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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 73 records · Page 4

A simple formula for estimating Stark widths of neutral lines

A simple formula for the prediction of Stark widths of neutral lines similar to the semiempirical method of Griem (1968) for ion lines is presented. This formula is a simplification of the quantum-mechanical classical path impact theory and can be used for complicated atoms for which detailed calculations are not readily available, provided that the effective position of the closest interacting level is known. The expression does not require the use of a computer. The formula has been applied to a limited number of neutral lines of interest, and the width obtained is compared with the much more complete calculations of Bennett and Griem (1971). The agreement generally is well within 50% of the published value for the lines investigated. Comparisons with other formulas are also made. In addition, a simple estimate for the ion-broadening parameter is given.

Freudenstein, S. A.↗

Medium controlled aggregative growth as a key step in mesoporous silica nanoparticle formation

Near monodisperse mesoporous silica nanoparticles (MSN) represent a promising and rapidly developing type of mesoporous silica materials; however, the vast data on their synthesis remains unorganized and ill-understood. We systematically studied the formation of MSN under basic and neutral conditions using various temperatures, CTAB concentrations, hydrolyzing agents (triethanolamine, ammonia, phosphate buffers), and media with different colloidal stabilization properties (with ethanol as a cosolvent and monovalent salts). In the typical conditions for the preparation of stable MSN colloids, the particle size was controlled by colloidal stabilization by the medium (solvent type, ionic strength, and surfactant concentration) in agreement with the “aggregative growth” mechanism, rather than by solely the hydrolysis and condensation rates conventionally used for data interpretation in the classical nucleation theory. Medium properties (pH, ion types and concentration, polarity) also defined the efficiency of silica-surfactant cooperative self-assembly, which directly affected the porosity, mesopore size and pore wall thickness. Interestingly, this traditional silica-surfactant route showed a limited effect on the particle size, emphasizing the dominating role of colloidal stabilization in the studied reaction conditions. In situ pH measurements showed that every reaction medium has unique pH evolution profiles depending on the buffer capacity, hydrolysis and condensation rates. Reaction systems that fail to maintain the working pH can lead to non-porous products or undesired particle morphology and size distribution. The established particle formation mechanism allowed us to formulate comprehensive guidelines for preparing relatively concentrated colloids of near monodisperse (PDI 5–15%) mesoporous 30–700 nm silica spheres with variable porosity and mesopore size. Here, these findings will be particularly useful in designing new mesoporous silica-containing materials for biomedical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Insight into the deformation features and capacity loss mechanisms of lithium-ion pouch cells under spherical indentation conditions

Mechanical deformation under extreme conditions is one of the important reasons for the failure of lithium-ion batteries in automotive application. However, the deformation features and component failure of lithium-ion cells to external loading has never been a design consideration. Here, in this study, we conduct spherical indentation tests on a dozen of lithium-ion cells with different capacities under different control mode conditions to investigate their deformation features and capacity loss mechanisms. The experimental results show that, under mechanical deformation conditions, internal faults of cells occur in stages, and energy accumulation and sudden release are two key processes of cell's mechanical failure. The cells' state of charge is the main factor affecting their thermal runaway behaviors. In addition, a finite element model is developed to simulate the deformation features and the failure mechanism of key components of lithium-ion pouch cells; the 3D x-ray computed tomography is employed to demonstrate its internal configuration. With this model, the force-strain response, the deformation features as well as the size of the failure area of lithium-ion cells under spherical indentation conditions are accurately predicted. In 3D x-ray computed tomography images, unique mud cracks in cooper current collector are observed, and the influence mechanisms of the isolated fragments on the cell capacities are revealed. These results may provide useful information for the mechanical structure design of the components of lithium-ion pouch cells.

