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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Toroidal modeling of anisotropic thermal transport and energetic particle effects on stability of resistive plasma resistive wall mode

Effects of anisotropic thermal transport on the linear stability of the resistive plasma resistive wall mode (RPRWM) are investigated by the magnetohydrodynamic-kinetic hybrid code MARS-K [Liu et al., Phys. Plasmas 15, 112503 (2008)], including the kinetic contribution from energetic particles (EPs). It is found that thermal transport can further stabilize the RPRWM in the presence of drift kinetic contributions from EPs. This is different from the fluid model, which always predicts destabilization of the mode by thermal transport. Furthermore, the thermal transport effect is found to amplify the role played by an adiabatic term, associated with the radial distribution of EPs’ birth energy, in modifying the mode stability as well as the mode eigenfunction. The shape of the equilibrium profiles of EPs, in particular that of the temperature, is also found to strongly affect the mode stabilization. This profile effect is more pronounced in the absence of thermal transport. MARS-K computations show that the stabilizing effect by thermal transport is more likely to occur at slower plasma rotation and lower EP energy.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Hybrid simulation of energetic particles interacting with magnetohydrodynamics using a slow manifold algorithm and GPU acceleration

The hybrid method combining particle-in-cell and magnetohydrodynamics can be used to study the interaction between energetic particles and global plasma modes. In this paper we introduce the M3D-C1-K code, which is developed based on the M3D-C1 finite element code solving the magnetohydrodynamics equations, with a newly developed kinetic module simulating energetic particles. The particle pushing is done using a new algorithm by applying the Boris pusher to the classical Pauli particles to simulate the slow-manifold of particle orbits, with long-term accuracy and fidelity. The particle pushing can be accelerated using GPUs with a significant speedup. The moments of the particles are calculated using the δƒ method, and are coupled into the magnetohydrodynamics simulation through pressure or current coupling schemes. Several linear simulations of magnetohydrodynamics modes driven by energetic particles have been conducted using M3D-C1-K with the δƒ method, including fishbone, toroidal Alfvén eigenmodes and reversed shear Alfvén eigenmodes. Good agreement with previous results from other eigenvalue, kinetic and hybrid codes have been achieved.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

A Universal Model of Cation Effects in Electrocatalysis

Electrolyte cations are conventionally viewed as inert spectators in electrocatalysis. However, a wealth of observations show that catalytic rates are often highly sensitive to cation identity. Despite their prevalence, these cation effects have resisted a unified mechanistic explanation, with different physical phenomena implicated across reaction chemistries, catalyst compositions, and choice of solvent. In this perspective, we describe a general framework for understanding cation effects in electrocatalysis based on electrostatics. We argue that cations influence reaction rates by modifying the strength of the electric field present at the catalyst surface, which alters the energetics of adsorbed intermediates and transition states according to their dipole moments and polarizabilities. The magnitude of this field depends on how cations arrange at the electrode surface, controlled by their size, shape, solvation, and packing efficiency. Cations that can arrange more densely result in a steeper potential drop at the electrode surface and consequently a stronger electric field. Our model further identifies two criteria for observing cation effects: (1) the operating potential must be negative of the electrode’s potential of zero total charge, ensuring that cations accumulate at the interface, and (2) the energetics of the kinetically relevant elementary step must be field sensitive. This framework reconciles previously inconsistent trends, including why cation effects appear only for some catalysts, why reaction selectivity is sensitive to cation identity, and why activity can increase with cation size on certain metals but decrease on others. Supported by kinetic measurements, spectroscopy, and atomistic simulations, the model provides both conceptual value for building intuition about catalysis at charged interfaces and predictive value for anticipating trends for new reactions, catalysts, and electrolytes. We conclude by highlighting the importance of electric fields across electrochemical, thermochemical, and biological catalysis and propose that considering the electrostatic environment around active sites offers new opportunities for improving activity and selectivity.

cation effects↗
DOE OSTI2020

Stability and Control of Burning Tokamak Plasmas with Resistive Walls (Second Year Report/ Final Report)

