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At least 235 records · Page 13

Oxidation Kinetics of Chemically Vapor-Deposited Silicon Carbide in Wet Oxygen

The oxidation kinetics of chemically vapor-deposited SiC in dry oxygen and wet oxygen (P(sub H2O) = 0.1 atm) at temperatures between 1200 C and 1400 C were monitored using thermogravimetric analysis. It was found that in a clean environment, 10% water vapor enhanced the oxidation kinetics of SiC only very slightly compared to rates found in dry oxygen. Oxidation kinetics were examined in terms of the Deal and Grove model for oxidation of silicon. It was found that in an environment containing even small amounts of impurities, such as high-purity Al2O3 reaction tubes containing 200 ppm Na, water vapor enhanced the transport of these impurities to the oxidation sample. Oxidation rates increased under these conditions presumably because of the formation of less protective sodium alumino-silicate scales.

Opila, Elizabeth J.↗

Simplified Two-Time Step Method for Calculating Combustion Rates and Nitrogen Oxide Emissions for Hydrogen/Air and Hydorgen/Oxygen

A simplified single rate expression for hydrogen combustion and nitrogen oxide production was developed. Detailed kinetics are predicted for the chemical kinetic times using the complete chemical mechanism over the entire operating space. These times are then correlated to the reactor conditions using an exponential fit. Simple first order reaction expressions are then used to find the conversion in the reactor. The method uses a two-time step kinetic scheme. The first time averaged step is used at the initial times with smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, temperature, and pressure. The second instantaneous step is used at higher water concentrations (> 1 x 10(exp -20) moles/cc) in the mixture which gives the chemical kinetic time as a function of the instantaneous fuel and water mole concentrations, pressure and temperature (T4). The simple correlations are then compared to the turbulent mixing times to determine the limiting properties of the reaction. 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 are used to calculate the necessary chemical kinetic times. This time is regressed over the complete initial conditions using the Excel regression routine. Chemical kinetic time equations for H2 and NOx are obtained for H2/air fuel and for the H2/O2. A similar correlation is also developed using data from NASA s Chemical Equilibrium Applications (CEA) code to determine the equilibrium temperature (T4) as a function of overall fuel/air ratio, pressure and initial temperature (T3). High values of the regression coefficient R2 are obtained.

Molnar, Melissa↗

Summary of Simplified Two Time Step Method for Calculating Combustion Rates and Nitrogen Oxide Emissions for Hydrogen/Air and Hydrogen/Oxygen

A simplified single rate expression for hydrogen combustion and nitrogen oxide production was developed. Detailed kinetics are predicted for the chemical kinetic times using the complete chemical mechanism over the entire operating space. These times are then correlated to the reactor conditions using an exponential fit. Simple first order reaction expressions are then used to find the conversion in the reactor. The method uses a two time step kinetic scheme. The first time averaged step is used at the initial times with smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, temperature, and pressure. The second instantaneous step is used at higher water concentrations (greater than l x 10(exp -20)) moles per cc) in the mixture which gives the chemical kinetic time as a function of the instantaneous fuel and water mole concentrations, pressure and temperature (T(sub 4)). The simple correlations are then compared to the turbulent mixing times to determine the limiting properties of the reaction. 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 are used to calculate the necessary chemical kinetic times. This time is regressed over the complete initial conditions using the Excel regression routine. Chemical kinetic time equations for H2 and NOx are obtained for H2/Air fuel and for H2/O2. A similar correlation is also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium temperature (T(sub 4)) as a function of overall fuel/air ratio, pressure and initial temperature (T(sub 3)). High values of the regression coefficient R squared are obtained.