25 ENERGY STORAGE↗

Sputtering of SO2 by high energy ions

Sputtering yields of solid SO2 by high energy ions were measured in order to study the mechanism for sputtering dielectrics with ions in the electronic stopping power region. The incident ions were helium and fluorine with energies ranging from 1.5 MeV to 25 MeV. Yields as high as 7000 SO2 molecules/incident F ion were measured; the 1.5 MeV He-4 beam had a sputtering yield of 50. The data are compared to yield measurements made on UF4 and H2O targets. There is a striking similarity in the yield as a function of the incident F energy for all three targets. The data compare favorably with theoretical yield curves based on a new model for the sputtering which considers the electronic excitations induced in the target by the incident beam. Measurements and calculations of this sort are also useful in understanding processes which occur on the surface of Jupiter's satellite Io, which is covered with SO2 frost and bombarded by energetic ions trapped in the Jovian magnetosphere.

Lepoire, D. J.↗

Compositional Impact of Io Volcanic Emissions on Jupiter's Magnetosphere and the Icy Galilean Moons

The magnetospheric ion population of Jupiter is dominated by the 1000 kg/s of iogenic material constantly ejected by IO volcanism as neutral gas (approx. 1 kg/s goes out as high speed dust grains), subsequent atmospheric losses to the IO torus, and radial transport of torus ions throughout the magnetosphere. As that magnetosphere is greatly distended in radial size by the iogenic plasma loading, so are surfaces of the other Galilean moons also significantly, and perhaps even dominantly, affected by iogenic plasma bombardment, e.g. at the level up to 0.2 kg/s heavy ions (mostly O and S) onto Europa as per local plasma ion measurements. In comparison, cometary impacts onto IO deliver about 0.02 kg/s of impact ejecta to Europa via ballistic transfer through the Jupiter system. The magnetosphere of this system operates as a powerful engine to produce and transport ions from the IO source to the surfaces of these other moons, and any future orbiter missions to these moons must account for surface distributions of the iogenic material and its chemical effects before real assessments can be made of sensible chemical materials otherwise arising from primordial formation and subsequent evolution of these moons. This is a fundamental problem of space weathering that must be addressed for all planetary bodies with thin atmospheres and direct surface exposure to their space plasma environments. Long-standing debates from Galileo Orbiter measurements about the origins of hydrate sulfates at Europa present examples of this problem, as to whether the sulfates arise from oceanic minerals or from iogenic sulfur chemistry. Any orbiter or landed mission to Europa for astrobiological investigations would further need to separate the potential chemical biosignatures of life or its precursors from the highly abundant background of iogenic material. Although no single ion carries a tag identifying it as of iogenic or other origin, the elemental abundance distributions of ions to be measured throughout the jovian magnetosphere and in the local moon environments can act as tracers if we know from direct measurements and models the distributions at the mostly likely sources, i.e. at IO. However, our knowledge of these abundances are very limited from earlier in-situ and remote measurements, mainly confined to major (S, O) and some minor (Na, K, Cl) species with abundances at or above a few percent relative to O. Future in-situ plasma measurements by the planned Jupiter Europa Orbiter and Jupiter Ganymede Orbiter missions should extend the abundance coverage to minor and even trace elemental species. For Europa astrobiological investigations it is also important to specify iogenic inputs and surface processing of isotopic species. We discuss the range of abundance distributions arising from models for IO hot volcanic emissions, and from the subsequent dynamics of ion injection, magnetospheric transport, and icy moon surface bombardment.

Cooper, John↗

Site-Selective Modification of Lanthanum Oxychloride to Modulate Halide-Ion Conduction