This research will focus on quantitative prediction of the stability, control, and equilibrium state evolution in toroidal burning plasmas. The stability of long pulse burning plasmas is highly sensitive to the physics of resonant layers in the plasma, sources of momentum and ow, kinetic effects of energetic particles, and boundary conditions at the wall, including feedback control and error fields. In ITER in particular, the low toroidal ow equilibrium state, sustained primarily by energetic alpha particles from fusion reactions, will require the consideration of all of these key elements to predict quantitatively the stability and evolution. The principal investigators on this proposal are leading experts in the relevant theoretical and computational areas, and aim to perform computations guided by analytic modeling, to address this physics in realistic configurations. The overall goal is to understand the key physics mechanisms that describe resistive toroidal burning plasmas, surrounded by a resistive wall, under active feedback control. With the physics of the energetic ions, resonant layers, resistive wall, and toroidal momentum transport included, this study will extend from recent publications in theory and simulation of individual effects and move toward predictive modeling for burning plasmas.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2023

Stability and Control of Burning Tokamak Plasmas with Resistive Walls (Final Report)

This research has focused on quantitative prediction of the stability, control, and equilibrium state evolution in toroidal burning plasmas. The stability of long pulse burning plasmas is highly sensitive to the physics of resonant layers in the plasma, sources of momentum and flow, kinetic effects of energetic particles, and boundary conditions at the wall, including feedback control and error fields. In ITER in particular, the low toroidal flow equilibrium state, sustained primarily by energetic alpha particles from fusion reactions, will require the consideration of all of these key elements to predict quantitatively the stability and evolution. The principal investigators on this proposal are leading experts in the relevant theoretical and computational areas, and aimed to perform computations guided by analytic modeling, to address this physics in realistic configurations. The overall goal is to understand the key physics mechanisms that describe resistive toroidal burning plasmas, surrounded by a resistive wall, under active feedback control. With the physics of the energetic ions, resonant layers, resistive wall, and toroidal momentum transport included, this study will extend from recent publications in theory and simulation of individual effects and move toward predictive modeling for burning plasmas.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2022

Photoinduced charge transfer in the Zn-methanol cation studied with selected-ion photofragment imaging

The Zn + (methanol) ion molecule complex produced by laser vaporization is studied with photofragment imaging at 280 and 266 nm. Photodissociation produces the methanol cation CH 3 OH + via excitation of a charge-transfer excited state. Surprisingly, excitation of bound excited states produces the same fragment via a curve crossing prior to separation of products. Significant kinetic energy release is detected at both wavelengths with isotropic angular distributions. Similar experiments are conducted on the perdeuterated methanol complex. The Zn + cation is a minor product channel that also exhibits significant kinetic energy release. Finally, an energetic cycle using the ionization energies of zinc and methanol together with the kinetic energy release produces an upper limit on the Zn + -methanol bond energy of 33.7 ± 4.2 kcal/mol (1.46 ± 0.18 eV).

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

Toward Understanding and Controlling Organic Reactions on Metal Oxide Catalysts

Metal oxides have structurally complex surfaces on which a variety of adsorption site types can occur, including cation sites, anion sites, oxygen vacancy sites, and Brønsted acid sites. These sites can catalyze the catalytic transformation of organic molecules via diverse routes, thus enabling H abstraction, O abstraction, C–C bond formation, and other reactions. This Perspective provides an update on recent advances and future directions for various organic reactions on metal oxide catalyst surfaces, particularly for C–H activation of alkanes and for C–C bond formation with organic oxygenate reactants. Here, we put emphasis on the molecular scale details, on the active site structures required to enable the formation of kinetically relevant transition states, energetic descriptors, as well as contemporary ideas to enable low activation energies. This progress has been enabled by specialized experiments and the increased capabilities of modern electronic structure calculations.

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

Experimental Verification of Ir 5d Orbital States and Atomic Structures in Highly Active Amorphous Iridium Oxide Catalysts

