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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Monitoring Operational States of a Nuclear Reactor Using Seismoacoustic Signatures and Machine Learning

Monitoring nuclear reactors is an important safety and security task with growing requirements. We explore the possibility of using seismic and acoustic data for inferring the power level of an operating reactor. Continuous data recorded at a single seismoacoustic station that is located about 50 m away from a research reactor was visualized and analyzed. The data show a clear correlation between seismoacoustic features and reactor main operational states. We designed a workflow that includes two machine learning (ML) models to classify the reactor operational states (OFF, transition, and ON) and estimate reactor power levels (10%, 30%, 50%, 70%, and 90%). We applied and compared five ML algorithms for the reactor OFF-transition-ON and four approaches for the power level classification. We also compared the performance of ML models trained with seismic-only, acoustic-only, and both types of data. Five-fold cross validations were implemented to assure a thorough evaluation of the model performances. Additionally, the results show the extreme boosting gradient algorithm worked best for the first model, whereas random forests performed best for the second model. Combining seismic and acoustic data leads to better performance than using a single type of data. Seismic data contributed more than acoustic data for both models. We reached an accuracy of 0.98 for reactor OFF and ON. The accuracies for the transition state and power levels are less optimal with a minimum accuracy of 0.66. However, our results suggest seismic and acoustic data contain useful information about the transition state as well as power levels. Seismic and acoustic data could be integrated with other observations to improve monitoring performance.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2024

Thermally sensitive state change ionic redox transistor

A thermally sensitive ionic redox transistor comprises a channel, a reservoir layer, and an electrolyte layer disposed between the channel and the reservoir layer. A conductance of the channel is varied by changing concentration of ions in the channel layer. The electrolyte layer is configured to undergo a state change at a state transition temperature. Below the state transition temperature, ions in the electrolyte layer are substantially immobile. Above the state transition temperature, ions can move freely between the reservoir layer and the channel across the electrolyte layer in response to a voltage being applied between the channel and the reservoir layer. When the device is cooled below the state transition temperature or temperature range, the ions are trapped in one or more of the layers because the electrolyte layer loses its ionic conductivity. A state of the redox transistor can be read by measuring the conductance of the channel.

Ashby, David Scott↗
DOE OSTI2022

Cybersecurity vulnerability mitigation framework

Systems, methods, and computer media for mitigating cybersecurity vulnerabilities of systems are provided herein. A current cybersecurity maturity of a system can be determined based on maturity criteria. The maturity criteria can be ranked based on importance. Solution candidates for increasing the cybersecurity maturity of the system can be determined based on the ranking. The solution candidates specify cybersecurity levels for the maturity criteria. A present state value reflecting the current cybersecurity maturity of the system can be calculated. For the solution candidates, an implementation state value and a transition state value can be determined. The implementation state value represents implementation of the maturity levels of the solution candidate, and the transition state value represents a transition from the present state value to the implementation state value. Based on the transition state values, a solution candidate can be selected for the system, and the system can be modified accordingly.

