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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 631 records · Page 35
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Correlated spin canting in ordered core-shell Fe 3 O 4 / Mn x Fe 3 - x O 4 nanoparticle assemblies

Polarization-analyzed small-angle neutron-scattering methods are used to determine the spin arrangements and experimental length scales of magnetic correlations in ordered three-dimensional assemblies of ~7.4-nm-diam core-shell Fe 3 O 4 /Mn x Fe 3–x O 4 nanoparticles. In moderate to high magnetic fields, the assemblies display a canted magnetic structure where the canting direction is coherent from nanoparticle to nanoparticle, in contrast to the less extended, more single-particle-like behavior for similar ferrite assemblies. The observed magnetic scattering is modeled by assuming that the interparticle dipolar coupling combined with Zeeman effects in a field leads to nanoparticle domains with preferred net spin alignments relative to packing symmetry axes. Over a range of fields and temperatures, the model qualitatively explains the observed scattering anomalies in terms of clusters that vary in area and thickness, highlighting the complex structures adopted in real, dense nanoparticle systems. Here, the clusters often have a strong two-dimensional magnetic character which is attributed to structural stacking faults and the resulting influence of interparticle dipolar interactions for these magnetically soft nanoparticles.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Temporal mismatches in flight activity patterns between Pipistrellus kuhlii and Prays oleae in olive farms: Implications for biocontrol services potential

Abstract Biocontrol services are widely recognized to provide key incentives for bat conservation. However, we have virtually no information on whether and how disruptions in bat‐mediated biocontrol services are driven by mismatches between the temporal activity patterns of insectivorous bats and insect pests. We investigated the temporal relationship between the nightly activity patterns of the common pipistrelle bat ( Pipistrellus kuhlii ) and the olive fruit moth ( Prays oleae ). Temporal mismatches between species pairs were estimated as the time difference (expressed as a percentage of the night) at which P. kuhlii and P. oleae reached 50% of their abundance. The study was carried out during spring, summer, and fall between 2017 and 2019 in 60 olive farms representing increasing levels of structural simplification (as a surrogate of agricultural intensification). Olive farms were classified as exhibiting high (i.e. HIGH olive farms; n = 27), intermediate (MID; n = 18), and low (LOW; n = 15) structural complexity. Temporal mismatches between the activity levels of P. kuhlii and P. oleae varied between seasons and types of olive farms, being comparatively lower in summer than in spring and fall. Furthermore, summer was the only season in which temporal mismatches between species pairs differed between types of olive farms, with higher temporal mismatches found in LOW than in HIGH and MID olive farms. Overall, our work demonstrates the existence of temporal mismatches between the nightly activity patterns of P. kuhlii and P. oleae . Furthermore, it demonstrates that the structural simplification of olive farms increases temporal mismatches between species pairs, particularly in summer when bat‐mediated biocontrol services are most needed. Synthesis and applications . Future research should consider mismatches between the temporal activity patterns of insectivorous bats and insect pests. Otherwise, the actual impact of agricultural intensification on bat‐mediated biocontrol services as well as the economic impact of their loss on the agriculture industry might be underestimated. To enhance biocontrol services, we propose increasing the availability of suitable roosting and foraging sites as well as conserving areas of remnant native woodland and scattered hollow‐bearing trees.

Herrera, José M.↗
DOE OSTI2022

Tunable CHA/AEI Zeolite Intergrowths with A Priori Biselective Organic Structure‐Directing Agents: Controlling Enrichment and Implications for Selective Catalytic Reduction of NOx

Abstract A novel ab initio methodology based on high‐throughput simulations has permitted designing unique biselective organic structure‐directing agents (OSDAs) that allow the efficient synthesis of CHA/AEI zeolite intergrowth materials with controlled phase compositions. Distinctive local crystallographic ordering of the CHA/AEI intergrowths was revealed at the nanoscale level using integrated differential phase contrast scanning transmission electron microscopy (iDPC STEM). These novel CHA/AEI materials have been tested for the selective catalytic reduction (SCR) of NOx, presenting an outstanding catalytic performance and hydrothermal stability, even surpassing the performance of the well‐established commercial CHA‐type catalyst. This methodology opens the possibility for synthetizing new zeolite intergrowths with more complex structures and unique catalytic properties.

