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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 OSTI2023

Operando Mechanistic Studies of CO 2 Hydrogenation by Ruthenium Complexes Using High-Pressure NMR Spectroscopy

As a result of increased energy demands, the ability to both reduce carbon dioxide with dihydrogen to formate and conduct the reverse reaction with the same catalyst is of interest as a method for potential fuel generation and use. Ruthenium bis(diphosphine) complexes with and without pendant amines were reacted with mixtures of CO 2 /H 2 gases in the presence of added base to catalytically yield formate; when the base was triethylamine, the reaction was found to be reversible. The reactions were monitored using high-pressure operando 1 H and 31 P{ 1 H} NMR spectroscopy at 18 °C in THF under 40 atm of a 1:1 mixture of H 2 and CO 2 . The rate of production of formate was correlated with the observation of specific organometallic species by NMR spectroscopy under catalytic conditions, including a hydrido–dihydrogen complex. From this operando study, a mechanism is proposed with two competing catalytic cycles for which the predominant cycle is dependent on which base and catalyst are used. Finally, the role of the base is shown to be vital for both catalytic rate and reversibility of the chemical transformation, indicating base selection should be carefully considered.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1970

Perception of the upright and susceptibility to motion sickness as functions of angle of tilt and angular velocity in off-vertical rotation

Motion sickness susceptibility of four normal subjects was measured in terms of duration of exposure necessary to evoke moderate malaise (MIIA) as a function of velocity in a chair rotated about a central axis tilted 10 deg with respect to gravitational upright. The subjects had little or no susceptibility to this type of rotation at 2.5 and 5.0 rpm, but with further increases in rate, the MIIA endpoint was always reached and with ever shorter test durations. Minimal provocative periods for all subjects were found at 15 or 20 rpm. Higher rotational rates dramatically reversed the vestibular stressor effect, and the subjects as a group tended to reach a plateau of relatively low susceptibility at 40 and 45 rpm. At these higher velocities, furthermore, the subjects essentially lost their sensation of being tilted off vertical. In the second half of the study, the effect of tilt angle was varied while the rotation rate was maintained at a constant 17.5 rpm. Two subjects were completely resistant to symptoms of motion sickness when rotated at 2.5 deg off vertical; with greater off-vertical angles, the susceptibility of all subjects increased sharply at first, then tapered off in a manner reflecting a Fechnerian function.

Earl F. Miller II↗
DOE OSTI2024

Modeling Rate Dependent Volume Change in Porous Electrodes in Lithium-Ion Batteries

Automotive manufacturers are working to improve individual cell, module, and overall pack design by increasing the performance, range, and durability, while reducing cost. One key piece to consider during the design process is the active material volume change, its linkage to the particle, electrode, and cell level volume changes, and the interplay with structural components in the rechargeable energy storage system. As the time from initial design to manufacture of electric vehicles decreases, design work needs to move to the virtual domain; therefore, a need for coupled electrochemical-mechanical models that take into account the active material volume change and the rate dependence of this volume change need to be considered. In this study, we illustrated the applicability of a coupled electrochemical-mechanical battery model considering multiple representative particles to capture experimentally measured rate dependent reversible volume change at the cell level through the use of an electrochemical-mechanical battery model that couples the particle, electrode, and cell level volume changes. By employing this coupled approach, the importance of considering multiple active material particle sizes representative of the distribution is demonstrated. The non-uniformity in utilization between two different size particles as well as the significant spatial non-uniformity in the radial direction of the larger particles is the primary driver of the rate dependent characteristics of the volume change at the electrode and cell level.

Electrochemistry↗
NASA NTRS1981

Assessment of variations in thermal cycle life data of thermal barrier coated rods

The reported study had the purpose to examine variations in cyclic life and in adhesive/cohesive coating strength. Possible effects of heating rate, stress reversal, temperature level, and ceramic deposition methods on coating life were also investigated. Life cycle data for 22 thermal barrier coated rods were examined and found to be statistically modeled by normal or log-normal distributions. The sample mean was 1330 cycles with a standard deviation of 520 cycles. Adhesive/cohesive pulloff strength data for 20 thermal barrier coated flat head piston specimens were taken. The average pulloff stress was 9 MPa with a standard deviation of 4.2 MPa. It was found that variations in heating rate can produce significant variations in the life cycle data.

