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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 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Multimodal Imaging of Autofluorescent Sites Reveals Varied Chemical Speciation in SSZ-13 Crystals

In this report a multimodal imaging study of chabazite is used to analyse emissive deposits. A notable difference is seen in the morphology of agglomerated surface deposits and larger subsurface deposits. Comparison of the distribution of organic residue throughout the crystal volume and XRF mapping is demonstrating that a fluorescence-based technique can also be used to indirectly comment on the compositional chemistry of the inorganic framework. A multimodal imaging study of chabazite is used to show the distribution of and discriminate between different emissive deposits arising as a result of the detemplation process. Confocal imaging, 3D fluorescence lifetime imaging, 3D multispectral fluorescence imaging, and Raman mapping are used to show three different types of emissive behaviours each characterised by different spatial distributions, trends in lifetime, spectral signals, and Raman signatures. A notable difference is seen in the morphology of agglomerated surface deposits and larger subsurface deposits, which experience lifetime augmentation due to spatial confinement. The distribution of organic residue throughout the crystal volume is comparable to XRF mapping that shows Si enrichment on the outer edges and higher Al content through the centre, demonstrating that a fluorescence-based technique can also be used to indirectly comment on the compositional chemistry of the inorganic framework.

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

Ultra-Confined Environments May Restrict the Possible Configurations of Supported Metal Complexes

Here, the rotation frequencies of amido ligands are highly sensitive to the electronic structure of d 0 transition metal complexes and have been used to study ligand donor properties. While attempting to study the donor properties of silanolate ligands in a silica-supported Cr complex, we observed highly restricted motions due to the added steric hindrance from the support, with only approximately half of the amides rotating on a 50 ms time scale. Surprisingly, when the same species is grafted into narrow 2.2 nm pores, all amido ligands are able to rotate. Density functional theory calculations suggest that confinement may limit the possible coordination sites and the configuration of the formed surface species, potentially enabling the formation of conformationally homogeneous surface site populations.

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

Size-dependent chiro-optical properties of CsPbBr 3 nanoparticles

Chiral metal halide perovskites have garnered substantial interest because of their promising properties for application in optoelectronics and spintronics. Understanding the mechanism of chiral imprinting is paramount for optimizing their utility. To elucidate the nature of the underlying chiral imprinting mechanism, we investigated how the circular dichroism (CD) intensity varies with nanoparticle size for quantum confined sizes of colloidal CsPbBr 3 perovskite nanoparticles (NPs) capped by chiral β-methylphenethylammonium bromide ligands. We find that the CD intensity decreases strongly with increasing NP size, which, along with the shape of the CD spectra, points to electronic interactions between ligand and NP as the dominant mechanism of chiral imprinting in smaller NPs. We observe that as the NP size increases and crosses the quantum confinement threshold, the dominant mechanism of chirality transfer switches and is dominated by surfaces effects, e.g., structural distortions. Furthermore, these findings provide a benchmark for quantitative models of chiral imprinting.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Low-mode nonuniformity in direct-drive ICF implosions due to laser smoothing techniques employed on OMEGA

For successful laser-direct-drive inertial confinement fusion implosions, the laser irradiation must be highly uniform over the target surface. On OMEGA, multiple laser beams are used to illuminate targets quasi-uniformly. High-mode-number nonuniformities due to laser speckle on each individual beam are reduced by splitting each beam into two orthogonal polarizations (i.e., polarization smoothing, or PS) and a range of wavelengths (i.e., smoothing by spectral dispersion) that are dispersed at the target plane. However, cross-beam energy transfer (CBET) is sensitive to both the polarizations and wavelengths of the interacting beams, so the interplay between CBET and the laser-smoothing schemes results in unique intensity variation across each beam profile, which is a systematic source of low-mode drive nonuniformity on OMEGA. Here, we model these effects and find that the predicted ℓ = 1 mode in the laser-absorption distribution is consistent with the systematic core-flow direction that has been determined from the OMEGA implosion database. We also observe good agreement with the measured core-flow directions for two specific sets of implosions (one with PS, the other without PS) when we also account for the measured beam mispointing and the beam power imbalance.

