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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 865 records · Page 48
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Adsorption Studies of Dimetridazole and Metronidazole onto Biochar Derived from Sugarcane Bagasse: Kinetic, Equilibrium, and Mechanisms

Biochar derived from sugarcane bagasse was prepared at different pyrolysis temperatures and holding times for adsorption of dimetridazole and metronidazole from aqueous solution. The optimal pyrolysis temperature and holding time were 500 °C and 120 min, respectively. The removal efficiencies of dimetridazole and metronidazole were 98.0% and 88.8%, respectively, at biochar dosage of 4.0 g L{sup −1} and solution temperature of 30 °C. Kinetics data were fitted by four kinetics models, and results indicated that adsorption was governed by pseudo-second-order kinetics. Adsorption is a multi-step process that involves film diffusion and pore filling. In addition, five isotherm models were employed to describe the adsorption equilibrium. Brunauer–Emmett–Teller model presented better fitting for the adsorption equilibrium, and the maximum adsorption capacities were 72.17 and 23.61 mg g{sup − 1} for dimetridazole and metronidazole, respectively. The calculated values of ΔG{sup 0} and ΔH{sup 0} indicated the non-spontaneous and exothermic nature of the adsorption process at the range of temperature studied. Thermodynamic studies also revealed that physical and chemical adsorptions were co-action. The adsorption mechanisms of dimetridazole and metronidazole onto biochar were mainly hydrogen bonding and π–π interaction. All the results revealed that sugarcane bagasse biochar can be used as alternative to costly adsorbents for the removal of dimetridazole and metronidazole from aqueous solution.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Experimental data based combinatorial kinetic simulations for predictions of synergistic catalyst mixtures

Physical mixtures of catalysts can sometimes show synergistic activity which exceeds the sum of the activities of the same amount of catalysts employed separately. However, identifying such synergistic mixtures is non-trivial. Not all mixtures display synergy, and the number of combinations that are possible (even for binary mixtures of equal portions) scales very rapidly, and thus they would be costly to screen experimentally. In this work, we show that it is possible to predict synergistic mixtures using combinatorial kinetic simulations based on experimental data collected on individual catalysts. The data was first collected for conditions-of-interest under low conversions (also called near differential conditions, such that each condition approximates a small volume in a non-differential conditions reactor) to build a library of kinetic models (one model for each catalyst). This data was then used for combinatorial kinetic simulations of non-differential reactor scale conversions, and successfully predicted the qualitative behavior of two synergistic physical mixtures. The capability was utilized in the present work in the context of converting CO, C 3 H 6 , and NO species in simulated car exhaust, but is a general approach. We provide equations to estimate the costs of the screening method as well as the combinatorial kinetics method and show that the costs of identifying synergistic physical mixtures become much lower with the combinatorial kinetics method even before ten catalysts of interest. The cost of using prediction by the combinatorial kinetics method continue to become lower (relative to screening) when more catalysts are added -- and even more so if mixtures beyond two components, or consideration of multiple catalyst ratios, is of interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Flame ignition in the counterflow configuration: Reassessing the experimental assumptions

The counterflow configuration is widely used to study experimentally premixed and non-premixed flame ignition, with the advantage being that the data can be modeled using quasi one-dimensional codes. In this study, experiments and direct numerical simulations were carried out in order to assess the validity of the assumptions of the one-dimensional formulation. Experimentally, particle image velocimetry, shadowgraph, and a high-speed camera were employed to characterize the flow field before ignition, and to capture the ignition position and further evolution of the flame. The modeling involved axisymmetric numerical simulations using detailed molecular transport and chemical kinetic models. We report both experiments and simulations revealed that if solid surfaces are present in the vicinity of the jets exit, the flow separates generating recirculation zones that are unstable and result in the bifurcation of the flow field. As a result, for a given set of boundary conditions at the burners’ exits, there exists two possible stable states of the flow field which have different velocity and scalars distribution, and the fuel concentration at which ignition occurs was determined to differ for these two states. A novel approach is proposed to correct for the unavoidable radial non-uniformity of the temperature profile at the exit of the heated jet and the conditions that do not result in bifurcation are outlined, so that the results from one-dimensional codes can be compared to the data with confidence.