In iridium oxide catalysts, the electronic states whose energies are in the range of energetics and charge transfer kinetics of the oxygen evolution reaction (OER) originate from the Ir 5d orbital states. However, the understanding of the atomic structures and orbital states underlying catalytic reactivity in amorphous iridium oxide oxygen evolving catalysts (Ir-OECs) is incomplete compared to that of crystalline oxides, owing to a lack of direct experimental verification. Here, we present experimental approaches using resonant inelastic X-ray scattering (RIXS) to directly access Ir 5d orbital excitations at the Ir L 3 edge and atomic pair distribution function (PDF) measurements to characterize electronic and coordination structures at the atomic scale. The so-called iridium blue layer (IrBL) and IrO x were formed from the organometallic precursor complex [Cp*Ir(H 2 O) 3 ]SO 4 and the inorganic precursor IrCl 3 , respectively. Ex situ IrBL and IrO x films for RIXS and PDF measurements were prepared by conditioning electrodeposited films at a low voltage. The incident energy RIXS profile of IrO x exhibited extra weak resonantly enhanced excitation below 2 eV energy loss. The feature was clearly different from a single high-energy excitation above 3 eV of IrBL related to the interband transition between π- and σ-antibonding states. The atomic structure refinement based on PDF measurements revealed the atomic structure domains to have edge- and corner-shared IrO 6 octahedra with trigonal-type distortion. Furthermore, density functional theory calculations guided by the refined atomic structures shed light on the electronic structure corresponding to experimental results, including insulating and metallic phases in ex situ IrBL and IrO x films, respectively. Our study establishes different Ir 5d orbital states and atomic structures in two amorphous Ir oxide OER catalysts in their reduction states.

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

Interplay between copper redox and transfer and support acidity and topology in low temperature NH 3 -SCR

Low-temperature standard NH 3 -SCR over copper-exchanged zeolite catalysts occurs on NH 3 -solvated Cu-ion active sites in a quasi-homogeneous manner. As key kinetically relevant reaction steps, the reaction intermediate Cu II (NH 3 ) 4 ion hydrolyzes to Cu II (OH)(NH 3 ) 3 ion to gain redox activity. The Cu II (OH)(NH 3 ) 3 ion also transfers between neighboring zeolite cages to form highly reactive reaction intermediates. Via operando electron paramagnetic resonance spectroscopy and SCR kinetic measurements and density functional theory calculations, we demonstrate here that such kinetically relevant steps become energetically more difficult with lower support Brønsted acid strength and density. Consequently, Cu/LTA displays lower Cu atomic efficiency than Cu/CHA and Cu/AEI, which can also be rationalized by considering differences in their support topology. By carrying out hydrothermal aging to eliminate support Brønsted acid sites, both Cu II (NH 3 ) 4 ion hydrolysis and Cu II (OH)(NH 3 ) 3 ion migration are hindered, leading to a marked decrease in Cu atomic efficiency for all catalysts.

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

Study of Alfvén eigenmode stability in Quasi-Poloidal Stellarator (QPS) plasma using a Landau closure model

The aim of this study is to analyze the linear stability of Alfvén eigenmodes (AE) in the QPS device heated by a tangential neutral beam injector (NBI). The analysis is performed using the gyro-fluid code FAR3d, that solves the reduced MHD equations for the thermal plasma coupled with moments of the kinetic equation for the energetic particles (EP). The AE stability is calculated in several operational regimes of the tangential NBI: EP β between 0.001 and 0.1, EP energy between 12 and 180 keV and different radial locations of the beam. The analysis is performed for vacuum and finite β equilibria as well as QPS configurations with two and three periods. The EP β threshold in the vacuum case is 0.001 and the AE frequency is lower as the energy of the EP population decreases. Toroidal Alfvén eigenmodes with f = 80–120 kHz and elliptical AE between f = 120–350 kHz are triggered between the middle-outer plasma region ($r/a \gt 0.5$). The AE stability improves in the simulations with finite β equilibria and three period configurations with respect to the vacuum case with two periods because the continuum gaps are slender, leading to a higher threshold of the EP β, above 0.03 for the AEs triggered by the helical mode families. Helical effects are not strong enough to destabilize Helical Alfvén eigenmodes, the AEs with the largest growth rates are triggered by the n = 1 and n = 2 toroidal families.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Grand challenges in low temperature plasmas

Low temperature plasmas (LTPs) enable to create a highly reactive environment at near ambient temperatures due to the energetic electrons with typical kinetic energies in the range of 1 to 10 eV (1 eV = 11600K), which are being used in applications ranging from plasma etching of electronic chips and additive manufacturing to plasma-assisted combustion. LTPs are at the core of many advanced technologies. Without LTPs, many of the conveniences of modern society would simply not exist. New applications of LTPs are continuously being proposed. Researchers are facing many grand challenges before these new applications can be translated to practice. In this paper, we will discuss the challenges being faced in the field of LTPs, in particular for atmospheric pressure plasmas, with a focus on health, energy and sustainability.

atmospheric pressure plasmas↗
DOE OSTI2025

Kinetic analyses for solid-state phase transition of metastable amorphous-AlO x (2.5 < x ≤ 3.0) nanostructures into crystalline alumina polymorphs