Crossed beam scattering↗
DOE OSTI2025

Pathways for Nucleation and Growth in Confined Spaces and at Interfaces

Mineral crystallization is central to myriad natural processes from the formation of snowflakes to stalagmites, but the molecular-scale mechanisms are often far more complex than models reflect. Feedbacks between the hydro-, bio-, and geo-spheres drive complex crystallization processes that challenge our ability to observe and quantify them, motivating an expansion of crystallization theories. Here, in this article, we discuss how the driving forces and timescales of nucleation are influenced by factors ranging from simple geometric confinement to distinct interfacial solution structures involving solvent organization, electrical double layers, and surface charging effects. Taken together, these ubiquitous natural phenomena can preserve metastable intermediates, drive precipitation of undersaturated phases, and modulate crystallization in time and space.

biosphere↗
DOE OSTI2021

Maximizing the Catalytic Performance of Pd@Au x Pd 1- x Nanocubes in H 2 O 2 Production by Reducing Shell Thickness to Increase Compositional Stability

We report a simple route based upon seed-mediated growth to the synthesis of Pd@Au x Pd 1-x (0.8≤x≤1) core–shell nanocubes. Benefiting from the well-defined {100} facets and an optimal Au/Pd ratio for the surface, the nanocubes bearing a shell made of Au 0.95 Pd 0.05 work as an efficient electrocatalyst toward H 2 O 2 production, with high selectivity of 93–100 % in the low-overpotential region of 0.4–0.7 V. When the Au 0.95 Pd 0.05 alloy is confined to a shell of only three atomic layers in thickness, the electrocatalyst is able to maintain its surface structure and elemental composition, endowing continuous and stable production of H2O2 during oxygen reduction at a high rate of 1.62 mol g( Pd+Au ) -1 h -1 . This work demonstrates a versatile route to the rational development of active and durable electrocatalysts based upon alloy nanocrystals.

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

Electrochemical reactivity of atomic and molecular species under solid-state confinement

The nanoconfinement of electrochemically-active guest species in host solid state electrode materials provides opportunities to tune mass transport between the bulk electrolyte and inner surface of the electrode, enhance electron-transfer rates, and/or improve the stability and dispersion of active material. Here, this review summarizes recent experimental and theoretical electrochemical studies of three types of nanoconfined guest species: (1) ion adsorption of electrolyte ions, (2) confined redox-active molecules, and (3) electrocatalytic reactions of confined ions/solvents and catalytic particles. The examples discussed in this review illustrate how the confinement of guest species within enclosed spaces with nanoscale dimensions – such as pores, pockets, channels, and interlayers – can lead to improved electrochemical performance.

25 ENERGY STORAGE↗
DOE OSTI2024

Deposition of ultrathick heavy-metal alloys on rotating substrates by high-power impulse magnetron sputtering: Target erosion effects

Sputter deposition of ultrathick (≈20μm) Au–Ta alloy coatings on sphero-cylindrical substrates is key for the fabrication of hohlraums for magnetically assisted inertial confinement fusion. In this work, we study the deposition of AuTa 4 alloy coatings onto rotating substrates. We use high-power impulse magnetron sputtering (HiPIMS) in a constant peak target voltage mode. Results show that the target erosion state has a strong impact on the dominant crystallographic phase, microstructure, surface morphology, and electrical resistivity of AuTa 4 films. This is due to effects of changes in the confining magnetic field with target erosion on the HiPIMS discharge characteristics and the sputter source output. We quantify these effects via plasma diagnostics and discuss the optimization of HiPIMS deposition of ultrathick films for cases when target erosion effects dominate film properties.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Solid-state NMR and theoretical studies illuminate lanthanum borohydride C–H borylation catalysts confined within a zeolite

Zeolite-supported single-site lanthanum borohydride catalyzes C–H borylation of hydrocarbons, while the related silica-supported complex is inactive under comparable conditions. The identical composition of support-La(BH 4 ) 2 (THF) 2 sites in the two materials implies that the support bestows underlying structural features onto La that are required for bond activation catalysis, yet the nature of these effects, which could include confinement effects and/or electronic modulation of the site itself, remains to be identified. We used solid-state nuclear magnetic resonance (SSNMR) spectroscopy and molecular dynamics simulations with machine-learning potentials (ML-MD) to analyze the electronic and steric effects imparted by the faujasite support on the precatalyst structure to correlate with catalytic activity. ML-MD simulations show that THF dissociates from La under the influence of confinement, leading to coordinatively unsaturated sites in the zeolite pores. Then, the La complex grafts on Brønsted acid sites (La BAS ) or isolated silanols (La SiO ) or remains physisorbed in the zeolite pores. Catalytic studies comparing compounds supported on faujasite zeolites containing or lacking BAS and/or silanols show that only the former complexes lead to active sites, ruling out confinement as the sole requirement for catalysis. The DFT calculations and ML-MD simulations also reveal that the surface-lanthanum coordination number is two (bidentate) for La BAS , with the metal center forming long, flexible bonds to two oxygen atoms bridging Si and Al, but only one oxygen atom (monodentate) for La SiO . The structure–activity relationship identifies confined, BAS-grafted species as active sites and provides important guidance for the design of enhanced atom-efficient catalysts.