Gourisetti, Sri Nikhil Gupta↗
DOE OSTI2021

Analysis and prediction of reaction kinetics using the degree of rate control

“Degree of rate control” (DRC) analysis provides a quantitative approach for analysing the kinetics of multi-step reaction mechanisms that has been widely applied to both heterogeneous and homogeneous catalysis research, as well as electrocatalysis. The DRC of any given transition state or intermediate is defined as a partial derivative such that it approximately equals the fractional increase in net rate to the product of interest per differential decrease in its standard-state free energy for that species (÷RT), holding constant the standard-state free energies of all other transition states and intermediates. Even very complex mechanisms usually have only a few species with non-zero DRCs and are thus the species whose interactions with the catalyst most strongly affect the net rate. These key DRC values thus offer a simple and intuitive route to optimize catalyst materials, especially with the assistance of computational methods like density functional theory (DFT). These high-DRC species are also the species whose energetics must be most accurately measured or calculated to achieve an accurate kinetic model for any reaction mechanism. In simple cases with a single “rate-determining step”, the DRC for its transition state (TS) is + 1. Catalyst-bound intermediates, on the other hand, often have negative DRCs equal to a small integer times their fractional occupancy of catalyst sites. The apparent activation energy equals a weighted average of the standard-state enthalpies (relative to reactants) of all the species (intermediates, transition states and products) in the reaction mechanism, each weighted by its DRC (+RT). It has been shown that the apparent transfer coefficient in electrocatalysis, an inverted form of the Tafel slope, is a weighted average of the number of electrons transferred to generate each intermediate or product species in the mechanism, weighted again by the DRC. Quantitative analysis of kinetic isotope effects (KIEs, or the ratio of net rates for different reactant isotopes) in complex mechanisms has shown that the logarithm of the KIE equals the weighted average over all species in the mechanism of the difference between the two isotopes in their standard-state free energies (÷RT), again weighted by the DRC. The reaction orders with respect to fluid-phase concentrations of reactants, products and intermediates have also been proven to be directly related to DRCs. Thus, there are numerous experimental observables which equate to short linear combinations of DRCs, so that combinations of experimental measurements might provide access to DRC values. Since its invention for transition states in 1994 and its generalization to include intermediates in 2009, the DRC has thus far mainly been calculated for microkinetic models based either entirely on DFT or on DFT with the key energies (i.e., those for high-DRC species) being fine-tuned to match experiments. The relationships summarized in this work provide new opportunities for using experiments earlier in the development and optimization of microkinetic models that require input from computational catalysis.

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

Radical–Radical Reactions in Molecular Weight Growth: The Phenyl + Propargyl Reaction

The mechanism for hydrocarbon ring growth in sooting environments is still the subject of considerable debate. The reaction of phenyl radical (C 6 H 5 ) with propargyl radical (H 2 CCCH) provides an important prototype for radical–radical ring-growth pathways. We studied this reaction experimentally over the temperature range of 300–1000 K and pressure range of 4–10 Torr using time-resolved multiplexed photoionization mass spectrometry. We detect both the C 9 H 8 and C 9 H 7 + H product channels and report experimental isomer-resolved product branching fractions for the C 9 H 8 product. We compare these experiments to theoretical kinetics predictions from a recently published study augmented by new calculations. Here, these ab initio transition state theory-based master equation calculations employ high-quality potential energy surfaces, conventional transition state theory for the tight transition states, and direct CASPT2-based variable reaction coordinate transition state theory (VRC-TST) for the barrierless channels. At 300 K only the direct adducts from radical–radical addition are observed, with good agreement between experimental and theoretical branching fractions, supporting the VRC-TST calculations of the barrierless entrance channel. As the temperature is increased to 1000 K we observe two additional isomers, including indene, a two-ring polycyclic aromatic hydrocarbon, and a small amount of bimolecular products C 9 H 7 + H. Our calculated branching fractions for the phenyl + propargyl reaction predict significantly less indene than observed experimentally. We present further calculations and experimental evidence that the most likely cause of this discrepancy is the contribution of H atom reactions, both H + indenyl (C 9 H 7 ) recombination to indene and H-assisted isomerization that converts less stable C 9 H 8 isomers into indene. Especially at low pressures typical of laboratory investigations, H-atom-assisted isomerization needs to be considered. Regardless, the experimental observation of indene demonstrates that the title reaction leads, either directly or indirectly, to the formation of the second ring in polycyclic aromatic hydrocarbons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1998

Reveal, A General Reverse Engineering Algorithm for Inference of Genetic Network Architectures

