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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Concerted cycloaddition reactions: a study using the parabolic model and quantum chemical modeling

Concerted cycloaddition reactions were studied by the method of intersecting parabolas (M3IP) and quantum chemical calculations. Experimental data were processed within the framework of the M3IP method and an algorithm for calculating the activation energies (E) and rate constants (k) for reactions from the enthalpies of reactions was developed. The parameters E and k for twelve cycloaddition reactions not studied previously were calculated. Factors affecting the activation energies were established and evaluated; these include the enthalpy of reaction, substituents, and the molecular structure of reactants. Quantum chemical modeling and topological analysis of transition states (TS) of six concerted cycloaddition reactions were performed. Depending on structure of the starting olefins, the TS of reactions can have either a symmetric or asymmetric geometry. This influences their electronic structures, the energies of chemical bonds, and the activation energies of reactions. A comparison of the activation energy values obtained from the M3IP and DFT(B3lyp/6-311++G** ) calculations revealed good agreement between them.

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

Chemical modelling of Delayed Ettringite Formation for assessment of affected concrete structures

Delayed Ettringite Formation (DEF) modelling is addressed in the context of structural analysis. First, a chemical model is specified to simulate the effects of the heating of concrete in terms of reactions involving sulfates, aluminates and alkalis. It can be decomposed into: dissolution of primary sulfoaluminates at high temperature, fixation of aluminates in hydrogarnet or carboaluminates, and formation of delayed ettringite at low temperature. The influences of alkalis, temperature and water saturation on these reactions are taken into account. The main result of this model is the amount of delayed ettringite. The parameters of the proposed chemical model are fitted on a large number of experiments taken from the literature. The chemical model is then coupled with a nonlinear mechanical model based on poro-mechanics modelling. An application of chemo-mechanical coupling shows the features and benefits of such modelling to help practitioners in the management of structures affected by DEF.

36 MATERIALS SCIENCE↗
DOE OSTI2013

A THREE-PHASE CHEMICAL MODEL OF HOT CORES: THE FORMATION OF GLYCINE

A new chemical model is presented that simulates fully coupled gas-phase, grain-surface, and bulk-ice chemistry in hot cores. Glycine (NH{sub 2}CH{sub 2}COOH), the simplest amino acid, and related molecules such as glycinal, propionic acid, and propanal, are included in the chemical network. Glycine is found to form in moderate abundance within and upon dust-grain ices via three radical-addition mechanisms, with no single mechanism strongly dominant. Glycine production in the ice occurs over temperatures {approx}40-120 K. Peak gas-phase glycine fractional abundances lie in the range 8 Multiplication-Sign 10{sup -11}-8 Multiplication-Sign 10{sup -9}, occurring at {approx}200 K, the evaporation temperature of glycine. A gas-phase mechanism for glycine production is tested and found insignificant, even under optimal conditions. A new spectroscopic radiative-transfer model is used, allowing the translation and comparison of the chemical-model results with observations of specific sources. Comparison with the nearby hot-core source NGC 6334 IRS1 shows excellent agreement with integrated line intensities of observed species, including methyl formate. The results for glycine are consistent with the current lack of a detection of this molecule toward other sources; the high evaporation temperature of glycine renders the emission region extremely compact. Glycine detection with ALMA is predicted to be highly plausible, for bright, nearby sources with narrow emission lines. Photodissociation of water and subsequent hydrogen abstraction from organic molecules by OH, and NH{sub 2}, are crucial to the buildup of complex organic species in the ice. The inclusion of alternative branches within the network of radical-addition reactions appears important to the abundances of hot-core molecules; less favorable branching ratios may remedy the anomalously high abundance of glycolaldehyde predicted by this and previous models.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2026

Enabling accurate chemical modeling of shocked energetic materials using a machine learning interatomic potential