Cui, Jinlei [Ames Laboratory, and Iowa State Univ.↗
DOE OSTI2021

Cylindrical Confinement of Nanocolloidal Cholesteric Liquid Crystal

The organization of nanocolloidal liquid crystals in constrained geometries has fundamental and practical importance, since under confinement, liquid crystals contain stable topological defects that can serve as templates for nanoparticle organization. Three-dimensional confinement of cholesteric (Ch) liquid crystals formed by cellulose nanocrystals (CNCs) have been extensively studied; however, their two-dimensional confinement remains underinvestigated. In this work, we report the results of systematic experimental studies of two-dimensional confinement of Ch–CNC liquid crystal in cylindrical capillaries with varying inner diameters. Confinement resulted in phase separation of the Ch–CNC liquid crystal into a Ch shell formed by concentric CNC pseudolayers with the helicoidal axis perpendicular to the inner surface of the capillary walls, and a micrometer-diameter isotropic core thread running parallel to the long axis of the capillary. The morphology of the confined Ch–CNC liquid crystal varied when progressively increasing the degree confinement. Finally, we show that phase separation of the Ch–CNC liquid crystal into a Ch shell and an isotropic core is preserved in flexible capillary tubing, suggesting the applicability of this system for the fabrication of flexible optical waveguides.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Aerosol Optical Tweezers Elucidate the Chemistry, Acidity, Phase Separations, and Morphology of Atmospheric Microdroplets

Aerosol particles represent unique chemical environments because of their high surface area-to-volume ratio that promotes the effects of interfacial chemistry in confined environments. Properties such as viscosity, diffusivity, water content, pH, and morphology—following liquid–liquid phase separation—can strongly alter how a particle interacts with condensable vapors and reactive trace gases, thus modifying its continual evolution and environmental effects. Our understanding of this chemical evolution of atmospheric particulate matter and its environmental impacts is largely limited by our ability to directly observe how these critical particle properties respond to the addition or reactive uptake of new chemical components. Aerosol optical tweezers (AOT) stably trap particles in focused laser beams, providing positional control and the retrieval of many of these critical properties required to understand and predict the chemistry of aerosolized microdroplets. The analytical power of the AOT stems from the retrieval of the cavity-enhanced Raman spectrum induced by the trapping laser. Analysis of the whispering gallery modes (WGMs) that resonate as a standing wave around the droplet’s interface, provide high accuracy measurements of the droplet’s size, refractive index (and thus a measurement of composition), and can distinguish between core–shell, partially engulfed, and homogeneous morphologies. In this study, we have advanced the ability to determine the properties of the core and shell phases in biphasic droplets, including obtaining high-accuracy pH measurements. These capabilities were applied to perform AOT physical chemistry experiments on authentic secondary organic aerosol (SOA) produced directly in the AOT chamber by ozonolysis of terpene vapors. The propensity of the SOA to phase separate as a shell from a wide range of nonpolar to polar core phases was observed, along with the discovery of a stable emulsified state of SOA particles in an aqueous salt droplet. Micron-thick SOA shells did not impede the gain or loss of water or squalane from the core to the surrounding air, indicating no significant diffusional limitations to condensational growth or partitioning even under dry conditions. These experiments formed the foundation of a new framework that predicts how the phase-separated morphology of complex aerosols containing organic carbon evolves during continual atmospheric oxidation processes. Increases in oxidation state will quickly drive conversion from a partially engulfed to core–shell morphology that has dramatically different chemical reactivity since the core phase is completely concealed by the shell. The recent advances in the experimental capabilities of the AOT technique such as presented here enable novel experimental methodologies that provide insights into the chemistry and multidimensional properties of aerosol microdroplets, and how these coevolve and respond to continual chemical reactions.