Marek, C. John↗

A multiscale packed-bed reactor model for sustainable ethylene production via chemical looping oxidative coupling of methane

The rising global warming concerns and shale gas discovery have prompted research in the direction of greenhouse gas (GHG), such as methane, reduction and conversion. Oxidative coupling of methane (OCM) offers a pathway to low carbon-intense valorization of methane while producing ethylene, a chemical regarded as central to the petrochemical industry. Even after decades of OCM discovery, researchers keep understanding the process and underlying chemical reactions in a pursuit to achieve industrial viability for OCM. Here, in general, OCM suffers from low C 2 selectivity, yield and reactor temperature runaways due to highly exothermic nature of its reactions. Computational Fluid Dynamics (CFD) tools help analyze spatial gradients within the reactor to deeply understand the diffusion of species, mass and heat transfer phenomena. Furthermore, challenges associated with scaling up such as hot spot formation and parametric sensitivity can be addressed without having to expend on costly experiments. The current paper presents a multiscale packed-bed reactor CFD model coupled with a chemical kinetic model for the chemical looping OCM. The CFD model includes two scales i.e., macroscale for catalyst bed and microscale for individual pellets. Moreover, a chemical kinetic model based on 10 gas-phase reactions is integrated with the CFD model. An additional surface reaction for the formation of gas-phase oxygen from catalyst surface is added to account for the absence of feed oxygen. The model is calibrated against experimental results. The calibrated model captures trends in CH 4 conversion, C 2 selectivity and C 2 yield within a ± 4.35 % range across a temperature range of 700-900 °C. Moreover, model fidelity is evaluated by varying key computational parameters such as mesh resolution and time step size. The model is also verified by varying the inlet methane concentration and the gas hourly space velocity (GHSV) and comparing the results with literature. A sensitivity analysis and scale-up of the current model is undergoing.

Chemical looping↗

Autoignition study of iso -cetane/tetralin blends at low temperature

iso-Cetane and tetralin are the two fuel components commonly considered in literature diesel surrogates, and are hydrocarbon classes representative of iso-alkanes and naphthoaromatics, respectively. Since both surrogate components are involved in the key reactions controlling the autoignition reactivity of diesel surrogates, autoignition studies of iso-cetane, tetralin, and their blending behavior at low temperatures can be helpful in developing/refining chemical kinetic models of diesel surrogates, in order to better predict diesel ignition response under low temperature combustion conditions. In this investigation, autoignition experiments of iso-cetane, tetralin, and their binary mixtures at varying blending ratios have been conducted in a rapid compression machine (RCM) in the temperature/pressure range of 630–930 K and 10–20 bar. For the neat fuel components, the newly-acquired RCM data have been compared with the literature experimental results at some overlapping conditions. In addition, a chemical kinetic model describing the oxidation of iso-cetane and tetralin compiled/updated from the diesel surrogate model developed by Lawrence Livermore National Laboratory is used to simulate the experimental datasets. It is shown that this model exhibits good agreement with the experimental results of tetralin and also predicts the total ignition delay times of iso-cetane at lower temperatures reasonably well. However, the current model fails to fully capture the increase of total ignition delay time with increasing amount of tetralin in the binary blends observed in the present RCM experiments. Therefore, chemical kinetic analyses of the current model are conducted to help identify possible reasons leading to the discrepancies between simulations and experiments. Furthermore, the chemical kinetic interactions between iso-cetane and tetralin are explored by including additional cross-reactions among iso-cetane, tetralin, and their fuel fragments in the current model to assess their effects on model predictions. As a result, based on the chemical kinetic analysis results, future direction for model refinements is discussed.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DME-Propane Ignition Delay Time Measurements at Mixing Controlled Compression Ignition Engine-Relevant Conditions