42 ENGINEERING↗
DOE OSTI2014

SU-E-QI-11: Measurement of Renal Pyruvate-To-Lactate Exchange with Hyperpolarized 13C MRI

Purpose: Previous work [1] modeling the metabolic flux between hyperpolarized [1-13C]pyruvate and [1-13C]lactate in magnetic resonance spectroscopic imaging (MRSI) experiments failed to account for vascular signal artifacts. Here, we investigate a method to minimize the vascular signal and its impact on the fidelity of metabolic modeling. Methods: MRSI was simulated for renal metabolism in MATLAB both with and without bipolar gradients. The resulting data were fit to a two-site exchange model [1], and the effects of vascular partial volume artifacts on kinetic modeling were assessed. Bipolar gradients were then incorporated into a gradient echo sequence to validate the simulations experimentally. The degree of diffusion weighting (b = 32 s/mm{sup 2}) was determined empirically from 1H imaging of murine renal vascular signal. The method was then tested in vivo using MRSI with bipolar gradients following injection of hyperpolarized [1-{sup 13}C]pyruvate (∼80 mM at 20% polarization). Results: In simulations, vascular signal contaminated the renal metabolic signal at resolutions as high as 2 × 2 mm{sup 2} due to partial volume effects. The apparent exchange rate from pyruvate to lactate (k{sub p}) was underestimated in the presence of these artifacts due to contaminating pyruvate signal. Incorporation of bipolar gradients suppressed vascular signal and improved the accuracy of kp estimation. Experimentally, the in vivo results supported the ability of bipolar gradients to suppress vascular signal. The in vivo exchange rate increased, as predicted in simulations, from k{sub p} = 0.012 s-{sup 1} to k{sub p} = 0.020-{sup 1} after vascular signal suppression. Conclusion: We have demonstrated the limited accuracy of the two-site exchange model in the presence of vascular partial volume artifacts. The addition of bipolar gradients suppressed vascular signal and improved model accuracy in simulations. Bipolar gradients largely affected kp estimation in vivo. Currently, slow-flowing spins in small vessels and capillaries are only partially suppressed, so further improvement is possible. Funding support: Seed Grant from the Radiological Society of North America, GE Healthcare, University of Wisconsin Graduate School.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

The Argon Power Cycle, a zero emission, flexible and reliable power generation technology

The proposed project was aimed at assisting in the development of the Argon Power Cycle (APC), a zero emission, flexible, and efficient power generation technology. In the effort of bringing the APC to the market, NTS proposed in the scope of this project several partial but key activities to advance the development of the APC. These tasks encompassed 1) the analysis of the market, developing a techno-economic model with integrated market inputs, 2) further optimization of our chemical kinetics models for more accurate simulation of the process and 3) scale up of our original prototype to a larger, commercially viable platform. NTS expanded on this scope of work to secure additional R&D funding in amounts north of $7M, carry out customer discovery with the sponsorship of the NSF and grow the team’s engineering talent.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2016

Parameterization of a Cookoff Model for LX-07

A thermal decomposition model for PBX 9501 (95% HMX, 2.5% Estane® binder, 2.5% BDNPA/F nitro-plasticizer) was implemented by Dickson, et. al. The objective in this study is to estimate parameters associated with this kinetics model so it can be applied to carry out thermal ignition predictions for LX-07 (90% HMX, 10% Viton binder). LX-07 thermal ignition experiments have been carried out using the “Sandia Instrumented Thermal Ignition Apparatus”, SITI. The SITI design consists of solid cylinders (1” diameter × 1” height) of high explosive (HE) confined by a cylindrical aluminum case. An electric heater is wrapped around the outer surface of the case. This heater produces a temperature heating ramp on the outer surface of the case. Internal thermocouples measure the HE temperature rise from the center to locations close to the HE-aluminum interface. The energetic material is heated until thermal ignition occurs. A two–dimensional axisymmetric heat conduction finite element model is used to simulate these experiments. The HE thermal decomposition kinetics is coupled to a heat conduction model trough the definition of an energy source term. The parameters used to define the HE thermal decomposition model are optimized to obtain a good agreement with the experimental time to thermal ignition and temperatures. Also, heat capacity and thermal conductivity of the LX-07 mixture were estimated using temperatures measured at the center of the HE before the solid to solid HMX phase transition occurred.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
DOE OSTI2016