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

Efficient analysis of magnetic field line behavior in toroidal plasmas

The confinement of plasmas in tokamaks and stellarators depends on magnetic field lines lying in nested toroidal surfaces. The transition near the plasma edge away from the lines lying in magnetic surfaces defines properties of divertors. The transition in time defines properties of disruptions. Divertor design and disruption analyses require a detailed understanding of these transitions. The use of a Fourier transform coupled with a Gaussian window function allows far more information to be extracted about these transitions using far shorter field line integrations than can be obtained using traditional methods based on Poincaré plots. The physics of divertors and disruptions is reviewed to clarify why the type of information that can be gained from more efficient methods of analysis is of central importance to the fusion program based on magnetic confinement.

Boozer, Allen H. [Columbia Univ., New York, NY (Un↗
DOE OSTI2024

Machine learning assisted prediction of tungsten heavy alloy plasma facing component performance for fusion energy applications

Tungsten and tungsten heavy alloys (WHAs), known for their remarkably high hardness, durability, and corrosion resistance, play a critical role in the thriving development of nuclear fusion reactors in recent years. However, the exploration in tungsten alloys for the nuclear-related applications has been limited by the difficulty of manufacturing and the complexity of experiments to reproduce the environment of nuclear reaction. Therefore, this project aims to utilize nanoscale simulation methods such as density functional theory (DFT) and molecular dynamics (MD) with the help of machine learning techniques to not only understand the mechanisms of tungsten alloys but also allow us to computationally predict their mechanical behaviors under extreme environments. One critical problem of the application of WHAs in nuclear reactors is the surface melting. In the current design of the SPARC reactor, the WHA, W97Ni2.1Fe0.9 or W97NiFe, is chosen to be the first wall components to confine the plasma where the particles are fiercely moving and colliding into each other to create nuclear fusion reaction. This process will generate extremely high heat flux onto these WHA tiles, leaving high surface temperature that could possibly melt the surface of the WHA tiles, As illustrated in Fig. 1(a). a laser experiment previously done illustrates that a rough surface damage would be made after the surface melting where the matrix area mainly composed of nickel and iron as shown in Fig. 1(b), will first melt and then leave vacancies between these tungsten grains. Unfortunately, these kinds of roughness on the first-wall components could be deadly to the plasma inside a Tokmak reactor because the heat that is supposed to dissipate at a designed ratio through the tiles may in turn be excessively absorbed and accumulated on any uneven area of the surface, which will eventually make the whole nuclear reaction fail. In this project, we will introduce a machine learning potential, Allegro, based on DFT calculation and then build a MD model for W-Ni-Fe alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Modeling fast ion losses due to tearing and internal kink perturbations in MAST-U

Fast ion (FI) loss properties in the presence of tearing mode and internal kink perturbations are numerically investigated for discharges in the MAST-U spherical tokamak, utilizing the MARS-F magnetohydrodynamic stability code and the REORBIT test particle guiding-center orbit-following module. Here, tracing about 100 000 particle markers sampled from the equilibrium distribution of the neutral-beam injection induced FIs, it is found that about 10% out of the total strike the limiting surface (including the divertor surface) in MAST-U discharge 46943, assuming a maximum perturbation of 100 G inside the plasma (corresponding to ~6 G at the Mirnov probe location at the outboard mid-plane). Detailed particle tracing, assuming a uniform initial distribution in the 2D phase space (at given radial locations), reveals that initially counter-current FIs launched near the plasma edge are subject to significant prompt losses, while almost all initially co-current ions remain well confined at the assumed perturbation level. Most lost FIs strike the lower-half of the limiting surface. Finite gyro-radius effects prevent lost ions from striking the top-outer corner of the super-X divertor chamber. A scan of the perturbation level (based on discharge 45163) reveals, not surprisingly, an approximately linear scaling of the particle loss fraction (for counter-current FIs) with respect to the perturbation amplitude.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Molecular Structure of Adsorbed Water Phases in Silica Nanopores

