end gas that occurs due to thermal stratification. Chemical kinetic simulations were performed to better understand the experimental results. For HCA, intermediate-temperature heat release had a greater impact on autoignition reactivity than low-temperature heat release, while the opposite was observed for HO. For both fuels, NO enhances the magnitude of low-temperature heat release via NO + HO 2 → NO 2 + OH. The effect of NO on reactivity was stronger for HCA because OH produced from NO helped to overcome the OH quenching effect of cyclopentane, a main species in HCA. In contrast, HO had relatively strong inherent low-temperature chemistry arising from iso-octane, which reduced the impact of NO on reactivity. For the range of NO mole fractions tested in this study, in-cylinder NO increased fuel’s knock propensity, especially for fuels with mild low-temperature chemistry.

Autoignition↗
NASA NTRS1984

Analytic modeling of a spray diffusion flame

A detailed model for a spray diffusion flame is described. The model is based on the boundary layer form of the equations of motion, with droplet transport accounted for using a discretized droplet size distribution function. Interphase transport of mass and energy are accounted for, with a flame-sheet model used to describe the combustion process on a droplet scale. Near dynamic equilibrium is assumed for the description of droplet transport; droplets can diffuse relative to the gas phase. Gas-phase mixing is accounted for using a two-equation turbulence model; buoyancy effects are included, with a temperature fluctuation equation used to account for buoyancy effects on turbulence structure. Thermal radiation from gas-phase CO2 and H2O is included. Gas-phase chemical kinetics are modeled using a 20-reaction, 10-species version of the advanced quasi-global chemical kinetics formulation. Results are compared with data for a vaporizing Freon spray and a pentane spray flame. It is shown that the computational approach provides a reasonably valid picture of the overall development of a spray diffusion flame, and, furthermore, provides a useful tool for the parametric examination of the spray combustion process.

Harsha, P. T.↗
NASA NTRS1988

Theoretical studies of solar lasers and converters

The geometry and setup for the n-C3F7I iodine laser are illustrated. The mathematical modeling of this system is described. The chemical kinetics are summarized. A sensitivity analysis was performed on the parameters occurring in the differential equations describing the chemical kinetics.

Heinbockel, John↗
DOE OSTI2020

Ignition delay time and speciation of dibutyl ether at high pressures

Dibutyl ether (DBE) is a promising biofuel due to its high cetane number (~ 100) and high volumetric energy density (31.6 MJ/L). It could either be used directly in compression ignition engines or blended with other conventional or renewable fuels. Oxidation and pyrolysis kinetics of DBE are not well known, particularly at high pressures. In this work, we have experimentally investigated the chemical kinetics of DBE in three domains: (a) ignition delay time measurements in a rapid compression machine over T = 550–650 K, P = 10, 20, 40 bar, φ = 0.5, 1; (b) ignition delay time measurements in a shock tube over T = 900–1300 K, P = 20, 40 bar, φ = 0.5, 1; (c) laser-based carbon monoxide speciation measurements in a shock tube during DBE pyrolysis and oxidation over T = 1100–1400 K, P = 20 bar. Pressure time-histories measured in RCM experiments exhibited unique 3-stage and 4-stage ignition behavior predominantly at fuel-lean conditions. Experimental data were compared with the predictions of two recent chemical kinetic models of DBE. Sensitivity analyses were carried out to identify key reactions which may have caused the discrepancy between experiments and simulations. We found that the rate of decomposition of DBE may need to be revisited to improve the oxidative and pyrolytic predictions of DBE kinetic model.

09 BIOMASS FUELS↗
DOE OSTI2026

A GPU-based compressible combustion solver for applications exhibiting disparate space and time scales

High-speed chemically active flows pose significant computational challenges due to their disparate space and time scales, with stiff chemistry often dominating simulation time. While modern scientific computing programs achieve exascale performance by leveraging graphics processing units (GPUs), existing GPU-based compressible combustion solvers face critical limitations in memory management, load balancing, and handling the highly localized nature of chemical reactions. To this end, we present a high-performance compressible reacting flow solver built on the AMReX framework and optimized for multi-GPU settings. Here, our approach addresses three GPU performance bottlenecks: memory access patterns through column-major storage optimization, computational workload variability via a bulk-sparse integration strategy for chemical kinetics, and multi-GPU load distribution for adaptive mesh refinement applications. The solver adapts existing matrix-based chemical kinetics formulations to multi-grid contexts. Using representative combustion applications, including 2D and 3D detonations and a 3D jet-in-crossflow configuration, we demonstrate 1.4–5× performance improvements over initial implementations on an in-house cluster of NVIDIA H100 GPUs, and near-ideal weak scaling on the Frontier supercomputer (Oak Ridge Leadership Computing Facility) with up to 1024 AMD Instinct MI250X GPUs. Roofline analysis reveals substantial improvements in arithmetic intensity for both convection (∼ 10 ×) and chemistry (∼ 4 ×) routines, confirming efficient utilization of GPU memory bandwidth and computational resources.

42 ENGINEERING↗