Bello‐Jurado, Estefanía↗
DOE OSTI2022

Tunable CHA/AEI Zeolite Intergrowths with A Priori Biselective Organic Structure‐Directing Agents: Controlling Enrichment and Implications for Selective Catalytic Reduction of NOx

Abstract A novel ab initio methodology based on high‐throughput simulations has permitted designing unique biselective organic structure‐directing agents (OSDAs) that allow the efficient synthesis of CHA/AEI zeolite intergrowth materials with controlled phase compositions. Distinctive local crystallographic ordering of the CHA/AEI intergrowths was revealed at the nanoscale level using integrated differential phase contrast scanning transmission electron microscopy (iDPC STEM). These novel CHA/AEI materials have been tested for the selective catalytic reduction (SCR) of NOx, presenting an outstanding catalytic performance and hydrothermal stability, even surpassing the performance of the well‐established commercial CHA‐type catalyst. This methodology opens the possibility for synthetizing new zeolite intergrowths with more complex structures and unique catalytic properties.

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

Real-time interface investigation on degradation mechanism of organic light-emitting diode by in-operando X-ray spectroscopies

Understanding the chemical evolution at the interface of organic light-emitting diodes (OLEDs) under working conditions is critical for addressing device failure and further improving performance. In this work, an in-operando approach was developed employing synchrotron-based X-ray absorption spectroscopy (XAS) to investigate the electronic structures and chemical degradation mechanisms of a model tris(8-hydroxyquinoline) aluminum (Alq 3 )-based OLED device under working condition. The results identify that Mg atoms from the electrode migrate into the Alq 3 organic layer under a potential bias and replace Al atom sites, forming the unstable Mgq 3 species which lead to device degradation. Here, the findings from the classic and simple model device elucidate the degradation mechanisms occurred at the interface of OLED devices, which may facilitate the development of more efficient and stable OLED devices with complex structures.

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

Material Developments for 3D/4D Additive Manufacturing (AM) Technologies

Additive Manufacturing (AM), or 3D printing, is a unique technology in which structurally complex objects can be easily manufactured. While AM allows for the creation of intricate 3D objects, these objects are inactive and motionless. With recent incorporation of a “pre-programmed functionality’’ to the 3D printed objects, a new concept has emerged, 4D printing. Specifically, the 4D printing technology enables a static 3D printed object to change its shape, functionality or property over time upon exposure to a specific stimulus such as heat, stress, light, pH, and moisture, etc. We designed and produced compact 3D/4D printable materials that can be used as (a) structural components of the unmanned aerial vehicles (UAVs), and (b) as hydrogen storage materials that supply hydrogen to a fuel cell to expand the operational reach, namely flight time, and endurance of the UA Vs.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Material Developments for 3D/4D Additive Manufacturing (AM) Technologies

Additive Manufacturing (AM), or 3D printing, is a unique technology in which structurally complex objects can be easily manufactured. While AM allows for the creation of intricate 3D objects, these objects are inactive and motionless. With recent incorporation of a “pre-programmed functionality” to the 3D printed objects, a new concept has emerged, 4D printing. Specifically, the 4D printing technology enables a static 3D printed object to change its shape, functionality or property over time upon exposure to a specific stimulus such as heat, stress, light, pH, and moisture, etc. We designed and produced compact 3D/4D printable materials that can be used as (a) structural components of the unmanned aerial vehicles (UAVs), and (b) as hydrogen storage materials that supply hydrogen to a fuel cell to expand the operational reach, namely flight time, and endurance of the UAVs.

08 HYDROGEN↗
DOE OSTI2023

Structural and Mechanistic Basis for the Inactivation of Human Ornithine Aminotransferase by (3 S ,4 S )-3-Amino-4-fluorocyclopentenecarboxylic Acid

Ornithine aminotransferase (OAT) is overexpressed in hepatocellular carcinoma (HCC), and we previously showed that inactivation of OAT inhibits the growth of HCC. Recently, we found that (3S,4S)-3-amino-4-fluorocyclopentenecarboxylic acid (5) was a potent inactivator of γ-aminobutyric acid aminotransferase (GABA-AT), proceeding by an enamine mechanism. Here we describe our investigations into the activity and mechanism of 5 as an inactivator of human OAT. We have found that 5 exhibits 10-fold less inactivation efficiency (k inact /K I ) against hOAT than GABA-AT. A comprehensive mechanistic study was carried out to understand its inactivation mechanism with hOAT. pK a and electrostatic potential calculations were performed to further support the notion that the α,β-unsaturated alkene of 5 is critical for enhancing acidity and nucleophilicity of the corresponding intermediates and ultimately responsible for the improved inactivation efficiency of 5 over the corresponding saturated analogue (4). Intact protein mass spectrometry and the crystal structure complex with hOAT provide evidence to conclude that 5 mainly inactivates hOAT through noncovalent interactions, and that, unlike with GABA-AT, covalent binding with hOAT is a minor component of the total inhibition which is unique relative to other monofluoro-substituted derivatives. Furthermore, based on the results of transient-state measurements and free energy calculations, it is suggested that the α,β-unsaturated carboxylate group of PLP-bound 5 may be directly involved in the inactivation cascade by forming an enolate intermediate. Overall, compound 5 exhibits unusual structural conversions which are catalyzed by specific residues within hOAT, ultimately leading to an enamine mechanism-based inactivation of hOAT through noncovalent interactions and covalent modification.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Understanding the Impacts of Support–Polymer Interactions on the Dynamics of Poly(ethyleneimine) Confined in Mesoporous SBA-15