Understanding the complex chemistry of organic materials under dynamic compression is important for many applications, but it is challenging due to the large number of reactions occurring at various time scales. Here, in this study, we develop a machine learning potential based on Chebyshev polynomials to study the insensitive energetic material 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) under detonation. We discuss a strategy for constructing diverse training data needed to capture the complex chemistry of TATB. Our potential demonstrates strong transferability across a wide range of thermodynamic conditions and other explosives, enabling accurate and reliable chemical modeling of organic materials under extreme conditions. The efficiency of our approach allows for simulations over several nanoseconds and for large system sizes, providing detailed insights into the chemistry of shocked TATB. The model accurately reproduces experimental Hugoniot equation of state data, and our simulations reveal the rapid formation of nitrogen-rich carbon clusters following shock. The methods and datasets developed here offer a robust framework for accurate chemical modeling of other shocked organic energetic materials.

Chemistry↗
DOE OSTI2022

CFD-Chemical Model of One-Third Scale Demonstration of DOE Sealed Canister with ATR Fuel

Road-ready and final disposition packaging configurations for the advanced test reactor (ATR) fuel currently specifies storage within helium backfilled DOE sealed standard canisters. The aluminum cladding of the ATR fuel contains an oxyhydroxide layer of boehmite/bayerite that generates hydrogen when subjected to irradiation. Understanding the effect of this hydrogen buildup over time to important for long term storage considerations. Previous modeling efforts have built a coupled CFD-chemical model to simulate the temperature gas phase concentrations within the DOE sealed standard canisters. A demonstration case for these DOE sealed canisters will be eventually performed with a one-third scale mockup that has been instrumented with thermocouples and gas concentration probes. This study seeks to model the planned canister for validation of the previously developed model, such that confidence in its long-term prediction can be increased. The deployment of the instrumented lid for online monitoring in intended for a period of 10+ years based on previous monitoring of commercial fuel storage; however, the model is still run for the previously used 50-year storage periods. This case is modeled with a G-value using a bi-linear function such that it decreases at higher dose rates to be consistent with experiments. Validation efforts of the model would likely revolve around the results for the 1st year, so the results of this timeframe are also highlighted. For dried fuel of the nominal decay heat (18W), the predicted hydrogen concentration is 0.19% after 1 year, 0.91% after 10 years, and 2.8% after 50 years, with a maximum pressure of 1.26 atm. Consistent with previous modeling, the decay heat of the fuel is the main factor that influences the results. For undried fuel in pure helium, the hydrogen concentration ranges from 0.23 to 1.2% after 1 year, 1.25-6.2% after 10 years and 8.8 to 18.84% after 50 years. For dried fuel in pure helium the hydrogen concentration ranges from 0.06% to 0.34% after 1 year, 0.35-2.11% after 10 years and 0.95 to 6.6% after 50 years. While long-term results in the presence of residual air are mostly the same, early reactions with O 2 can delay significant production of H 2 until it is consumed to form more water vapor, lowering the range to 0.14 to 1.0% after 1 year. The maximum absolute pressure that is reached across any scenario is 2.06 atm. In the event of residual air, the presence of nitric acid is possible in the range of 18-131 ppm after 1 year, 174-1180 ppm after 10 years, and 586-3500 ppm after 50 years. As long as the fuel is sufficiently dried, or of nominal decay heat, a 4% lower flammability limit of hydrogen will not be reached within a 10-year monitoring period.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Guide to CFD-Chemical Model for Spent Fuel Storage

This outlines the steps that were used to create the CFD model in Star-CCM+ to simulate the 50 year thermal history of ATR fuel stored in DOE sealed canisters. Then this goes through the steps to set up the processing the model results for the one-way coupled Cantera chemical model. The next part describes the process for setting up the 50-year Cantera model in Python. The goal of this is to document the procedure for quality assurance, as well as in the event another person will need to run the process to generate additional results.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2017

Inflow, Outflow, Yields, and Stellar Population Mixing in Chemical Evolution Models