Hendricks, R. C.↗
DOE OSTI2020

Interfacial solvation and slow transport of hydrated excess protons in non-ionic reverse micelles

This work employs molecular dynamics simulations to investigate the solvation and transport properties of hydrated excess protons (with a hydronium-like core structure) in non-ionic Igepal CO-520 reverse micelles of various sizes in a non-polar solvent. Multiscale Reactive Molecular Dynamics (MS-RMD) simulations were used to describe vehicular and hopping diffusion during the proton transport process. As detailed herein, an excess proton shows a marked tendency to localize in the interfacial region of micellar water pools. Slow proton transport was observed which becomes faster with increasing micellar size. Further analysis reveals that the slow diffusion of an excess proton is a combined result of slow water diffusion and the low proton hopping rate. This study also confirms that a low proton hopping rate in reverse micelles stems from the interfacial solvation of hydrated excess protons and the immobilization of interfacial water. The low water density in the interfacial region makes it difficult to form a complete hydrogen bond network near the hydrated excess proton, and therefore locks in the orientation of hydrated proton cations. The immobilization of the interfacial water also slows the relaxation of the overall hydrogen bond network.

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

Synchrotron Imaging of Pore Formation in Li Metal Solid-State Batteries Aided by Machine Learning

High-rate capable, reversible lithium metal anodes are necessary for next generation energy storage systems. In situ tomography of Li/LLZO/Li cells is carried out to track morphological transformations in Li metal electrodes. Machine learning enables tracking the lithium metal morphology during galvanostatic cycling. Nonuniform lithium electrode kinetics are observed at both electrodes during cycling. Hot spots in lithium metal are correlated with microstructural anisotropy in LLZO. Mesoscale modeling reveals that regions with lower effective properties (transport and mechanical) are nuclei for failure. Advanced visualization combined with electrochemistry represents an important pathway toward resolving non-equilibrium effects that limit rate capabilities of solid-state batteries.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Vertical GaN Superjunction Diode on Sapphire with Kilovolt Dynamic Breakdown Voltage

The development of superjunction structures for use in vertical wide bandgap power devices promise to break the 1-D material limits. Additionally, the possibility of utilizing heteroepitaxial GaN-on-Sapphire wafer for vertical devices can significantly trim the material and device cost. This work introduces a quasi-vertical GaN-on-Sapphire superjunction PN diode design utilizing sputtered p-NiO on the etched GaN fins for superjunction formation. DC breakdown voltage is shown to vary with superjunction charge imbalance and significantly exceed the expected 1-D planar limit of 350V given the epilayer design used. A maximum breakdown voltage of 840 V is extracted for near charge balance conditions limited by leakage current. Dynamic breakdown of the device is characterized as a function of reverse voltage slew rate. A maximum dynamic breakdown voltage of 1160 V under a reverse voltage slew rate of 2000 V/μs is found.

Porter, Matthew↗
DOE OSTI2022

CO 2 hydrogenation: Selectivity control of CO versus CH 4 achieved using Na doping over Ru/m-ZrO 2 at low pressure

By doping 1%Ru/m-ZrO 2 with sodium, selectivity tuning between CO and CH 4 during CO 2 hydrogenation was achieved by controlling the relative rates of reverse water-gas shift and CO methanation. By increasing basicity through Na loading: (1) the formate C-H bond is weakened in DRIFTS of adsorbed CO, accelerating C-H bond formation of formate and promoting CO formation at the Ru/m-ZrO 2 interface; and (2) the coverage of Na increases on ensembles of Ru atoms responsible for methanation. Increasing Na content shifts selectivity from CH 4 (useful for synthetic natural gas) to CO, which can be used for Fischer-Tropsch synthesis or methanol-to-gasoline. Electronic modification of formate is likely due to enhanced basicity (strengthening bonding between catalyst and the-CO 2 function of formate and weakening C-H). In conclusion, no electron transfer from Na to Ru was detected in XANES. DRIFTS as a function of time and XPS results showed that Na exacerbates site blocking and deactivation.

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

Direct Deoxygenation of Phenol over Fe-Based Bimetallic Surfaces Using On-the-Fly Surrogate Models

We present an accelerated nudged elastic band (NEB) study of phenol direct deoxygenation (DDO) on Fe-based bimetallic surfaces using a recently developed Gaussian process regression (GPR) calculator. Our test calculations demonstrate that the GPR calculator achieves up to 3 times speedup compared to conventional density functional theory calculations while maintaining high accuracy, with energy barrier errors below 0.015 eV. Using GPR-NEB, we systematically examine the DDO mechanism on pure Fe(110) and surfaces modified with Co and Ni in both top and subsurface layers. Our results show that subsurface Co and Ni substitutions preserve favorable thermodynamics and kinetics for both C–O bond cleavage and C–H bond formation, comparable to those on the pure Fe(110) surface. In contrast, top-layer substitutions generally increase the C–O bond cleavage barrier, render the step endothermic, and result in significantly higher reverse reaction rates, making DDO unfavorable on these surfaces. This work demonstrates the effectiveness of GRR-accelerated transition state searches for complex surface reactions and provides insights into rational design of bimetallic catalysts for selective deoxygenation.