Design principles for solid-state halide-ion conduction remain poorly defined despite the increasing importance of halide ions as charge carriers in a variety of energy storage and electrochemical computing technologies. Here, we employ a siteselective modification strategy in which aliovalent cations are preferentially introduced at the La 3+ crystallographic site of LaOCl in the 2c Wyckoff position, enabling controlled generation of chloride vacancies and modification of lattice dynamics to enhance chloride-ion conductivity. Aliovalent substitution of La 3+ with Mg 2+ , Ca 2+ , and Sr 2+ generates charge-compensating Cl vacancies while preserving the matlockite crystal structure. X-ray excited optical luminescence measurements with Dy 3+ as a reporter chromophore evidence vacancy-derived midgap electronic states and an extended energy range of radiation-less Auger electron emission corresponding to substantial modification of electronic structure and local electrostatic potentials. Ca alloying at 8−10 at. % increases the chloride-ion conductivity by three- to 4 orders of magnitude as compared to unalloyed LaOCl, whereas comparable amounts of Sr- and Mg-alloying in LaOCl imbue less pronounced conductivity enhancements. Temperature-dependent Raman spectroscopy measurements reveal that Ca- and Sr-alloying substantially soften the La−Cl sublattice and yield a more compliant crystal lattice that can deform to accommodate Cl-ion migration. Structure solutions derived from Rietveld refinements to powder Xray diffraction reveal larger O−La−Cl bond-angle deviations and enhanced out-of-plane cation displacements for Ca- and Sr-alloyed compositions as compared to Mg-alloyed LaOCl. Such local distortions enhance chloride-ion mobility by reshaping and flattening vacancy migration energy landscapes and by modulating lattice dynamics governing anion conduction. We further illustrate that coalloying of Ca with Mg and Sr induces a nonmonotonic conductivity−defect stoichiometry relationship that can be rationalized based on cooperative interactions. Together, these results establish site-selective aliovalent alloying of LaOCl as an effective route to halide-ion solid electrolytes and provide broadly generalizable design principles for site-selective modification to induce vacancy formation and lattice softening to engender facile anion transport

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atmospheric measurements using the LAMP lidar during the LADIMAS campaign

The results of the LAtitudinal DIstribution of Middle Atmosphere Structure (LADIMAS) experiment have provided a unique data set to improve our understanding of the middle atmosphere. The project included shipboard and rocket range coordinated measurements between 70 deg N to 65 deg S to study the structure, dynamics, and chemistry of the atmosphere. Results on important dynamical processes, such as gravity waves, tidal components, as well as the formation of the layers of meteoric ion and neutral species, were obtained with lidar, digisonde, microwave radiometer, and spectrometers. The cooperative study of the atmosphere was undertaken by researchers from several laboratories, including Penn State University (PSU), University Bonn, University Wuppertal, Lowell University, and others. Several of the parameters studied have never been measured before over such a wide range of latitudes. Instruments were assembled aboard the German research vessel RV POLARSTERN while this vessel was sailing from the Arctic to the Antarctic seas between 8 Oct. 1991 - 2 Jan. 1992. This paper presents an introduction to the data gathered by the PSU investigation with the Lidar Atmospheric Measurements Program (LAMP) lidar.

Philbrick, C. R.↗

Method bacterial endospore quantification using lanthanide dipicolinate luminescence

A lanthanide is combined with a medium to be tested for endospores. The dipicolinic acid released from the endospores binds the lanthanides, which have distinctive emission (i.e., luminescence) spectra, and are detected using photoluminescence. The concentration of spores is determined by preparing a calibration curve generated from photoluminescence spectra of lanthanide complex mixed with spores of a known concentration. A lanthanide complex is used as the analysis reagent, and is comprised of lanthanide ions bound to multidentate ligands that increase the dipicolinic acid binding constant through a cooperative binding effect with respect to lanthanide chloride. The resulting combined effect of increasing the binding constant and eliminating coordinated water and multiple equilibria increase the sensitivity of the endospore assay by an estimated three to four orders of magnitude over prior art of endospore detection based on lanthanide luminescence.

Ponce, Adrian↗

Practical Battery Thermal Modeling Techniques

Lithium-ion batteries are thermo-electrochemical devices, whereby nearly every facet of their functionality and performance are thermally driven. As a result, it is important to have thermal modeling techniques that effectively capture the intricacies of both the electrochemical nature of the battery and also the complex thermal network that typically results from the design of the battery thermal management system. Here we present a thermal modeling workflow and a set of general assumptions for how to construct a thermal model of a Li-ion battery pack. We use a 14-cell bank of 18650-format Li-ion cells, loosely based on a proposed alternative battery design for Orion, as the example. Although the workflow is performed with Thermal Desktop and related utilities, the focus of this presentation is less about software specific techniques, but rather is focused on the assumptions and conditions that should be used in a model (regardless of the tool used to build the model). Example cases and results will be presented for charge, discharge, and thermal runaway.