Solid-solid phase change materials (SS-PCMs) hold promise for energy storage/dissipation in batteries and energetic materials. Yet, phase change kinetics for SS-PCMs undergoing metastable to semi-stable/stable phase transformations remain relatively ill-studied because trapping metastable phases remain challenging. Recently, we demonstrated the kinetic entrapment and stabilization of a highly disordered and amorphous Al-oxide phase m-AlO x @C (x~2.5-3.0) via laser ablation synthesis in solution (LASiS). We report here, to our knowledge, the first chemical kinetics analysis for S-S phase transition of the m-AlO 3 @C nanocomposites (< 5–8 nm sizes) into semi-stable equilibrium alumina phases (θ/γ-Al 2 O 3 ) via disproportionation reaction, while releasing excess trapped gases. Our results indicate the atomic density of the AlO 3 structures to be ~5–10 times less than that of the final Al 2 O 3 phases, which led to the hypothesis of a volume shrinkage process during their phase transition. Temperature-dependent X-ray diffraction studies reveal the high-temperature phase transition for m-AlO 3 → θ/γ-Al 2 O 3 to follow contracting volume kinetics model, thereby validating our earlier hypothesis. Using the geometric volume contraction model, reaction kinetics analyses from Arrhenius plots reveal the activation energy barrier for the phase transition to be ~270±11 kJ/mol. This makes the activation energy barrier nearly identical to the oxidation of micron-sized Al particles.

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

Effect of energetic ions on edge-localized modes in tokamak plasmas

The most efficient and promising operational regime for the International Thermonuclear Experimental Reactor tokamak is the high-confinement mode. In this regime, however, periodic relaxations of the plasma edge can occur. These edge-localized modes pose a threat to the integrity of the fusion device. Here we reveal the strong impact of energetic ions on the spatio-temporal structure of edge-localized modes in tokamaks using nonlinear hybrid kinetic–magnetohydrodynamic simulations. A resonant interaction between the fast ions at the plasma edge and the electromagnetic perturbations from the edge-localized mode leads to an energy and momentum exchange. Energetic ions modify, for example, the amplitude, frequency spectrum and crash timing of edge-localized modes. The simulations reproduce some observations that feature abrupt and large edge-localized mode crashes. The results indicate that, in the International Thermonuclear Experimental Reactor, a strong interaction between the fusion-born alpha particles and ions from neutral beam injection, a main heating and fast particle source, is expected with predicted edge-localized mode perturbations. This work advances the understanding of the physics underlying edge-localized mode crashes in the presence of energetic particles and highlights the importance of including energetic ion kinetic effects in the optimization of edge-localized mode control techniques and regimes that are free of such modes.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Identifying Dense NiSe 2 /CoSe 2 Heterointerfaces Coupled with Surface High-Valence Bimetallic Sites for Synergistically Enhanced Oxygen Electrocatalysis

Constructing heterostructures with abundant interfaces is essential for integrating the multiple functionalities in single entities. Herein, the synthesis of NiSe 2 /CoSe 2 heterostructures with different interfacial densities via an innovative strategy of successive ion injection is reported. The resulting hybrid electrocatalyst with dense heterointerfaces exhibits superior electrocatalytic properties in an alkaline electrolyte, superior to other benchmarks and precious metal catalysts. Advanced synchrotron techniques, post structural characterizations, and density functional theory (DFT) simulations reveal that the introduction of atomic-level interfaces can lower the oxidation overpotential of bimetallic Ni and Co active sites (whereas Ni$^{2+}$ can be more easily activated than Co$^{2+}$) and induce the electronic interaction between the core selenides and surface in situ generated oxides/hydroxides, which play a critical role in synergistically reducing energetic barriers and accelerating reaction kinetics for catalyzing the oxygen evolution. Hence, the heterointerface structure facilitates the catalytic performance enhancement via increasing the intrinsic reactivity of metallic atoms and enhancing the synergistic effect between the inner selenides and surface oxidation species. This work not only complements the understanding on the origins of the activity of electrocatalysts based on metal selenides, but also sheds light on further surface and interfacial engineering of advanced hybrid materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Reaction Profiles and Kinetics for Radical–Radical Hydrogen Abstraction via Multireference Coupled Cluster Theory