The blend of dimethyl ether (DME, CH 3 OCH 3 ) and propane (C 3 H 8 ) is a potentially renewable fuel mixture that has the potential to replace diesel in compression ignition engines. The combination can potentially reduce particulate and greenhouse gas emissions compared to a conventional diesel engine operating under similar conditions. However, detailed conceptual and simulation studies must be conducted before adopting a new fuel on a compression ignition engine. For these simulations, accurate chemical kinetic models are necessary. However, the validity of chemical kinetic mechanisms in the literature is unknown for mixing controlled compression ignition (MCCI) engine operating conditions. Hence, in this work, we studied the ignition of dimethyl ether (DME) and propane blends in a shock tube at MCCI engine conditions. Ignition delay time (IDT) data was collected behind the reflected shock for DME-propane mixtures for heavy-duty compression ignition (CI) engine parameters. Undiluted experiments spanning temperatures of 700 to 1100 K and pressures of 55 to 84 bar for various blends (100% CH 3 OCH 3 / 0% C 3 H 8, 100% C 3 H 8 / 0% CH 3 OCH 3 , 60% CH 3 OCH 3 / 40% C 3 H 8 ) of DME and propane were combusted in synthetic air (21% O 2 / 79% N 2 ). Some experiments were conducted at higher pressures (90-120 bar) to understand model performance at these conditions. Comparisons of IDT were made with the predictions of recent chemical kinetic mechanisms for DME-propane mixture, including the Aramco3.0, NUIG, and Dames et al. mechanisms. All mechanisms overpredicted IDT compared to experimental values. Sensitivity analysis was conducted with Dames et al. model, and critical reactions sensitive to IDT of DME-propane mixture near 100 bar are outlined.

Mohammed, Zuhayr Pasha↗

Probing intermediate temperature heat release in autoignition of C3-C4 iso-alcohol/gasoline blends

In this work, we report an experimental and modeling study on the blending effects of C3–C4 iso-alcohols, namely iso-propanol and iso-butanol, on the characteristics of intermediate temperature heat release (ITHR) for a research-grade gasoline (FACE-F) in a rapid compression machine operating at diluted/stoichiometric fuel loading, compressed pressure of 43 bar, and compressed temperatures from 700 to 970 K. Changes in ITHR behavior are characterized through ITHR extent and evolution at 0 to 30 vol% iso-alcohol blending levels. Experimental observations reveal the strong promoting and decelerating effects on ITHR extent and evolution, respectively, within the low-temperature regime for both iso-alcohols, with stronger effects seen for iso-propanol; within the intermediate-temperature regime, the influence of both iso-alcohols diminishes greatly. Comprehensive chemical kinetic modeling is undertaken using a recently developed gasoline surrogate/alcohol model in conjunction with a five-component gasoline surrogate (FGF-LLNL), with good agreement obtained with the experiments for all the blends. Sensitivity, rate of production and flux analyses highlight the importance of chemical kinetic interactions via both fuel-specific and non-fuel-specific reactions. Disabling all the chemical kinetic interactions between iso-alcohol and FGF-LLNL in carbonated/non-fuel-specific species leads to somewhat extended ITHR duration and reduced ignition reactivity. Direct comparison between FGF-LLNL/iso-propanol and FGF-LLNL/iso-butanol blends is also made, where iso-propanol and iso-butanol are found to influence ITHR characteristics via significantly different chemical kinetic interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

SHOCK TUBE IGNITION STUDIES OF RENEWABLE DIESEL FUELS FOR MEDIUM AND HEAVY-DUTY TRANSPORTATION

Currently extensive research on alternative fuels is being conducted due to their increasing demand to reduce greenhouse emissions. One renewable fuel studied in this work is dimethyl ether (DME) blended with propane(C3H8) as a potential mixture for heavy-duty engines used in semi-trucks. The blend has the potential to drastically reduce particulate and greenhouse gas emissions compared to a conventional diesel engine operating under similar conditions. To develop the use of mixture, one must conduct detailed conceptual and simulation studies before progressing to detail studies in CFD, engine modifications, and live testing. For simulations, accurate high-fidelity chemical kinetic models are necessary. However, the validity of the chemical kinetic mechanism for operating conditions of a heavy-duty mixing-controlled compression (MCCI) engine was widely unknown until recent work presented here and published. In this work, we studied the ignition of DME and propane blends in a shock tube under MCCI engine conditions. Ignition delay time (IDT) gathered behind the reflected shock for DME-propane mixtures for heavy-duty compression ignition (CI) engine parameters. Testing was conducted for undiluted varieties spanning from temperatures of 700 to 1100 K at pressures ranging from 55 to 84 bar for various blends (100% CH3OCH3, 100% C3H8, 60% CH3OCH3/ 40% C3H8) of DME and propane were combusted in synthetic air (21% O2/ 79% N2). Several experiments were conducted at higher pressures (90-120 bar) to improve the model performance and accuracy. The ignition delay times (IDTs) were compared to recent mechanisms, including Aramco3.0, NUIG, and Dames et al. A common trend among the mechanisms was overpredicted experimental IDTs. Further studies were conducted by a sensitivity analysis using the Dames et al. model, and critical reactions sensitive to IDTs of DME-propane mixture near 60 bar are outlined. Chemical analysis was conducted on the NTC region to explain chemical kinetics which is critical for developing MCCI heavy duty engines.