lithium-ion battery↗

Development of the first 1 GHz niobium-tin quarter-wave cavity

Niobium-Tin (Nb3Sn) is a promising alternative to pure niobium for low-beta ion accelerators due to low RF losses even at high frequencies. At 4.5 K, the expected Bardeen-Cooper-Schrieffer resistance of Nb3Sn is a few nano-Ohms at 1 GHz, with two orders of magnitude improvement compared to pure niobium. The low Nb3Sn RF losses allow the use of higher frequency, much smaller cavities while maintaining 4.5 K operation that is compatible with cryocoolers. This work aims to demonstrate the feasibility of coating a high-frequency 1 GHz, compact quarter-wave cavity. The development of this cavity has the potential to transform low-beta ion accelerators through size reductions and by enabling the replacement of large helium cryoplants with small plug-in cryocoolers. We have designed, built, and tested a 1GHz Nb3Sn coated quarter-wave cavity. Nb3Sn coating has been performed once by vapor diffusion at Fermilab. Cryogenic cold tests show a quality factor of ~1E9 at low accelerating electric fields or ~7 times higher than the theoretical limit for pure niobium at 1GHz. This first coating does not yet meet our quality factor or gradient goals; however, we plan to continue to develop this cavity.

Zhou, Yang [Argonne]↗

Compact Submillimeter-Wave Receivers Made with Semiconductor Nano-Fabrication Technologies

Advanced semiconductor nanofabrication techniques are utilized to design, fabricate and demonstrate a super-compact, low-mass (<10 grams) submillimeter-wave heterodyne front-end. RF elements such as waveguides and channels are fabricated in a silicon wafer substrate using deep-reactive ion etching (DRIE). Etched patterns with sidewalls angles controlled with 1 deg precision are reported, while maintaining a surface roughness of better than 20 nm rms for the etched structures. This approach is being developed to build compact 2-D imaging arrays in the THz frequency range.

Silicon micromachining↗

Dissociative Ionization and Product Distributions of Benzene and Pyridine by Electron Impact

We report a theoretical study of the dissociative ionization (DI) and product distributions of benzene (C6H6) and pyridine (C5H5N) from their low-lying ionization channels. Our approach makes use of the fact that electronic motion is much faster than nuclear motion allowing DI to be treated as a two-step process. The first step is the electron-impact ionization resulting in an ion with the same nuclear geometry as the neutral molecule. In the second step, the nuclei relax from the initial geometry and undergo unimolecular dissociation. For the ionization process we use the improved binary-encounter dipole (iBED) model [W.M. Huo, Phys. Rev. A64,042719-I (2001)]. For the unimolecular dissociation, we use multiconfigurational self-consistent field (MCSCF) methods to determine the steepest descent pathways to the possible product channels. More accurate methods are then used to obtain better energetics of the paths which are used to determine unimolecular dissociation probabilities and product distributions. Our analysis of the dissociation products and the thresholds of their productions for benzene are compared with the recent dissociative photoionization meausurements of benzene by Feng et al. [R. Feng, G. Cooper, C.E. Brion, J. Electron Spectrosc. Relat. Phenom. 123,211 (2002)] and the dissociative photoionization measurements of pyridine by Tixier et al. [S. Tixier, G. Cooper, R. Feng, C.E. Brion, J. Electron Spectrosc. Relat. Phenom. 123,185 (2002)] using dipole (e,e+ion) coincidence spectroscopy.

Dateo, Christopher E.↗

High- Q Nanophotonic Resonators on Diamond Membranes using Templated Atomic Layer Deposition of TiO 2

Integrating solid-state quantum emitters with nanophotonic resonators is essential for efficient spin-photon interfacing and optical networking applications. While diamond color centers have proven to be excellent candidates for emerging quantum technologies, their integration with optical resonators remains challenging. Conventional approaches based on etching resonators into diamond often negatively impact color center performance and offer low device yield. In this work, we developed an integrated photonics platform based on templated atomic layer deposition of TiO 2 on diamond membranes. Our fabrication method yields high-performance nanophotonic devices while avoiding etching wavelength-scale features into diamond. Moreover, this technique generates highly reproducible optical resonances and can be iterated on individual diamond samples, a unique processing advantage. Our approach is suitable for a broad range of both wavelengths and substrates and can enable high-cooperativity interfacing between cavity photons and coherent defects in diamond or silicon carbide, rare earth ions, or other material systems.