Chemical evolution models are powerful tools for interpreting stellar abundance surveys and understanding galaxy evolution. However, their predictions depend heavily on the treatment of inflow, outflow, star formation efficiency (SFE), the stellar initial mass function, the SN Ia delay time distribution, stellar yields, and stellar population mixing. Using flexCE, a flexible one-zone chemical evolution code, we investigate the effects of and trade-offs between parameters. Two critical parameters are SFE and the outflow mass-loading parameter, which shift the knee in [O/Fe]–[Fe/H] and the equilibrium abundances that the simulations asymptotically approach, respectively. One-zone models with simple star formation histories follow narrow tracks in [O/Fe]–[Fe/H] unlike the observed bimodality (separate high- α and low- α sequences) in this plane. A mix of one-zone models with inflow timescale and outflow mass-loading parameter variations, motivated by the inside-out galaxy formation scenario with radial mixing, reproduces the two sequences better than a one-zone model with two infall epochs. We present [X/Fe]–[Fe/H] tracks for 20 elements assuming three different supernova yield models and find some significant discrepancies with solar neighborhood observations, especially for elements with strongly metallicity-dependent yields. We apply principal component abundance analysis to the simulations and existing data to reveal the main correlations among abundances and quantify their contributions to variation in abundance space. For the stellar population mixing scenario, the abundances of α -elements and elements with metallicity-dependent yields dominate the first and second principal components, respectively, and collectively explain 99% of the variance in the model. flexCE is a python package available at https://github.com/bretthandrews/flexCE.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2017

Quantum chemical modeling of possible reactions of mononuclear iron nitrosyl complex [Fe(SC(NH{sub 2}){sub 2}){sub 2}(NO){sub 2}]Cl•H{sub 2}O in an aqueous solution

Possible reactions of the mononuclear iron nitrosyl complex [Fe(SC(NH{sub 2}){sub 2}){sub 2}(NO){sub 2}]Сl•H{sub 2}O in an aqueous solution were studied using quantum chemical modeling. The electronic structures of the possible intermediates were examined by the NBO and AIM methods. The substitution of the thio ligand in the iron—sulfur nitrosyl complex by a water molecule and the formation of dimeric intermediate complexes were found to facilitate the NO-donation process.

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

Quantum-chemical modeling of possible reactions of Roussin’s red esters with aryl ligands in DMSO solution

Possible reactions of Roussin’s red esters [Fe{sub 2}(μ-SC{sub 6}H{sub 4}R){sub 2}(NO){sub 4}], where R = H, o-NH{sub 2}, m-NO{sub 2}, m-OH, or m-NH{sub 2}, in DMSO solution were investigated by quantum chemical modeling. It was shown that in these systems, numerous reactions can occur, including NO donation, ligand substitution, and decomposition into mononuclear iron nitrosyl complexes. The resulting compounds are also NO donors.

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

Chemical Modeling of ATR Fuel in DOE Standard Canisters with Borated Stainless Steel Corrosion

Road-ready and final disposition packaging configurations for the ATR fuel dictates storage within helium backfilled sealed DOE standard canisters. The packaging configuration for the DOE canisters places 10 ATR elements within a Type 1a basket, and three baskets are loaded within each DOE canister. In order to provide a criticality control mechanism, these stainless baskets are proposed to be built with 1-2 weight percentage of boron. This report seeks to identify effects of corrosion of this basket material over time. The primary reaction found through surveying literature was the oxidation of the iron in steel by water to produce some hydrogen. This reaction was built into the previous chemical model of the DOE canister to assess additional hydrogen and pressure build up over time. Literature for non-borated stainless steel, and carbon steel has shown that irradiation increases the rate of corrosion, and it is assumed a similar effect would occur with borated stainless steel. Due to the wide range of results in literature, and the variation of the corrosion with boron content, a wide range of corrosion rates was tested in the model from 80 nm/yr up to 1800 nm/yr.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Microscale Mechanical‐Chemical Modeling of Granular Salt: Insights for Creep