Aromatic compounds↗
DOE OSTI2022

Resolving Charge Distribution for Compositionally Heterogeneous Battery Cathode Materials

The isostructural nature of Li-layered cathodes allows for accommodating multiple transition metals (TMs). However, little is known about how the local TM stoichiometry influences the charging behavior of battery particles thus impacting battery performance. In this work, we develop heterogeneous compositional distributions in polycrystalline LiNi 1–x–y Mn x Co y O 2 (NMC) particles to investigate the interplay between local stoichiometry and charge distribution. These NMC particles exhibit a broad, continuous distribution of local Ni/Mn/Co stoichiometry, which does not compromise the global layeredness. The local Mn and Ni concentrations in individual NMC particles are positively and negatively correlated with the electrochemically induced Ni oxidation, respectively, whereas the Co concentration does not impose a clear effect on the Ni oxidation. The resulting material delivers excellent reversible capacity, rate capability, and cycle life at high operating voltages. Engineering Ni/Mn/Co distribution in NMC particles may provide a path toward controlling the charge distribution and thus chemomechanical properties of polycrystalline battery particles.

25 ENERGY STORAGE↗
DOE OSTI2022

Simultaneous enhancement of thermally activated delayed fluorescence and photoluminescence quantum yield via homoconjugation

A critical challenge facing thermally activated delayed fluorescence (TADF) is to facilitate rapid and efficient electronic transitions while ensuring a narrow singlet–triplet energy gap (ΔE ST ) in a single luminophore. We present a TADF-active iptycene that clearly demonstrates that homoconjugation can be harnessed as a viable design strategy towards answering this challenge. A homoconjugated analogue of an established quinoxaline-based TADF luminophore has been produced by fusing three of these luminophores together across a shared triptycene core. Homoconjugation was confirmed by electrochemistry, and as a direct consequence of this phenomenon we observed synergistic improvements to photoluminescence quantum yield (Φ PL ), radiative rate of singlet decay ($k^{S}_{r}$), delayed fluorescence lifetime (τ TADF ), and rate of reverse intersystem crossing (k rISC ), all while narrowing the ΔE ST . The enhancement is rationalised with TD-DFT calculations including spin–orbit coupling (SOC). A facile synthesis, the ubiquity of the pyrazine motif in state-of-the-art TADF materials of all colours, and the extent of the overall performance enhancement leads to a great potential for generality.

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

Probing the lattice structure of dynamically compressed and released single crystal iron through the alpha to epsilon phase transition

In this work, experiments using broadband Laue x-ray diffraction (XRD) were used to examine the lattice structure of dynamically compressed [100]-oriented single crystal iron samples at the Dynamic Compression Sector at the Advanced Photon Source. These experiments used 1 μm thick iron single crystal samples sandwiched between a polyimide ablator and a polycarbonate window. A 100 J, 10 ns duration laser pulse incident on the polyimide ablator was used to shock compress the iron samples to initial stresses greater than 25 GPa, exceeding the ~13 GPa alpha (body-centered-cubic or bcc structure) to epsilon (hexagonal-close-packed or hcp structure) phase transition stress. XRD measurements were performed at various times relative to the shock wave entering the iron sample: early times, <~150 ps while the initial shock waves propagated through the iron; intermediate times, after the iron equilibrated with the ablator and window reaching a plateau stress state (12 or 17 GPa) lasting several nanoseconds; and late times, during uniaxial strain release. The early time measurements show that in <~150 ps, the high-pressure hcp phase is relaxed with a c/a ratio of 1.61, contrary to previous laser shock experiments where a c/a ratio of 1.7 was inferred. In the plateau stress state and partially released states, XRD measurements showed that the hcp structure retained a c/a ratio of 1.61 with no observable changes in the microstructure. Upon stress release at ~1 GPa/ns release rate, the reverse phase transition (hcp to bcc) to the original single crystal orientation (implying a transformation memory effect) was observed to reach completion somewhere between 13 and 11 GPa, indicating little stress hysteresis under rapid uniaxial strain release. A similar memory effect for the reverse hcp to bcc transformation has been previously observed under hydrostatic compression. However, the bcc/hcp orientation relationships differ somewhat between dynamic and static compression experiments, implying that the transformation pathway under uniaxial dynamic strain differs from the Burgers mechanism.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Numerical Investigation of Butterfly Valve Performance in Variable Valve Sizes, Positions and Flow Regimes