Mohammed, Zuhayr Pasha↗

LSENS, The NASA Lewis Kinetics and Sensitivity Analysis Code

A general chemical kinetics and sensitivity analysis code for complex, homogeneous, gas-phase reactions is described. The main features of the code, LSENS (the NASA Lewis kinetics and sensitivity analysis code), are its flexibility, efficiency and convenience in treating many different chemical reaction models. The models include: static system; steady, one-dimensional, inviscid flow; incident-shock initiated reaction in a shock tube; and a perfectly stirred reactor. In addition, equilibrium computations can be performed for several assigned states. An implicit numerical integration method (LSODE, the Livermore Solver for Ordinary Differential Equations), which works efficiently for the extremes of very fast and very slow reactions, is used to solve the "stiff" ordinary differential equation systems that arise in chemical kinetics. For static reactions, the code uses the decoupled direct method to calculate sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of dependent variables and/or the rate coefficient parameters. Solution methods for the equilibrium and post-shock conditions and for perfectly stirred reactor problems are either adapted from or based on the procedures built into the NASA code CEA (Chemical Equilibrium and Applications).

Radhakrishnan, K.↗

Fast algorithms for combustion kinetics calculations: A comparison

To identify the fastest algorithm currently available for the numerical integration of chemical kinetic rate equations, several algorithms were examined. Findings to date are summarized. The algorithms examined include two general-purpose codes EPISODE and LSODE and three special-purpose (for chemical kinetic calculations) codes CHEMEQ, CRK1D, and GCKP84. In addition, an explicit Runge-Kutta-Merson differential equation solver (IMSL Routine DASCRU) is used to illustrate the problems associated with integrating chemical kinetic rate equations by a classical method. Algorithms were applied to two test problems drawn from combustion kinetics. These problems included all three combustion regimes: induction, heat release and equilibration. Variations of the temperature and species mole fraction are given with time for test problems 1 and 2, respectively. Both test problems were integrated over a time interval of 1 ms in order to obtain near-equilibration of all species and temperature. Of the codes examined in this study, only CREK1D and GCDP84 were written explicitly for integrating exothermic, non-isothermal combustion rate equations. These therefore have built-in procedures for calculating the temperature.

Radhakrishnan, K.↗

Prediction of hydrodynamics and chemistry of confined turbulent methane-air flames with attention to formation of oxides of nitrogen

A formulation of the governing partial differential equations for fluid flow and reacting chemical species in a tubular combustor is presented. A numerical procedure for the solution of the governing differential equations is described, and models for chemical equilibrium and chemical kinetics calculations are presented. The chemical equilibrium model is used to characterize the hydrocarbon reactions. The chemical kinetics model is used to predict the concentrations of the oxides of nitrogen. The combustor consists of a cylindrical duct of varying cross sections with concentric streams of gaseous fuel and air entering the duct at one end. Four sample cases with specified inlet and boundary conditions are considered, and the results are discussed

Elghobashi, S.↗

Program Helps To Determine Chemical-Reaction Mechanisms

General Chemical Kinetics and Sensitivity Analysis (LSENS) computer code developed for use in solving complex, homogeneous, gas-phase, chemical-kinetics problems. Provides for efficient and accurate chemical-kinetics computations and provides for sensitivity analysis for variety of problems, including problems involving honisothermal conditions. Incorporates mathematical models for static system, steady one-dimensional inviscid flow, reaction behind incident shock wave (with boundary-layer correction), and perfectly stirred reactor. Computations of equilibrium properties performed for following assigned states: enthalpy and pressure, temperature and pressure, internal energy and volume, and temperature and volume. Written in FORTRAN 77 with exception of NAMELIST extensions used for input.