Given the immanent gene expression mapping covering whole genomes during development, health and disease, we seek computational methods to maximize functional inference from such large data sets. Is it possible, in principle, to completely infer a complex regulatory network architecture from input/output patterns of its variables? We investigated this possibility using binary models of genetic networks. Trajectories, or state transition tables of Boolean nets, resemble time series of gene expression. By systematically analyzing the mutual information between input states and output states, one is able to infer the sets of input elements controlling each element or gene in the network. This process is unequivocal and exact for complete state transition tables. We implemented this REVerse Engineering ALgorithm (REVEAL) in a C program, and found the problem to be tractable within the conditions tested so far. For n = 50 (elements) and k = 3 (inputs per element), the analysis of incomplete state transition tables (100 state transition pairs out of a possible 10(exp 15)) reliably produced the original rule and wiring sets. While this study is limited to synchronous Boolean networks, the algorithm is generalizable to include multi-state models, essentially allowing direct application to realistic biological data sets. The ability to adequately solve the inverse problem may enable in-depth analysis of complex dynamic systems in biology and other fields.

Liang, Shoudan↗
DOE OSTI2025

Elucidation of Marcus Relationships for Hydride Transfer Reactions Involving Transition Metal Hydrides

The rate of hydride transfer from three Ir hydride complexes of the type Cp*Ir( R bpy)H + (Cp* = C 5 Me 5 ; R bpy = 4,4′-R-2,2′-bipyridine, R = OMe, H, CO 2 Me) to six N-methylacridinium ( R Acr + ) acceptors with electronically different substituents in the 2- or 2,7-positions were measured. Using the thermodynamic hydricity of the donors and the hydride affinity of the acceptors the thermodynamic driving forces for hydride transfer were determined. Brønsted plots, which correlate kinetic and thermodynamic hydricity, demonstrate distinct linear free energy relationships for each complex, with different Brønsted α values. Thus, at the same driving force hydride transfer from Cp*Ir( OMe bpy)H + is faster than for Cp*Ir(bpy)H + or Cp*Ir( CO2Me bpy)H + . Experimental and computational analyses are consistent with a concerted hydride transfer mechanism for all Ir complexes. As the thermodynamic driving force increases an earlier transition state is observed and all transition states also include π-stacking interactions between the donor and acceptor, which likely contribute to the different α values. The experimental data fits well to the Marcus model, enabling the determination of reorganization energies (λ) that range from 58 to 69 kcal mol -1 . These are lower than λ values for hydride transfer reactions involving organic donors and acceptors. This work provides a rare example of the correlation of kinetic and thermodynamic hydricity using only experimental data and shows that hydride transfer reactions involving metal hydrides can follow Marcus theory. Furthermore, the findings offer insight into controlling metal-catalyzed hydride transfer reactions, which is valuable for designing improved systems for a range of transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Product specific thermal degradation kinetics of bisphenol F epoxy in inert and oxidative atmospheres using evolved gas analysis–mass spectrometry

Knowledge of the degradation kinetics for polymer materials is important for understanding thermal stability. In this study, evolved gas analysis–mass spectrometry and pyrolysis gas-chromatography-mass spectrometry were evaluated for the potential to deliver additional insight into thermal degradation kinetics of diglycidal ether of bisphenol F (DGEBF) epoxy thermoset under inert and oxidative atmospheres. Degradation products of selected precursor ions were evaluated for their uniqueness to the specific precursor using extracted ion thermographs. Unique mass peaks, solely attributed to a single reaction pathway of a specific product, were determined from extracted ion thermographs and used to determine both activation energy (E a ) and pre-exponential factors for the specific primary reaction pathways. These primary reaction pathways for DGEBF epoxy degradation were then evaluated in the context of transition state theory (TST) and related transition state enthalpies (ΔH ‡ ) and entropies (ΔS ‡ ) of activation to further elucidate the degradation process. It was determined under pyrolysis conditions, as suggested by the E a , the formation of bisphenol F monomer was the rate-limiting step toward the formation of xanthene and phenol. In contrast, under thermo-oxidative conditions, reactions involving oxygen containing species were identified as the rate-limiting step for all observed products based on the large negative ΔS ‡ calculated from TST. This work demonstrates a powerful combination of technique and theory that can provide new insight into the degradation of polymer materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2007