Autoignition of methyl butanoate under engine relevant conditions

Here, this study reports the autoignition delay times of methyl butanoate in argon–air (i.e. Ar/O 2 = 3.76 by mole) mixtures under thermodynamic conditions relevant to compression ignition engines, using a rapid compression machine (RCM). The ignition delay times were obtained for the compressed temperature range of 833–1112 K and compressed pressures corresponding to 15, 30, 45, and 75 bar. In addition, the effect of fuel mole fraction on ignition delay times were experimentally studied by covering equivalence ratios corresponding to 0.25, 0.5, and 1.0 under realistic fuel loadings without additional dilution. For the range of conditions investigated, the ignition delay times exhibit an Arrhenius dependence on temperature and an inverse relationship with the compressed pressure. No evidence of two-stage ignition was observed in the current experiments, nor was a negative temperature coefficient trend seen in the ignition delay times. The experimental findings were compared to zero-dimensional simulations taking into account the full compression stroke and the heat loss characteristics of the RCM, using chemical kinetic models reported in the literature. The literature models were found to predict significantly higher reactivity when compared to the current experiments. Chemical kinetic analysis was then conducted to identify the reactions responsible for the mismatch between the experiments and the simulated results. Key reactions that could help obtain a better match between the experimental and simulated results were identified using both brute-force and global sensitivity analyses. In view of the large uncertainties associated with the low-temperature chemistry of methyl butanoate, additional studies are needed to update the kinetic parameters of the key reactions in order to improve the model comprehensiveness.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

A priori examination of reduced chemistry models derived from canonical stirred reactors using three-dimensional direct numerical simulation datasets

Data-driven approaches to construct reduced chemical kinetic models, that rely heavily on thermo-chemical datasets with full chemical kinetics, have been gaining popularity. Datasets from direct numerical simulations (DNS) under three-dimensional (3-D) realistic turbulent flow conditions are desirable but limited to carefully designed parametric conditions due to the computational cost. Constructing datasets from a large ensemble of zero-dimensional stirred reactors like perfectly stirred reactor (PSR) and partially stirred reactor (PaSR) is a computationally efficient solution to consider the turbulence-chemistry interactions and cover a broad range of parametric conditions. In this paper, we derive reduced chemistry models from solutions of a large number of PSR and PaSR reactors using autoencoder (AE) neural networks and principal component analysis (PCA), and conduct a priori examination of the reduced models in three temporally evolving 3-D DNS jet flames featuring local extinction and re-ignition. The results show that the reduced models derived from PaSR datasets, i.e., AE-PaSR and PCA-PaSR, generally show significant improvement over the ones derived from PSR datasets. Among all the reduced models, AE-PaSR shows the best agreement with DNS results on the reconstruction accuracy and the representation of temporally evolving local extinction and re-ignition events.

Zhang, Pei↗
DOE OSTI2024

The Effect of Spatially Varying Collision Frequency on the Development of the Rayleigh–Taylor Instability

Abstract The Rayleigh–Taylor (RT) instability is ubiquitously observed, yet has traditionally been studied using ideal fluid models. Collisionality can vary strongly across the fluid interface, and previous work demonstrates the necessity of kinetic models to completely capture dynamics in certain collisional regimes. Where previous kinetic simulations used spatially and temporally constant collision frequency, this work presents five-dimensional (two spatial, three velocity dimensions) continuum-kinetic simulations of the RT instability using a more realistic spatially varying collision frequency. Three cases of collisional variation are explored for two Atwood numbers: low to intermediate, intermediate to high, and low to high. The low-to-intermediate case exhibits no RT instability growth, while the intermediate-to-high case is similar to a fluid-limit kinetic case with interface widening biased toward the lower-collisionality region. A novel contribution of this work is the low-to-high collisionality case that shows significantly altered instability growth through an upward movement of the interface and damped spike growth due to increased free-streaming particle diffusion in the lower region. Contributions to the energy flux from the non-Maxwellian portions of the distribution function are not accessible to fluid models and are greatest in magnitude in the spike and regions of low collisionality. Increasing the Atwood number results in greater RT instability growth and reduced upward interface movement. Deviation of the distribution function from Maxwellian is inversely proportional to collision frequency and concentrated around the fluid interface. The linear phase of RT instability growth is well described by theoretical linear growth rates accounting for viscosity and diffusion.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2018

Nonstationary Model of a Low-Density Plasma Jet Ejected from a Stationary Plasma Thruster

A time-dependent problem on finding the parameters of a low-density plasma jet ejected from a stationary plasma thruster is analyzed. In contrast to earlier works in which a stationary problem was solved using a Crook-type kinetic model, a set of kinetic equations is derived at the accuracy level accepted in the kinetic theory with allowance for resonant charge-exchange interaction between ions and neutrals. A method to solve the obtained set of equations is developed and used to perform test simulations, some results of which are presented.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2013

GPU-accelerated Software Library for Unsteady Flamelet Modeling of Turbulent Combustion with Complex Chemical Kinetics