Bittker, D. A.↗

Kinetics-Informed Neural Networks

Chemical kinetics and reaction engineering consists of the phenomenological framework for the disentanglement of reaction mechanisms, optimization of reaction performance and the rational design of chemical processes. Here, we utilize feed-forward artificial neural networks as basis functions to solve ordinary differential equations (ODEs) constrained by differential algebraic equations (DAEs) that describe microkinetic models (MKMs). We present an algebraic framework for the mathematical description and classification of reaction networks, types of elementary reaction, and chemical species. Under this framework, we demonstrate that the simultaneous training of neural nets and kinetic model parameters in a regularized multi-objective optimization setting leads to the solution of the inverse problem through the estimation of kinetic parameters from synthetic experimental data. We analyze a set of scenarios to establish the extent to which kinetic parameters can be retrieved from transient kinetic data, and assess the robustness of the methodology with respect to statistical noise. Furthermore, this approach to inverse kinetic ODEs can assist in the elucidation of reaction mechanisms based on transient data.

36 MATERIALS SCIENCE↗

Development and evaluation of a skeletal mechanism for EHN additized gasoline mixtures in large Eddy simulations of HCCI combustion

Advanced Low Temperature Combustion modes, such as the Sandia proposed Additive-Mixing Fuel Injection (AMFI), can unlock significant potential to boost fuel conversion efficiency and ultimately improve the energy conversion of internal combustion engines. This is a novel improved combustion process that is enabled by supplying small (<5%) variable amounts of autoignition improver to the fuel to enhance the engine operation and control. Common, diesel-fuel ignition-quality enhancing additive, 2-ethylexyl nitrate (EHN), is doped into gasoline to enable Sandia LTGC + AMFI combustion. This manuscript focuses on the development of a reduced sub-mechanism for EHN chemical kinetics at engine relevant conditions that is implemented into a skeletal mechanism for chemical kinetic studies of gasoline surrogate fuels. The mechanism validation utilized zero-dimensional numerical simulations and comparison to shock tube ignition-delay data of pure and EHN-doped n-heptane. Additional validation is presented with Homogeneous Charge Compression-Ignition (HCCI) engine data of pure and EHN-doped research-grade E10 gasoline. Then, the mechanism was deployed in a 3-D computational fluid dynamics (CFD) using Large Eddy Simulations (LES) to model the HCCI engine experiments of 0.4% vol EHN additized E10 gasoline at several equivalence ratios. Simulations showed a very good performance of the mechanism, and the model accurately reproduced (a) the ignition point, (b) combustion phasing, (c) combustion duration, and (d) the peak of the heat release rates of the engine experiments. The results show that EHN promotes Low-Temperature Heat Release, ultimately driving the gasoline to autoignite at thermodynamic conditions where the fuel would not otherwise ignite. Overall, this work demonstrates a viable reduced chemical-kinetic mechanism for EHN and shows that it can be combined with a skeletal gasoline mechanism for CFD-LES analysis of well-mixed LTGC that matches well with experimental results. The CFD-LES analysis also shows the spatial distribution of EHN-fuel interactions that control the autoignition throughout the combustion chamber.