State-Chart Autocoder

A computer program translates Unified Modeling Language (UML) representations of state charts into source code in the C, C++, and Python computing languages. ( State charts signifies graphical descriptions of states and state transitions of a spacecraft or other complex system.) The UML representations constituting the input to this program are generated by using a UML-compliant graphical design program to draw the state charts. The generated source code is consistent with the "quantum programming" approach, which is so named because it involves discrete states and state transitions that have features in common with states and state transitions in quantum mechanics. Quantum programming enables efficient implementation of state charts, suitable for real-time embedded flight software. In addition to source code, the autocoder program generates a graphical-user-interface (GUI) program that, in turn, generates a display of state transitions in response to events triggered by the user. The GUI program is wrapped around, and can be used to exercise the state-chart behavior of, the generated source code. Once the expected state-chart behavior is confirmed, the generated source code can be augmented with a software interface to the rest of the software with which the source code is required to interact.

Clark, Kenneth↗
DOE OSTI2022

Nucleation Rate Theory for Coordination Number: Elucidating Water-Mediated Formation of a Zigzag Na 2 SO 4 Morphology

Predicting and controlling nanostructure formation during nucleation can pave the way to synthesizing novel energy materials via crystallization. However, such control over nucleation and crystallization remains challenging due to an inadequate understanding of critical factors that govern evolving atomistic structures and dynamics. Here, in this paper, we utilize coordination number as a reaction coordinate and rate theory to investigate how sodium sulfate, commonly known as a phase-change energy material, nucleates in a supersaturated aqueous solution. In conjunction with ab initio and force field-based molecular dynamics simulation, the rate theoretical analysis reveals that sodium sulfate from an initially dissolved metastable state transits to a heterogeneous mixture of prenucleated clusters and finally to a large cylindrical zigzag morphology. Measurements of Raman spectra and their ab initio modeling confirm that this nucleated morphology contains a few waters for every sulfate. Rate processes such as solvent exchange and desolvation exhibit high sensitivity to the evolving prenucleation/nucleation structures, providing a means to distinguish between critical nucleation precursors. Desolvation and forming the first-shell interionic coordination structure via monomer-by-monomer addition around sulfates are found to explain the formation of large nuclei. Thus, a detailed understanding of the step-by-step structure formation across scales has been achieved. This can be leveraged to predict nucleation-related structures and dynamics and potentially control the synthesis of novel phase-change materials for energy applications.

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

Magnetic Flux Plays an Important Role during a Black Hole X-Ray Binary Outburst in Radiative Two-temperature General Relativistic Magnetohydrodynamic Simulations

Abstract Black hole (Bh) X-ray binaries cycle through different spectral states of accretion over the course of months to years. Although persistent changes in the Bh mass accretion rate are generally recognized as the most important component of state transitions, it is becoming increasingly evident that magnetic fields play a similarly important role. In this article, we present the first radiative two-temperature general relativistic magnetohydrodynamics simulations in which an accretion disk transitions from a quiescent state at an accretion rate of M ̇ ∼ 10 − 10 M ̇ Edd to a hard-intermediate state at an accretion rate of M ̇ ∼ 10 − 2 M ̇ Edd . This huge parameter space in mass accretion rate is bridged by artificially rescaling the gas density scale of the simulations. We present two jetted BH models with varying degrees of magnetic flux saturation. We demonstrate that in “standard and normal evolution” models, which are unsaturated with magnetic flux, the hot torus collapses into a thin and cold accretion disk when M ̇ ≳ 5 × 10 − 3 M ̇ Edd . On the other hand, in “magnetically arrested disk” models, which are fully saturated with vertical magnetic flux, the plasma remains mostly hot with substructures that condense into cold clumps of gas when M ̇ ≳ 1 × 10 − 2 M ̇ Edd . This suggests that the spectral signatures observed during state transitions are closely tied to the level of magnetic flux saturation.