Radical-radical abstractions in hydrocarbon oxidation chemistry are disproportionation reactions that are generally exothermic with little or no barrier yet are underappreciated and poorly studied. Such challenging multireference electronic structure problems are tackled here using the recently developed state-specific multireference coupled cluster methods Mk-MRCCSD and Mk-MRCCSD(T), as well as the companion perturbation theory Mk-MRPT2 and the established MRCISD, MRCISD+Q, and CASPT2 approaches. Reaction paths are investigated for five prototypes involving radical-radical hydrogen abstraction: H + BeH → H 2 + Be, H + NH 2 → H 2 + NH, CH 3 + C 2 H 5 → CH 4 + C 2 H 4 , H + C2H 5 → H 2 + C 2 H 4 , and H + HCO → H 2 + CO. Full configuration interaction (FCI) benchmark computations for the H + BeH, H + NH 2 , and H + HCO reactions prove that Mk-MRCCSD(T) provides superior accuracy for the interaction energies in the entrance channel, with mean absolute errors less than 0.3 kcal mol(-1) and percentage deviations less than 10% over the fragment separations of relevance to kinetics. To facilitate combustion studies, energetics for the CH 3 + C 2 H 5 , H + C 2 H 5 , and H + HCO reactions were computed at each level of theory with correlation-consistent basis sets (cc-pVXZ, X = T, Q 5) and extrapolated to the complete basis set (CBS) limit. These CBS energies were coupled with CASPT2 projected vibrational frequencies along a minimum energy path to obtain rate constants for these three reactions. The rigorous Mk-MRCCSD(T)/CBS results demonstrate unequivocally that these three reactions proceed with no barrier in the entrance channel, contrary to some earlier predictions. Mk-MRCCSD(T) also reveals that the economical CASPT2 method performs well for large interfragment separations but may deteriorate substantially at shorter distances.

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

Subdiffusive High-Pressure Hydrogen Gas Dynamics in Elastomers

We report elastomeric rubber materials serve a vital role as sealing materials in the hydrogen storage and transport infrastructure. With applications including O-rings and hose liners, these components are exposed to pressurized hydrogen at a range of temperatures, cycling rates, and pressure extremes. High-pressure exposure and subsequent rapid decompression often lead to cavitation and stress-induced damage of the elastomer due to localization of the hydrogen gas. Here, we use all-atom classical molecular dynamics simulations to assess the impact of compositional variations on gas diffusion within the commonly used elastomer ethylene–propylene–diene monomer (EPDM). With the aim to build a predictive understanding of precursors to cavitation and to motivate material formulations that are less sensitive to hydrogen-induced failure, we perform systematic simulations of gas dynamics in EPDM as a function of temperature, gas concentration, and cross-link density. Our simulations reveal anomalous, subdiffusive hydrogen motion at pressure and intermediate times. We identify two groups of gas with different mobilities: one group exhibiting high mobility and one group exhibiting low mobility due to their motion being impeded by the polymer. With decreasing temperatures, the low-mobility group shows increased gas localization, the necessary precursor for cavitation damage in these materials. At lower temperatures, increasing cross-link density led to greater hydrogen gas mobility and a lower fraction of caged hydrogen, indicating that increasing cross-link density may reduce precursors to cavitation. Finally, we use a two-state kinetic model to determine the energetics associated with transitions between these two mobility states.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Verification of global gyrokinetic simulation of low frequency mode excited by thermal plasma in spherical tokamak

A low frequency Alfven eigenmode in the ST40 spherical tokamak (ST) is found to be resonantly excited by thermal ions from global gyrokinetic GTC simulations. The analyses of phase-space resonances and wave-particle energy exchanges show that the Beta-induced Alfvén-Acoustic Eigenmode (BAAE) is primarily driven unstable by thermal ions, but is stabilized by energetic particles (EPs). When all kinetic effects are artificially suppressed, GTC simulations in the ideal magnetohydrodynamic (MHD) limit confirm the existence of the MHD eigenmode with a frequency in the BAAEs gap, as previously found by the ideal MHD code NOVA. The kinetic effects of thermal ions induce a frequency downshift compared to the stable BAAE in the MHD simulations. These results support the verification for global gyrokinetic simulations of the BAAE in the ST. However, the simulations do not explain the experimental observations of the BAAE in the ST40, possibly owing to the limitation of the collisionless gyrokinetic Monte Carlo model for the EPs.

Alfvén eigenmode↗