Supported amines are a promising class of CO 2 sorbents offering large uptake capacities and fast uptake rates. Additionally, among supported amines, poly(ethyleneimine) (PEI) physically impregnated in the mesopores of SBA-15 silica is widely used. Within these composite materials, the chain dynamics and morphologies of PEI strongly influence the CO 2 capture performance, yet little is known about chain and macromolecule mobility in confined pores. Here, we probe the impact of the support–PEI interactions on the dynamics and structures of PEI at the support interface and the corresponding impact on CO 2 uptake performance, which yields critical structure–property relationships. The pore walls of the support are grafted with organosilanes with different chemical end groups to differentiate interaction modes (spanning from strong attraction to repulsion) between the pore surface and PEI. Combinations of techniques, such as quasi-elastic neutron scattering (QENS), 1 H T 1 –T 2 relaxation correlation solid-state NMR, and molecular dynamics (MD) simulations, are used to comprehensively assess the physical properties of confined PEI. We hypothesized that PEI would have faster dynamics when subjected to less attractive or repulsive interactions. However, we discover that complex interfacial interactions resulted in complex structure–property relationships. Indeed, both the chain conformation of the surface-grafted chains and of the PEI around the surface influenced the chain mobility and CO 2 uptake performance. By coupling knowledge of the dynamics and distributions of PEI with CO 2 sorption performance and other characteristics, we determine that the macroscopic structures of the hybrid materials dictate the first rapid CO 2 uptake, and the rate of CO 2 sorption during the subsequent gradual uptake stage is determined by PEI chain motions that promote diffusive jumps of CO 2 through PEI-packed domains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Experimental and computational study of thaumasite structure

The structure of thaumasite has been studied experimentally by means of a single crystal X-ray diffraction and FTIR methods, and theoretically using density functional theory (DFT) method. Very good agreement was achieved between calculated and experimental structural parameters. In addition, calculations offered the refinement of the positions of the hydrogen atoms. The detailed analysis of the hydrogen bonds existing in the thaumasite structure has been performed. Several types of hydrogen bonds have been classified. The water molecules coordinating Ca{sup 2+} cation act as proton donors in moderate O-H···O hydrogen bonds formed with CO₃⁻²and SO₄⁻² anions. The multiple O-H···O hydrogen bonds exist among water molecules themselves. Finally, relatively weak hydrogen bonds form water molecules with the OH groups from the coordination sphere of the Si(OH)₆⁻² anion. Further, calculated vibrational spectrum allowed complete assignment of all vibrational modes which are not available from the experimental spectrum that has a complex structure with overlapped bands, especially below 1500 cm⁻¹. Highlights: • The thaumasite structure was studied experimentally and using DFT method. • We used DFT method for the refinement of the positions of hydrogen atoms. • A detailed analysis of the hydrogen bonds was done. • A complete assignment of all bands to particular types of vibrations was done.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Measurement of Physicochemical Properties of Lignin

Lignin is an essential cell wall component of lignocellulose. Unlike other major components such as cellulose and hemicellulose, lignin is a noncarbohydrate biopolymer and contributes to cell wall rigidity and hydrophobicity. Lignin’s unique properties contribute to the transportation of water and minerals in plants and protect against microbial attacks, while the latter property hinders the conversion of carbohydrates in lignocellulose. Also, its heterogeneity and structural complexity are major recalcitrance factors in biomass conversion. Various approaches (including genetically engineered plants, pulping, pretreatments, and fractionation processes) have been proposed to reduce and/or remove lignin for effective conversion of lignocellulose. Recently, interest in the biorefinery concept considers lignin as a potential feedstock in many applications; however, the technologies necessary to facilitate the economic production of many lignin-based products is still in its infancy. For the effective utilization of lignocellulose, understanding the physicochemical properties of lignin is the first and last step. It not only provides the key information about lignin structures in the original plant cell wall, conversion products, or residues, but also explains how the modification and/or conversion process affects lignin and biomass in general. Many different lignin characteristics, including physicochemical, morphological, and thermal properties, can be measured by diverse analytical techniques. This chapter introduces analytical methods that measure several essential physicochemical properties of lignin, such as molecular weights by gel permeation chromatography (GPC), quantitative and qualitative information of structural properties (interunit linkages and aromatic subunits) by one-dimensional and two-dimensional nuclear magnetic resonance (NMR), and hydroxyl group content by 31P NMR.