The adsorption of water vapor in silica nanopores with different pore morphologies and surface hydrophilicities was studied to quantify the densities and thicknesses of the water sorption layers and deduce their molecular structures. Water adsorption to surface hydroxyls is described by a multilayer sorption model. At low pressure, the water adsorption isotherms are largely independent of pore size and the adsorbed amounts scale with the surface hydroxyl density. Adsorbed-phase densities corresponding to the adsorption of two water molecules per surface hydroxyl group are found in the first adsorbed water layer for a wide range of surface hydroxyl densities. The densities and layer thickness values found in narrow pores indicate that patchy adsorbed layers form if not enough water molecules exist for a full layer, which coexist with dry pore surface regions. This behavior indicates cooperative adsorption effects, i.e., a preference for the formation of hydrogen bonds between water molecules bound to surface hydroxyls. In narrow pores, pore condensation limits further growth of the sorption layer, and in larger pores and at the planar quartz surface, a second adsorbed water layer is formed, which can hold up to approximately 4 additional water molecules per surface hydroxyl group. The water molecules in these thicker adsorption layers arrange such that the sorption layer density is similar to the bulk water density. Pore confinement limitations on the sorption layers are observed in pores with radii of as large as 8 nm. Molecular dynamics modeling reveals two preferential orientations for water molecules adsorbing to surface hydroxyl groups and suggests an intralayer structuring in the adsorbed monolayer. Furthermore, adsorbed water molecules in the sorption layer are bonded to the surface hydroxyl group via the donation and acceptance of hydrogen bonds.

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

Moving beyond the Solvent-Tip Approximation to Determine Site-Specific Variations of Interfacial Water Structure through 3D Force Microscopy

Although interfacial solution structure impacts environmental, biological, and technological phenomena, including colloidal stability, protein assembly, heterogeneous nucleation, and water desalination, its molecular details remain poorly understood. Here, we visualize the three-dimensional (3D) hydration structure at the boehmite(010)-water interface using fast force mapping (FFM). Using a self-consistent scheme to decouple long-range tip-sample interactions from short-range solvation forces, we obtain the solution structure with lattice resolution. The results are benchmarked against molecular dynamics simulations that explicitly include the effects of the tip with different levels of approximation and systematically account for tip size, chemistry, and confinement effects. We find four laterally structured water layers within 1 nm of the surface, with the highest water densities at sites adjacent to hydroxyl groups. The key features beyond the first two layers can only be predicted using a full-scale simulation of the boehmite-water-silica system. Our findings further reveal a complex relationship between site-specific chemistry, water density, and long-range particle interactions; and present important advances toward quantitative data interpretation in 3D FFM.

36 MATERIALS SCIENCE↗
DOE OSTI2021

The dominant contribution of Southern Ocean heat uptake to time - evolving radiative feedback in CESM

Radiative feedbacks are found to vary with time in both historical records and future warming projections. Previous studies proposed two factors that determine the variation of radiative feedbacks: (i) the evolution of tropical sea surface warming patterns and (ii) the tropical-extratropical contrast of ocean heat uptake. Our results bridge the two factors by evaluating the remote impact from the extratropical ocean on tropical temperature patterns, accounting for the changes in radiative feedbacks. Based on the Green’s Function approach that quantifies the non-local contributions of regional ocean heat uptake, we show that the net radiative feedback evolution in CESM can be mostly attributed to the heat uptake variations in the Southern Ocean. The enhanced surface warming associated with the weakened heat uptake decades after quadrupling CO2 is not confined over the Southern Ocean, but extends to tropical Southeastern Pacific, which leads to decreasing tropospheric stability and more positive cloud feedbacks.

Lin, Yuan-Jen↗
DOE OSTI2019

Self-assembled Ag(111) nanostructures induced by Fermi surface nesting

Scanning tunneling microscopy measurements on Ag(111)/MoS 2 reveal atomically flat preferred, or “magic,” heights occurring at 6, 10, and 14 atomic layers. We note these results are consistent with Ag growth on a variety of semiconducting substrates and correlate with electronic energy savings in electronic structure calculations of freestanding Ag(111) films. Thus, under certain conditions, Ag will spontaneously form quantized structures independent of the substrate. To explain this, we have found Fermi surface nesting vectors in the bulk Ag band structure which account for these results and the fact Ag that is gapped along the surface normal. This model extends to a range of metallic systems which exhibit electronic confinement, epitaxial growth, and minimal strain. As with Au/MoS 2 , the Ag/MoS 2 system exhibits this behavior at unusually high temperatures so that these principles might be used for control over device features at the nanometer scale under standard fabrication conditions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