Modeling and simulation of turbulent combustion are computationally demanding and challenging problems due to the complexity of turbulent flows and the complex chemical reaction kinetics. Recent advances in high performance computing (HPC) has allowed simulations to utilize increasing computer power to obtain newer insights that were not feasible before. The arrival of GPUs and many-core processors is set to revolutionize the HPC landscape. This paper presents an unsteady flamelet software library developed for utilizing GPUs as an onboard accelerator while the flow solver continues to run on conventional host processors using legacy software. The software was architected to expose multiple levels of parallelism and concurrency available in the unsteady flamelet model which is also necessary to realize the full potential of these accelerators. While the model and its coupling with the flow solver have been known for some time, the potential to target these models and libraries for newer HPC architectures provides a greater incentive for pursuing combustion model development.

Sankaran, Ramanan↗
DOE OSTI2021

Experimental and computational investigations of ethane and ethylene kinetics with copper oxide particles for Chemical Looping Combustion

In this work, reaction pathways for the oxidation of methane, ethane, and ethylene with CuO was obtained by ReaxFF Molecular Dynamics (MD) simulations between temperatures of 1000 K and 2000 K. Experiments in a fixed-bed flow reactor were preformed with methane, ethane, and ethylene at temperatures ranging from 500 K to 1000 K with time-dependent species measurements from an Electron-Ionization Molecular Beam Mass Spectrometer (MBMS), and species validation with Gas Chromatography (GC) for detection of complete and intermediate combustion products. The MBMS and GC allow for the detection of oxygenated species and larger species produced from radical reformation. The simulation and experiment agree on the production of such species as CH 3 CHO, CH 2 O, CO, and H 2 O, which allow for the creation of simple C1 and C2 reaction pathways, which can be used in kinetic models of C2 species and larger fuels such as biofuels, which inherently depend on C1 and C2 kinetics and reaction pathway. The simulation and experiment disagree on the formation of C 2 H 2 , CH 3 OH, and CO 2 with large amounts of C 2 H 2 being measured in the ethylene oxidation simulations and CH 3 OH being formed in methane oxidation simulations, while neither species were experimentally found. In the case of CO 2 large amounts of CO 2 are rapidly produced in experiments with C2 fuels at 800 K, while little-to-no CO 2 was observed in simulations. This is believed to be resulting from the extremely short timescale of the simulations, preventing total oxidation of the fuel. Here, the differences in products produced between simulation and experiment allow for the potential to modify the ReaxFF potential functions to more accurately model the experimental products of Cu–H–O–C reaction kinetics.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2017

A prototype of an electric-discharge gas flow oxygen−iodine laser: I. Modeling of the processes of singlet oxygen generation in a transverse cryogenic slab RF discharge

The existing kinetic model describing self-sustained and electroionization discharges in mixtures enriched with singlet oxygen has been modified to calculate the characteristics of a flow RF discharge in molecular oxygen and its mixtures with helium. The simulations were performed in the gas plug-flow approximation, i.e., the evolution of the plasma components during their motion along the channel was represented as their evolution in time. The calculations were carried out for the O{sub 2}: He = 1: 0, 1: 1, 1: 2, and 1: 3 mixtures at an oxygen partial pressure of 7.5 Torr. It is shown that, under these conditions, volumetric gas heating in a discharge in pure molecular oxygen prevails over gas cooling via heat conduction even at an electrode temperature as low as ~100 K. When molecular oxygen is diluted with helium, the behavior of the gas temperature changes substantially: heat removal begins to prevail over volumetric gas heating, and the gas temperature at the outlet of the discharge zone drops to ~220–230 K at room gas temperature at the inlet, which is very important in the context of achieving the generation threshold in an electric-discharge oxygen−iodine laser based on a slab cryogenic RF discharge.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Mechanistic modelling of SARS-CoV-2 and other infectious diseases and the effects of therapeutics

Modern viral kinetic modeling and its application to therapeutics is a field that attracted the attention of the medical, pharmaceutical and modeling communities during the early days of the AIDS epidemic. Its successes lead to applications of modeling methods not only to HIV but a plethora of other viruses, such as hepatitis C virus (HCV), hepatitis B virus (HBV) and cytomegalovirus (CMV), which along with HIV cause chronic diseases, and viruses such as influenza, respiratory syncytial virus (RSV), West Nile virus (WNV), Zika virus, and SAR-CoV-2, which generally cause acute infections. Here we first review the historical development of mathematical models to understand HIV and HCV infections and the effects of treatment by fitting the models to clinical data. Furthermore, we then focus on recent efforts and contributions of applying these models towards understanding SARS-CoV-2 infection and highlight outstanding questions where modeling can provide crucial insights and help to optimize non-pharmaceutical and pharmaceutical interventions of the COVID-19 pandemic. The review is written from our personal perspective emphasizing the power of simple target cell limited models that provided important insights and then their evolution into more complex models that captured more of the virology and immunology. To quote Albert Einstein “Everything should be made as simple as possible, but not simpler”, and this idea underlies the modeling we describe below.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2013