Astronomy & Astrophysics↗
NASA NTRSDate not supplied

High Reynolds Number Testing of the NATO AVT-298 SWiFT Configuration at the National Transonic Facility

A high Reynolds number wind tunnel test of the NATO AVT-298 Swept Wing Flow Test (SWiFT) configuration was conducted in the National Transonic Facility at the NASA Langley Research Center during the summer of 2023. The SWiFT research model geometry has relevance to both blended/hybrid wing body (BWB/HWB) and unmanned combat aerial vehicle (UCAV) configurations, and the test campaign was the culmination of an international collaboration under the NATO AVT-298 research task group. The main objectives of the test were to investigate Reynolds number scaling effects on low-speed stability & control characteristics and to examine the onset and progression of flow separation on the wings particularly near the wing crank. Force & moment and surface pressure data were acquired at Mach numbers from 0.2 to 0.8, Reynolds numbers from 2.5 to 34 million, angles of attack from -3 to 20 degrees, and sideslip angles from -10 to 10 degrees. Boundary layer transition detection techniques utilizing static pressure taps, unsteady pressure transducers, and sublimating chemicals were used on the model in a free/natural transition state or a forced transition state using trip dots. Pressure sensitive paint was used to obtain a global surface pressure profile on the model and an advanced laser velocimetry technique was used to obtain velocity measurements in the wake downstream of the wing crank. The results from the test showed clear Reynolds number scaling effects on the maximum lift coefficient and pitching moment coefficient at Mach 0.2, while also capturing significant hysteresis effects. The data acquired from the test will ultimately help improve computational aerodynamic analysis and design tools for application to future BWB-type vehicle configurations.

NATO AVT-298↗
NASA NTRSDate not supplied

High Reynolds Number Testing of the NATO AVT-298 SWiFT Configuration at the National Transonic Facility

A high Reynolds number wind tunnel test of the NATO AVT-298 Swept Wing Flow Test (SWiFT) configuration was conducted in the National Transonic Facility at the NASA Langley Research Center during the summer of 2023. The SWiFT research model geometry has relevance to both blended/hybrid wing body (BWB/HWB) and unmanned combat aerial vehicle (UCAV) configurations, and the test campaign was the culmination of an international collaboration under the NATO AVT-298 research task group. The main objectives of the test were to investigate Reynolds number scaling effects on low-speed stability & control characteristics and to examine the onset and progression of flow separation on the wings particularly near the wing crank. Force & moment and surface pressure data were acquired at Mach numbers from 0.2 to 0.8, Reynolds numbers from 2.5 to 34 million, angles of attack from -3 to 20 degrees, and sideslip angles from -10 to 10 degrees. Boundary layer transition detection techniques utilizing static pressure taps, unsteady pressure transducers, and sublimating chemicals were used on the model in a free/natural transition state or a forced transition state using trip dots. Pressure sensitive paint was used to obtain a global surface pressure profile on the model and an advanced laser velocimetry technique was used to obtain velocity measurements in the wake downstream of the wing crank. The results from the test showed clear Reynolds number scaling effects on the maximum lift coefficient and pitching moment coefficient at Mach 0.2, while also capturing significant hysteresis effects. The data acquired from the test will ultimately help improve computational aerodynamic analysis and design tools for application to future BWB-type vehicle configurations.

BWB/HWB↗
DOE OSTI2023

The multichannel i -propyl + O2 reaction system: A model of secondary alkyl radical oxidation