Guleria, Gaurav↗

Physics Guided Simulation of Electrostatic Discharge: Technical Report

Triboelectrically-charged objects may create threshold sparks, electrostatic discharge (ESD) events, to equilibrate charge between themselves and other relatively charged objects. ESD events exhibit many complex physical phenomena. They are a nexus of several fields of physics with disparate characteristic scales: plasma physics, chemical kinetics, hydrodynamics, circuit models, etc. These scales can span many orders of magnitude from the varied collisions thermalizing information within a plasma on the $\mathcal{O}(fs/ps)$ to the physical size of the plasma channel on the $\mathcal{O}(100µm)$, to the speed of a nonlinear hydrodynamic wave propagating at $\mathcal{O}(µm, ns)$. These threshold ESD events may occur in situations of programmatic importance, delivering energy and power profiles to a “victim load” generating deleterious consequences. To predict and mitigate these consequences we must answer questions about the spark’s energy budget: how much energy goes into producing the spark channel; how much gets radiated away; how much energy is advected away into the hydrodynamics; and how much energy is delivered to a victim load. An ESD simulation toolset has been created and evolved in order to answer these questions. An appropriate, physics guided implementation for simulation can be done by gaining insight into its constituent physics and leveraging that intuition to choose a suitable numerical operator. We examine in detail the chemical kinetics, circuit discharge, and hydrodynamics to deter mine dominant regimes, values, timescales, and interactions to uncover the underlying physical dynamics. We also examine and propose model reduction schemes for high-dimensional chemical kinetics. We use past and current work with experimentally validated and theoretically-verified hydrodynamics to calculate applicability limits of the non-ionizing strong shock limit. We quantify the energy budget from a hydrodynamic perspective and demonstrate that a significant fraction of the stored energy is “earmarked” for hydrodynamic advection as an energy terminus. Lastly, we combine the constituent physics of an ESD event (chemical kinetics, circuit model, and hydrodynamics) into a cohesive, actionable toolset and obtain promising results from an isothermal test case. We then propose a viable, modular evolution of the ESD toolset based upon the performed examination of the physics uncovering dominant physical scales and the stiffness of the compositional differential system.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DME-Propane Blends Ignition Experiments and Modeling for Heavy-Duty Mixing Controlled Compression Engines

A blend of dimethyl ether (DME) and propane (C3H8) is being studied in a shock tube at heavy-duty engine conditions at 110 bar. Due to its intrinsic combustion properties, DME/propane blend can potentially replace diesel in mixing controlled compression ignition engines. A blend of DME/propane can reduce emissions in mixing controlled compression ignition in heavy-duty engines through modifications, which require simulations using a high-fidelity chemical kinetics model that can accurately predict the chemistry of the blend. An essential aspect of testing the chemical kinetics model is doing baseline fundamental chemistry studies on neat DME and propane, which include ignition delay time measurements. In this work, using a high-pressure shock tube, ignition delay times were gathered for DME/Propane blends at 110 bar diluted with AR to test chemical kinetic models published in the literature. These models include Aramco 3.0, NUIG V1.1, C3mech V3.3, and Dames et al. Comparisons with the experimental IDTs and models were conducted, and general agreement was observed. A sensitivity analysis was conducted, and important reactions were outlined.

Mohammed, Zuhayr Pasha [University of Central Flor↗

Kinetics and photochemistry Golden, D. M.

The data for chemical kinetics rate constants and photochemical cross sections taken from a compilation prepared in early 1985, entitled Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, is presented.

Demore, W. B.↗

An analysis of artificial viscosity effects on reacting flows using a spectral multi-domain technique

Standard techniques used to model chemically-reacting flows require an artificial viscosity for stability in the presence of strong shocks. The resulting shock is smeared over at least three computational cells, so that the thickness of the shock is dictated by the structure of the overall mesh and not the shock physics. A gas passing through a strong shock is thrown into a nonequilibrium state and subsequently relaxes down over some finite distance to an equilibrium end state. The artificial smearing of the shock envelops this relaxation zone which causes the chemical kinetics of the flow to be altered. A method is presented which can investigate these issues by following the chemical kinetics and flow kinetics of a gas passing through a fully resolved shock wave at hypersonic Mach numbers. A nonequilibrium chemistry model for air is incorporated into a spectral multidomain Navier-Stokes solution method. Since no artificial viscosity is needed for stability of the multidomain technique, the precise effect of this artifice on the chemical kinetics and relevant flow features can be determined.

Macaraeg, M. G.↗