Kinetics of the reduction of hematite (Fe{sub 2}O{sub 3}) by methane (CH{sub 4}) during chemical looping combustion: A global mechanism

Chemical-looping combustion (CLC) has emerged as a promising technology for fossil fuel combustion which produces a sequestration ready concentrated CO{sub 2} stream in power production. A CLC system is composed with two reactors, an air and a fuel reactor. An oxygen carrier such as hematite (94%Fe{sub 2}O{sub 3}) circulates between the reactors, which transfers the oxygen necessary for the fuel combustion from the air to the fuel. An important issue for the CLC process is the selection of metal oxide as oxygen carrier, since it must retain its reactivity through many cycles. The primary objective of this work is to develop a global mechanism with respective kinetics rate parameters such that CFD simulations can be performed for large systems. In this study, thermogravimetric analysis (TGA) of the reduction of hematite (Fe{sub 2}O{sub 3}) in a continuous stream of CH{sub 4} (15, 20, and 35%) was conducted at temperatures ranging from 700 to 825{degrees}C over ten reduction cycles. The mass spectroscopy analysis of product gas indicated the presence of CO{sub 2} and H{sub 2}O at the early stage of reaction and H{sub 2} and CO at the final stage of reactions. A kinetic model based on two parallel reactions, 1) first-order irreversible rate kinetics and 2) Avrami equation describing nucleation and growth processes, was applied to the reduction data. It was found, that the reaction rates for both reactions increase with, both, temperature and the methane concentration in inlet gas.

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

Pulse response analysis using the Y-procedure: A data science approach

We report that pulse response experiments can provide a wealth of data for transient kinetic studies of gas phase heterogeneous reactions, with the ability to paint a detailed picture of intrinsic reaction kinetics pertaining to complex catalytic mechanisms. A novel framework called the Y-Procedure was developed by Yablonsky et al. to extract information from non-steady-state kinetic data (Yablonsky et al., 2007). The Y-Procedure reconstructs the chemical transformation rate and gas composition in the catalytic zone with no a priori assumptions on the kinetic model and is used to relate changes in catalytic reaction rates and kinetic parameters to changes in a catalyst’s surface composition. This paper provides a detailed description of the data science work flow implemented in the Y-procedure through an experimental example of oxygen adsorption on platinum. Lastly, this powerful method, along with a robust list of pre-processing methodology, will enable deeper understanding of kinetic processes and mechanism to be derived from the TAP pulse response technique.

03 NATURAL GAS↗
DOE OSTI2022

Configuration Space Integration for Adsorbate Partition Functions: The Effect of Anharmonicity on the Thermophysical Properties of CO–Pt(111) and CH 3 OH–Cu(111)

A method for computing anharmonic thermophysical properties for adsorbates on metal surfaces has been extended to include libration, or frustrated rotation. Classical phase space integration is used with Monte Carlo sampling of the configuration space to obtain the partition function of CO on Pt(111) and CH 3 OH on Cu(111). A minima-preserving neural network potential energy surrogate is used within the integration routines. Direct state counting using discrete variable representation is used to benchmark the results. We find that the phase space integration approach is in excellent agreement with the direct state counting results. Comparison with standard models such as the harmonic oscillator indicates that anharmonicity contributes significantly to the thermodynamic properties of CH 3 OH on Cu(111). We find that there is also a considerable difference between the harmonic oscillator and phase space integration for CO on Pt(111), although the discrepancy can largely be attributed to the presence of multiple binding sites within the unit cell. We demonstrate that a multisite harmonic oscillator model might be sufficient for CO-Pt(111). A more thorough description of the potential energy surface, which can be achieved with phase space integration, is necessary for weakly bound adsorbates such as CH 3 OH. In conclusion, the thermophysical properties were used to calculate free energies of adsorption on the respective metals, and subsequently the equilibrium constants and Langmuir isotherms in relevant temperature ranges. The results show that the choice of model to obtain partition functions greatly affects the resulting surface coverages in kinetic models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