Abstract Microscale numerical modeling is potentially an effective approach for understanding salt creep, but it is quite challenging because natural salt grain boundaries can have complex and evolving geometry, and because contacts between these deformable salt mineral grains are dynamic as a result of compaction, chemical reaction, fluid flow, and heat transfer. In this study, we have overcome these challenges and developed a new microscale mechanical‐chemical (MC) model to analyze creep of salt at the microscale, accounting for coupled deformation, dynamic contacts, and chemical reaction in granular systems with realistic geometric representations. The MC model was realized by linking a new microscale mechanical code based on the numerical manifold method (NMM) to a reactive transport code named Crunch. We simulated the processes of reorganization of the salt grains, microfracturing, and pressure solution that contribute to creep at larger scales. Based on this first quantitative microscale model, we found that sharp corners of mineral grains can dominate the contact dynamics, microfracturing, and pressure solution when salt is compacted, thus governing the structural changes and porosity loss of the system. We found that pressure solution, which preferentially dissolves sharp corners and edges, can lead to relatively high porosity loss in the system, thus playing an important role in the creep of salt. Our analysis shows that the dynamic changes of salt granular systems involving grain relocation and pressure solution can occur repeatedly and continuously, thus contributing to longer‐term creep of salt at larger scales.

58 GEOSCIENCES↗
DOE OSTI2016

Toward the Development of a Fundamentally Based Chemical Model for Cyclopentanone: High-Pressure-Limit Rate Constants for H Atom Abstraction and Fuel Radical Decomposition

Theoretical aspects of the development of a chemical kinetic model for the pyrolysis and combustion of a cyclic ketone, cyclopentanone, are considered. We present calculated thermodynamic and kinetic data for the first time for the principal species including 2- and 3-oxo-cyclopentyl radicals, which are in reasonable agreement with the literature. Furthermore, these radicals can be formed via H atom abstraction reactions by H and Ö atoms and OH, HO 2 , and CH 3 radicals, the rate constants of which have been calculated. Abstraction from the β-hydrogen atom is the dominant process when OH is involved, but the reverse holds true for HO 2 radicals. We also determined the subsequent β-scission of the radicals formed, and it is shown that recent tunable VUV photoionization mass spectrometry experiments can be interpreted in this light. The bulk of the calculations used the composite model chemistry G4, which was benchmarked in the simplest case with a coupled cluster treatment, CCSD(T), in the complete basis set limit.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2014

Final Report: Development of a Chemical Model to Predict the Interactions between Supercritical CO2, Fluid and Rock in EGS Reservoirs

This report summarizes development of a coupled-process reservoir model for simulating enhanced geothermal systems (EGS) that utilize supercritical carbon dioxide as a working fluid. Specifically, the project team developed an advanced chemical kinetic model for evaluating important processes in EGS reservoirs, such as mineral precipitation and dissolution at elevated temperature and pressure, and for evaluating potential impacts on EGS surface facilities by related chemical processes. We assembled a new database for better-calibrated simulation of water/brine/ rock/CO2 interactions in EGS reservoirs. This database utilizes existing kinetic and other chemical data, and we updated those data to reflect corrections for elevated temperature and pressure conditions of EGS reservoirs.

15 GEOTHERMAL ENERGY↗
DOE OSTI2019

Quantum Chemical Modeling of Pressure-Induced Spin Crossover in Octahedral Metal-Ligand Complexes

Spin state switching on external stimuli is a phenomenon with wide applicability, ranging from molecular electronics to gas activation in nanoporous frameworks. Here, we model the spin crossover as a function of the hydrostatic pressure in octahedrally coordinated transition metal centers by applying a field of effective nuclear forces that compress the molecule towards its centroid. For spin crossover in first-row transition metals coordinated by hydrogen, nitrogen, and carbon monoxide, we find the pressure required for spin transition to be a function of the ligand position in the spectrochemical sequence. While pressures on the order of 1 GPa are required to flip spins in homogeneously ligated octahedral sites, we demonstrate a fivefold decrease in spin transition pressure for the archetypal strong field ligand carbon monoxide in octahedrally coordinated Fe 2+ in [Fe(II)(NH 3 ) 5 CO] 2+ .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Using Co-Optimized Machine Learned Manifolds for Modeling Chemically Reacting Flows