Yoo, Chang Geun↗
DOE OSTI2019

Tunable internal quantum well alignment in rationally designed oligomer-based perovskite films deposited by resonant infrared matrix-assisted pulsed laser evaporation

Hybrid perovskites incorporating conjugated organic cations enable unusual charge carrier interactions among organic and inorganic structural components, but are difficult to prepare as films due to disparate component chemical/physical characteristics (e.g., solubility, thermal stability). In this work, we demonstrate that resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) mitigates these challenges, enabling facile deposition of lead-halide-based perovskite films incorporating variable-length oligothiophene cations. Density functional theory (DFT) predicts suitable organic and inorganic moieties that form quantum-well-like structures with targeted luminescence or exciton separation/quenching. RIR-MAPLE-deposited films enable confirmation of these predictions by optical measurements, which further display excited state behavior transcending traditional quantum-well models—i.e., with appropriate selection of specially synthesized organic/inorganic moieties, intercomponent carrier transfer efficiently converts excitons from singlet to triplet states in organics for which intersystem crossing cannot ordinarily compete with recombination. These observations demonstrate the uniquely versatile excited-state behavior in hybrid perovskite quantum wells, and the value of integrating DFT, organic synthesis, RIR-MAPLE and spectroscopy for screening/preparing rationally devised complex structures.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Charge accumulation and solvation in $β$-NiOOH: Surface chemistry of an OER catalyst from ML-aided simulations

Electrochemical water splitting is a key technology for a sustainable energy transition, providing a route to store surplus electricity from renewable sources. A central bottleneck is the sluggish oxygen evolution reaction (OER), which drives the search for catalysts that are active, stable, and inexpensive enough for large-scale deployment. Within this context, pure and doped NiO x H y combine high activity with low cost, making them prime candidates for alkaline OER. Yet, despite extensive study, the atomistic structure of NiOOH under operando conditions and the associated reaction mechanisms remain debated. Here, we investigate the structural complexity of pure β-NiOOH, the scaffold for its doped derivatives. We systematically investigate the oxidation of the surface adsorbates via proton-coupled electron transfer steps across relevant facets and sites, identifying the most probable sequence of deprotonation events. Our results reveal asymmetric charge accumulation on Wulff-relevant surfaces and show how applied potential can promote morphological restructuring. Explicit solvation is included through machine-learning interatomic potential molecular dynamics of the NiOOH/water interface, which allows us to resolve the hydrophobic and hydrophilic character of different surfaces and the associated interfacial water structure. Together, these insights demonstrate how surface chemistry and solvation jointly govern the stability of NiOOH and the accumulation of surface charge, with possible implications for catalytic performance.

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

Functional Ion Pair Receptors Targeting Cesium, Lithium, Sulfate, and Uranyl (Final Technical Report)

The major goal of this project was the synthesis and study of receptors for key ions of interest to the DOE mission, namely cesium, lithium, sulfate, hydroxide, carbon dioxide/bicarbonate, and early actinides. The work, fundamental in nature, had as its objective achieving an increased understanding of how changes in receptor design could be used to optimize binding energies, ion specificity, complex structure, extraction efficiency, and substrate release. Within this broad paradigm, particular emphasis was placed on systems that could be used to sense the cesium cation in mixed aqueous media and act as extractants for the lithium cation and, separately, the carbon dioxide/bicarbonate and hydroxide anions in the form of ion pairs likely to be encountered under conditions of putative use in the field. The development of new nitrogen-rich ligands that act as receptors for early, high-valent actinide cations was also a major point of emphasis. The first in-plane actinide complexes were synthesized using a hexa-aza porphyrin analogue. The complexes exhibited an increase in the ligand–metal bonding covalency on passing from thorium(IV) to uranium(IV) to neptunium(IV) and illustrates how the use of appropriate porphyrinoid-like ligands could be used to modulate the covalency interactions between an f-element metal center and a ligand.