Reliability and efficiency of valves are necessary for precise control and sufficient heat-flow to heat application plants for the integrated energy systems of nuclear power plants (NPPs). Strategic Management Analysis Requirement and Technology (SMART) valves’ ability to control flow and assess environmental parameters stands out for these requirements. Their ability to sustain the downstream flow rate, prevent reverse flow, and maintain pressure in the heat transport loop is much more efficient with the integration of sensors and intelligent algorithms. For assessing valve performance and monitoring, mechanical design and operating conditions are two important parameters. In this study, the butterfly valves of three different sizes are simulated with water and steam using STAR-CCM+ in various flow regimes and positions to analyze performance parameters to strategize an automated control system for efficiently balancing the heat–transport network. Also, flow behavior is studied using velocity and pressure fields for valve–body geometry optimization. It can be observed, through performance parameters, that the valves are suitable for operation between 30° and 90° positions with significantly low loss coefficients and high flow coefficients, and the performance parameters follow a certain pattern in both water and steam flow in each scenario.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
NASA NTRS1975

Embrittlement of nickel-, cobalt-, and iron-base superalloys by exposure to hydrogen

Five nickel-base alloys (Inconel 718, Udimet 700, Rene 41, Hastelloy X, and TD-NiCr), one cobalt-base alloy (L-605), and an iron-base alloy (A-286) were exposed in hydrogen at 0.1 MN/sq m (15 psi) at several temperatures in the range from 430 to 980 C for as long as 1000 hours. These alloys were embrittled to varying degrees by such exposures in hydrogen. Embrittlement was found to be: (1) sensitive to strain rate, (2) reversible, (3) caused by large concentrations of absorbed hydrogen, and (4) not associated with any detectable microstructural changes in the alloys. These observations are consistent with a mechanism of internal reversible hydrogen embrittlement.

Gray, H. R.↗
NASA NTRS1982

Film-cooling effectiveness with developing coolant flow through straight and curved tubular passages

The data were obtained with an apparatus designed to determine the influence of tubular coolant passage curvature on film-cooling performance while simulating the developing flow entrance conditions more representative of cooled turbine blade. Data comparisons were made between straight and curved single tubular passages embedded in the wall and discharging at 30 deg angle in line with the tunnel flow. The results showed an influence of curvature on film-cooling effectiveness that was inversely proportional to the blowing rate. At the lowest blowing rate of 0.18, curvature increased the effectiveness of film cooling by 35 percent; but at a blowing rate of 0.76, the improvement was only 10 percent. In addition, the increase in film-cooling area coverage ranged from 100 percent down to 25 percent over the same blowing rates. A data trend reversal at a blowing rate of 1.5 showed the straight tubular passage's film-cooling effectiveness to be 20 percent greater than that of the curved passage with about 80 percent more area coverage. An analysis of turbulence intensity detain the mixing layer in terms of the position of the mixing interface relative to the wall supported the concept that passage curvature tends to reduce the diffusion of the coolant jet into the main stream at blowing rates below about. Explanations for the film-cooling performance of both test sections were made in terms differences in turbulences structure and in secondary flow patterns within the coolant jets as influenced by flow passage geometry.

Papell, S. S.↗
NASA NTRS1983

Deep discharge reconditioning: Pros and cons

Deep-discharge reconditioning (DDR) can be of great benefit to battery performance, especially in geosynchronous orbit, if performed properly and regularly, and can be essential to operation of batteries at the high depths of discharge (DOD) required to minimize weight. The procedure should be tailored to fit the nature of the degradation occuring during regular cycling. DDR is not without its drawbacks, however, and these differ depending on the normal DOD to be sustained and/or whether the discharge is done at the battery or the cell level. Battery-level discharge carries the minimum weight penalty but raises questions of the effects of low-rate cell reversal that as yet have no firm answers. Cell level discharge avoids cell reversal but carries significant penalties of weight and complexity. Thus no universal procedure or method of implementation of deep-discharge reconditioning is now available and thus the various approaches must be evaluated for each application.

Scott, W. R.↗
NASA NTRS1992

Quantitative fluorescence measurements of the OH radical in high pressure methane flames

A method for quantifying laser-induced fluorescence signals from the OH radical in high-pressure flames is presented. The fluorescence signal per unit OH mole fraction is modeled as a function of temperature, pressure, and overall flame stoichiometry. Known values of the collisional quenching cross sections as a function of temperature are used to model the electronic quench rate. The reverse A - X (1.0) Q15 transition is used with broadband collection to measure single-point fluorescence produced by a pulsed Nd:YAG-pumped, frequency-doubled dye laser. Laser absorption and thermocouples are used to measure absolute OH concentration and temperature, respectively, which are used to confirm the validity of the model. Measurements are made in CH4/O2/N2 flames up to 10 atm.

Battles, B. E.↗
NASA NTRS1996

Mathematical Model Of Variable-Polarity Plasma Arc Welding

Mathematical model of variable-polarity plasma arc (VPPA) welding process developed for use in predicting characteristics of welds and thus serves as guide for selection of process parameters. Parameters include welding electric currents in, and durations of, straight and reverse polarities; rates of flow of plasma and shielding gases; and sizes and relative positions of welding electrode, welding orifice, and workpiece.

Hung, R. J.↗