The i-propyl + O2 reaction mechanism has been investigated by definitive quantum chemical methods to establish this system as a benchmark for the combustion of secondary alkyl radicals. Focal point analyses extrapolating to the ab initio limit were performed based on explicit computations with electron correlation treatments through coupled cluster single, double, triple, and quadruple excitations and basis sets up to cc-pV5Z. The rigorous coupled cluster single, double, and triple excitations/cc-pVTZ level of theory was used to fully optimize all reaction species and transition states, thus, removing some substantial flaws in reference geometries existing in the literature. The vital i-propylperoxy radical (MIN1) and its concerted elimination transition state (TS1) were found 34.8 and 4.4 kcal mol−1 below the reactants, respectively. Two β-hydrogen transfer transition states (TS2, TS2′) lie above the reactants by (1.4, 2.5) kcal mol−1 and display large Born–Oppenheimer diagonal corrections indicative of nearby surface crossings. An α-hydrogen transfer transition state (TS5) is discovered 5.7 kcal mol−1 above the reactants that bifurcates into equivalent α-peroxy radical hanging wells (MIN3) prior to a highly exothermic dissociation into acetone + OH. The reverse TS5 → MIN1 intrinsic reaction path also displays fascinating features, including another bifurcation and a conical intersection of potential energy surfaces. An exhaustive conformational search of two hydroperoxypropyl (QOOH) intermediates (MIN2 and MIN3) of the i-propyl + O2 system located nine rotamers within 0.9 kcal mol−1 of the corresponding lowest-energy minima.

Chemistry↗
NASA NTRS2005

X-Ray and Radio Studies of Black Hole X-Ray Transients During Outburst Decay

Black hole (BH) and black hole candidate (BHC) transients are X-ray binary systems that typically undergo bright outbursts that last a couple months with recurrence times of years to decades. For this ADP project, we are studying BH/BHC systems during the decaying phases of their outbursts using the Rossi X-ray Taming Explorer (RXTE), the Chandra X-ray Observatory, and multi-wavelength facilities. These systems usually undergo state transitions as they decay, and our observations are designed to catch the state transitions. The specific goals of this proposal include: 1. To determine the evolution of the characteristic frequencies present in the power spectrum (such as quasi-periodic oscillations, QPOs) during state transitions in order to place constraints on the accretion geometry; 2. To contemporaneously measure X-ray spectral and timing properties along with flux measurements in the radio band to determine the relationship between the accretion disk and radio jets; 3. To extend our studies of X-ray properties of BHCs to very low accretion rates using RXTE and Chandra. The work performed under this proposal has been highly successful, allowing the PI to lead, direct, or assist in the preparation of 7 related publications in refereed journals and 6 other conference presentations or reports. These items are listed below, and the abstracts for the refereed publications have also been included. Especially notable results include our detailed measurements of the characteristic frequencies and spectral parameters of BH/BHCs after the transition to the hard state (see All A3, and A5) and at low flux levels (see A4). Our measurements provide one of the strongest lines of evidence to date that the inner edge of the optically thick accretion disk gradually recedes from the black hole at low flux levels. In addition, we have succeeded in obtaining excellent multi-wavelength coverage of a BH system as its compact jet turned on (see Al). Our results show, somewhat unexpectedly, that the radio jet does not turn on until the hard X-ray emission is well past its peak hard state level, strongly constraining theoretical models for hard X-ray production and the spectrum emitted by the jet. Finally, the X-ray/radio results in A2 led us to propose a general picture about the relationship between jet production and X-ray spectral states .

Tomsick, John A.↗
DOE OSTI2022

A Combined DFT, Energy Decomposition, and Data Analysis Approach to Investigate the Relationship Between Noncovalent Interactions and Selectivity in a Flexible DABCOnium/Chiral Anion Catalyst System

Developing strategies to study reactivity and selectivity in flexible catalyst systems has become an important topic of research. Herein, we report a combined experimental and computational study aimed at understanding the mechanistic role of an achiral DABCOnium cofactor in a regio- and enantiodivergent bromocyclization reaction. In this study, it was found that electron-deficient aryl substituents enable rigidified transition states via an anion–π interaction with the catalyst, which drives the selectivity of the reaction. In contrast, electron-rich aryl groups on the DABCOnium result in significantly more flexible transition states, where interactions between the catalyst and substrate are more important. An analysis of not only the lowest-energy transition state structures but also an ensemble of low-energy transition state conformers via energy decomposition analysis and machine learning was crucial to revealing the dominant noncovalent interactions responsible for observed changes in selectivity in this flexible system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