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

Crystal structure of [Th 3 (Cp*) 3 (O)(OH) 3 ] 2 Cl 2 (N 3 ) 6 : a discrete molecular capsule built from multinuclear organothorium cluster cations

An unusually large and structurally complex charge-neutral polynuclear cluster, hexa-μ 2 -azido-di-μ 3 -chlorido-hexa-μ 2 -hydroxido-di-μ 3 -oxido-hexakis(pentamethylcyclopentadienyl)hexathorium–diethyl ether–tetrahydrofuran (1/0.56/1.44), [Th 3 (C 10 H 15 ) 6 Cl 3 (N 3 ) 6 (OH) 6 O 2 ]·0.56C 4 H 10 O·1.44C 4 H 8 O or [Th 3 (Cp*) 3 (O)(OH) 3 ] 2 Cl 2 (N 3 ) 6 ·0.56C 4 H 10 O·1.44C 4 H 8 O (Cp* = [pentamethylcyclopentadienyl]) − , has been crystallized as a mixed tetrahydrofuran/diethyl ether solvate and structurally characterized. The molecule contains a number of unusual features, the most notable being a finite yet exceptionally long cyclic metal-azido chain. These rare features are the consequence of both sterically protecting Cp* ligands and highly bridging oxide and hydroxide ligands in the same system and illustrate the interesting new possibilities that can arise from combining organometallic and solvothermal f -block element chemistry.

Kelley, Steven P.↗
DOE OSTI2017

Toward High Fidelity LES Simulations of 5 x 5 PWR Fuel Bundle with Mixing Vane

The present work illustrates one example of a computational fluid dynamics (CFD) application in the nuclear engineering field. Since CFD is one of the most powerful tools available at the actual state of the art that could in principle help and assist the design process, a compromise should be established between the accuracy of the CFD numerical model (RANS - LES - DNS) and the computational cost of the simulations. In this spirit, this work will present the computational results from two different CFD model categories, Large Eddy Simulations (LES) and Reynolds-averaged Navier-Stokes (RANS) models. Both treat the flow turbulence issue in two separate ways, which differ mostly in the resolution of the turbulence statistics and the computational cost. The single-phase hydraulic problem presented involves the steady-state turbulent flow field modelling and resolution around a scaled PWR mixing vane grid, designed by Westinghouse and tested by Texas A and M University. The role of the mixing vane/spacer grid is to enhance the turbulent mixing and hence heat transfer of the core coolant around fuel bundles, thus increasing the departure of nucleate boiling-critical heat flux (DNB-CHF) point, as well as important structural functions for the rods bundles. The authors numerically studied the flow field characteristics at the region downstream of the spacer grids and validated their results to particle imagery velocimetry (PIV) measurements. Dominguez and Hassan performed two-dimensional time resolved PIV (TR-PIV) measurements within a 5 x 5 PWR rod bundle with spacer-grids that utilized a matching index of refraction (MIR) approach. Their averaged data showed a rather uniform direction velocity profile after the spacer grid while the downstream illustrated a no slip wall profile. The available PIV flow field experimental results from Texas A and M show complex structures of the flow field downstream the mixing vanes with the formation of secondary flows that tend to enhance the turbulent heat transfer, due to the mixing vanes geometry itself. Computational results will be validated with the available experimental data.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2020

Thermally induced cracking on the massive concrete structure of the NSLS II synchrotron and its engineering remediation

Synchrotron accelerator facilities such as the NSLS II require extreme stability, both transient (short-term) and quasi-static (long-term) to achieve the desired resolution performance. Consequently, even μm-level movements, particularly differential movements between locations in the concrete structure supporting the accelerator electron beam lattice (storage ring) or high sensitivity experiments (experimental floor) will lead to serious degradation of its performance. Differential settlement in the overall structure or structural movement exceeding anticipated levels will inevitably degrade the performance and will require intervention. Presented in this paper are the design philosophy of the NSLS II ring structure favoring a monolithic ring, the observed cracking behavior of the young NSLS II concrete following casting and in combination with extreme ambient temperature fluctuation, the results of a non-linear, high-fidelity numerical analysis used to emulate the observed cracking and establish the driving mechanism, the numerical analysis-based identification of the crack-arresting solution and finally the implementation of the remediation solution and the long-term performance of the adopted engineering solution. The multi-stage process revealed that computational methods such as non-linear finite element methods have the potential of providing engineering guidance even when complex structures and in combination with non-linear materials, such as steel reinforcement and concrete are involved.

42 ENGINEERING↗