Chemically reacting flows play a key role in a wide range of engineered systems, from chemical and polymer processing to combustion-based energy conversion technologies. Simulations of these flows involve solving a coupled set of partial differential equations for mass, momentum, energy, and all relevant chemical species in the system. Chemical reaction pathways may be extremely complex and involve hundreds or more intermediate species, with reactions that occur over timescales varying by several orders of magnitude - presenting a significant numerical stiffness challenge. The combination of these factors makes simulation of chemically reacting flows vastly more expensive than nonreactive simulations, and often makes direct solution of the governing equations intractable. It is necessary to apply lower-fidelity models in place of the detailed governing equations in order to reduce computational cost to enable reacting flow simulation tools to be used in the engineering design process. Many of the models employed for this purpose are based on reducing the dimension of the thermochemical state, motivated by the observation that the observed thermochemical states in a system lie on a low-dimensional manifold in thermochemical state space. This behavior occurs due to the fast equilibration of certain reactive and transport processes, and physics-based manifold models rely on idealized assumptions about the balance of timescales and the way in which chemistry and transport are coupled. In this work, we apply a novel method for data-driven manifold-based modeling that can leverage data from high-fidelity reacting flow simulations to improve model accuracy in cases where the physics-based modeling assumptions break down. The approach is designed to be broadly applicable across chemically reacting flow systems but is applied here to turbulent combustion modeling.

machine learning↗
DOE OSTI2014

ACTINIDE REMOVAL PROCESS SAMPLE ANALYSIS, CHEMICAL MODELING, AND FILTRATION EVALUATION

Filtration within the Actinide Removal Process (ARP) currently limits the throughput in interim salt processing at the Savannah River Site. In this process, batches of salt solution with Monosodium Titanate (MST) sorbent are concentrated by crossflow filtration. The filtrate is subsequently processed to remove cesium in the Modular Caustic Side Solvent Extraction Unit (MCU) followed by disposal in saltstone grout. The concentrated MST slurry is washed and sent to the Defense Waste Processing Facility (DWPF) for vitrification. During recent ARP processing, there has been a degradation of filter performance manifested as the inability to maintain high filtrate flux throughout a multi-batch cycle. The objectives of this effort were to characterize the feed streams, to determine if solids (in addition to MST) are precipitating and causing the degraded performance of the filters, and to assess the particle size and rheological data to address potential filtration impacts. Equilibrium modelling with OLI Analyzer{sup TM} and OLI ESP{sup TM} was performed to determine chemical components at risk of precipitation and to simulate the ARP process. The performance of ARP filtration was evaluated to review potential causes of the observed filter behavior. Task activities for this study included extensive physical and chemical analysis of samples from the Late Wash Pump Tank (LWPT) and the Late Wash Hold Tank (LWHT) within ARP as well as samples of the tank farm feed from Tank 49H. The samples from the LWPT and LWHT were obtained from several stages of processing of Salt Batch 6D, Cycle 6, Batch 16.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

H–D exchange between quercetin and solvent in the presence of Au{sup I} chloride complexes with DMSO: quantum chemical modeling

The pathways of H–D exchange between quercetin and solvent taking into account the effects of the medium are considered using quantum chemical calculations and the mechanism of selective H–D exchange reaction at the C(2′) position observed only in the presence of Au complexes is identified. It is shown that only the exchange processes in the A-ring have suffi- ciently low activation barriers. In the acidic and alkaline media, these processes occur at lower energies as compared with the reaction in the neutral system, which qualitatively agrees with the published experimental data. It was shown that the Au{sup I} chloride complex with DMSO is able to react with the C–H bond at the C(2′) position by the mechanism of electrophilic substitution under mild conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