42 ENGINEERING↗

The Role of Protons and Hydrides in the Catalytic Hydrogenolysis of Guaiacol at the Ruthenium Nanoparticle-water Interface

The mechanistic roles of free hydronium ions, surface hydrides, and interfacial protons during guaiacol hydrodeoxygenation (HDO) on ruthenium nanoparticles are established. As guaiacol adsorbs on Ru, it loses its strong aromaticity and undergoes a rapid H-shift from its hydroxyl to meta carbons (in relation to its hydroxyl group), leading enol and keto surface isomers to exist in chemical equilibrium. HDO occurs via a hydridic H-adatom (H*) attack to the enol, followed by a kinetically relevant C-O bond rupture step, during which water shuttles the hydroxyl proton, enabling its intramolecular attack to the methoxy, evolving a high charged [Ru(s)-(C6H5O-)…(H+)…OCH3]† transition state. The competing HYD begins with a rapid H* attack to the keto, before a second, kinetically relevant H* attack, without proton involvement. Water, despite shifting the thermodynamics towards the more polar surface keto, promotes HDO to a much greater extent than HYD, because of its dual catalytic roles—it mobilizes hydroxyl proton (Brønsted acid) to cleave the strong C-O bond, synchronizing with the Ru metal surface (base) function that stabilizes the resulting [Ru(s)-(C6H5O-)…(H+)…OCH3]† transition state, and the water layers solvate this charged transition state, further reducing its free energy. Free hydronium ions do catalyze a separate homogeneous enol-keto isomerization, but this reaction is kinetically unrelated to HDO catalysis. This mechanistic picture explains the strong effects of polar protic solvent in hydrodeoxygenation, highlighting (i) the requirements of surface hydrides and interfacial protons acting in tandem to complete a HDO turnover and (ii) the cooperative role of protic solvent and metal surface in breaking the aromaticity and stabilizing charged reactive precursors and transition states.

Shangguan, Junnan↗

Short- vs . long-range elastic distortion: structural dynamics of a [2 × 2] tetrairon( II ) spin crossover grid complex observed by time-resolved X-Ray crystallography

Spin crossover complexes (SCO) are among the most studied molecular switches due to their potential use in displays, sensors, actuators and memory components. A prerequisite to using these materials is the understanding of the structural changes following the spin transition at out-of-equilibrium conditions. So far, out-of-equilibrium studies in SCO solids have been focused on mononuclear complexes, though a growing number of oligonuclear SCO complexes showing cooperative effects are being reported. Here, we use time-resolved pink Laue crystallography to study the out-of-equilibrium dynamics of a [2 × 2] tetranuclear metallogrid of the form [Fe II 4 L Me 4 ](BF 4 ) 4 ·2MeCN ([L Me ] - = 4-methyl-3,5-bis{6-(2,2'-bipyridyl)}pyrazolate). The out-of-equilibrium spin state switching induced by a ps laser pulse demonstrates that the metallogrid exhibits a multi-step response similar to that reported for mononuclear complexes. Contrary to the mononuclear complexes, the metallogrid shows two types of elastic distortions at different time scales. The first is a short-range distortion that propagates over the entire Fe 4 grid complex during the ps time scale, and it is caused by the rearrangement of the coordination sphere of the photo-switching ion and the constant feedback between strongly linked metal ions. The second is a long-range distortion caused by the anisotropic expansion of the lattice during the ns time scale, observed in mononuclear materials. The structural analysis demonstrates that the long-range prevails over the short-range distortion, inducing the largest deformation of both the entire grid and the coordination sphere of each metal ion. The present study sheds light on the out-of -equilibrium dynamics of a non-cooperative oligonuclear complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