Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “surface energetics”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 847 records · Page 47
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Structure sensitivity of ammonia electro-oxidation on transition metal surfaces: A first-principles study

Ammonia electro-oxidation is a promising catalytic reaction for application in alkaline fuel cells. In this paper we study the trends in this reaction on the (1 0 0) facet of eight fcc transition metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh. We calculate from first-principles (DFT-GGA-PW91) the energetics for two mechanisms: (i) the N + N mechanism and (ii) the Gerischer-Mauerer mechanism. The onset potentials for both mechanisms are provided for both (1 0 0) and (1 1 1) facets. We also calculate the activation energies for the N-N bond-making non-Faradaic events on Cu, Pt, Pd, Ni, Ir, and Rh. We discover that N* – which is considered a poison for Pt(1 1 1) – is a reactive intermediate on Pt(1 0 0), allowing for a facile dimerization to N2 on Pt(1 0 0) at high potentials. We draw similar analyses for the structure sensitivity on the other metals, and we conclude with some general principles to guide catalyst design for this reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2014

The Bombardment History of 4 Vesta as Told by Sample Geochronology

The Dawn mission showed asteroid 4 Vesta to be an extensively cratered body, ancient in age, with craters in a variety of morphologies and preservation states [1-3]. Tying Vesta's relative crater ages to an absolute impact history can be accomplished through investigations of the HED (howardite, eucrite, diogenite) meteorites. Eucrites are crustal basalts and gabbros, diogenites are mostly orthopyroxenites representing lower crust or upper mantle materials, and howardites are mixed breccias containing both lithologies. Eucrite 53Mn-53Cr systematics show that the HED parent body globally differentiated by ~4.56 Ga and fully crystallized soon afterwards [4]. Much later, many eucrites were brecciated and heated by large impacts into the parent body surface. Disturbance ages in eucrites show that multiple large impacts occurred within 1 Gyr after crystallization, showing a history that largely resembles that of the Moon [5-7]. Dawn images also showed that Vesta is covered with a well-developed regolith that is spectrally similar to howardite meteorites [8]. Howardites are polymict regolith breccias made up mostly of clasts of eucrites and diogenites, but which also contain clasts formed by melting of the regolith by relatively large, energetic impact events. Impact-melt clast ages from howardites extend our knowledge of the impact history of Vesta, expanding on eucrite disturbance ages and helping give absolute age context to the observed crater-counts produced using Dawn data. The distribution of 40Ar-39Ar ages of impact-melt clasts in howardites shows that they formed within the time period 3.3-3.8 Ga [9]. These, and other impact-melted HED materials, have distinct age and compositional characteristics that suggest they formed in discrete impact events. In order to create these crystalline impact-melt products on the surface of Vesta, the impacts during this time period must have had velocities much higher than 5 km/s, the main belt average [10]. This is inconsistent with formation by a normal distribution of impact velocities and points instead to a unique period where high-velocity collisions were more frequent than currently observed. Until now, impact-reset ages in the HED meteorites have been be interpreted under the umbrella of the canonical lunar cataclysm where an increase in the absolute number of bombarding objects is responsible for creating larger absolute amounts of impact-affected and impact-melted rocks, statistically increasing their chances of being found on Earth and dated. However, the distribution of age among the howardite impact-melt clasts may not necessarily result from an increased number of impacts, but rather result from impacts of higher velocity. The changeover from a typical main belt velocity profile to this regime of increased velocity population at Vesta occurs contemporaneously with a similar transition at the Moon, indicating that howardite impact-melt clast ages reinforce the notion of a dynamically unusual episode of bombardment in the inner solar system beginning at around 4.0 Ga.

Cohen, B. A.↗
DOE OSTI2026

A Vibrational Probe of Electrical Doping in N2200 and Fermi-Level Alignment at Polymer Cathode/Metal Cocatalyst/Electrolyte Junctions

Hybrid (photo)­cathodes consisting of conjugated polymer and hydrogen evolution reaction (HER) cocatalysts are an emerging platform for low-cost solar fuel generation. Poly­{[N,N′-bis­(2-octyldodecyl)-naphthalene-1,4,5,8-bis­(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)}, known as P­(NDI2OD-T2) or N2200, is a promising electron accepting material for bulk heterojunction photocathodes. Unlike inorganic (photo)­electrodes, much less is known about the energetic alignment of conjugated polymer electrode/metal/electrolyte junctions. Here, in this work, we investigate the electrical doping behavior in an N2200 cathode and its Fermi-level alignment with gold nanoparticles, which is used here as a model for the hydrogen evolution metal cocatalyst. Through UV/visible, Raman, and attenuated total-reflectance infrared spectroelectrochemistry, we observe the impact of electrical doping on the vibrational frequencies of neutral, anion, and dianion species in N2200, which suggests that electron density changes within the corresponding naphthalene-diimide (NDI) units. Upon one-electron reduction, the $C=O$ stretching frequency of the NDI anion unit (polaron) shows a red shift by ∼ 68 cm –1 . Additionally, the $C=O$ stretching frequency of neutral units in the doped N2200 shows a minor red shift of ∼ 5 cm –1 , suggesting charge transfer from neighboring polaron units. Surface-enhanced Raman spectroscopy measurements of a gold nanoparticle-functionalized N2200 electrode revealed that the Au Fermi level only shifts with that of N2200 upon polaron formation; thus, the formal potential of polymer polaron formation determines the behavior of the catalyst Fermi level, which we posit will modulate reaction capability. This mechanistic study provides a new approach for understanding the nanometer-scale energetics at the conjugated polymer/cocatalyst junction and provides critical insights for the future design of HER (photo)­cathodes.

charge transfer↗
DOE OSTI2022

Improving Rare-Earth Mineral Separation with Insights from Molecular Recognition: Functionalized Hydroxamic Acid Adsorption onto Bastnäsite and Calcite

Enhancing the separation of rare-earth elements (REEs) from gangue materials in mined ores requires an understanding of the fundamental interactions driving the adsorption of collector ligands onto mineral interfaces. In this work, we examine five functionalized hydroxamic acid ligands as potential collectors for the REE-containing bastnäsite mineral in froth flotation using density functional theory calculations and a suite of surface-sensitive analytical spectroscopies. These include vibrational sum frequency generation, attenuated total reflectance Fourier transform infrared, Raman, and X-ray photoelectron spectroscopies. Differences in the chemical makeup of these ligands on well-defined bastnäsite and calcite surfaces allow for a systematic relationship connecting the structure to adsorption activity to be framed in the context of interfacial molecular recognition. Here we show how the intramolecular hydrogen bonding of adsorbed ligands requires the inclusion of explicit water solvent molecules to correctly map energetic and structural trends measured by experiments. We anticipate that the results and insights from this work will motivate and inform the design of improved flotation collectors for REE ores.

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

Surface vs Homogeneous Organo-Hafnium Catalyst Ion-Pairing and Ligand Effects on Ethylene Homo- and Copolymerizations

Heterogeneous catalysts have long dominated polyethylene and polypropylene production, but understanding their catalysis is challenged by uncertainties in active site structures and percentages. Surface-bound organometallic catalysts are an emerging strategy to combine successful homogeneous catalysts having well-understood structures, relatively high percentages of active sites, and exceptional control of selectivity, with the attractions of surface catalysts, to transition promising homogeneous systems to large-scale heterogeneous ones. Nevertheless, surface-bound olefin polymerization catalysts typically produce ultrahigh M w ’s but with low activity and comonomer selectivity. Here, we report the systematic synthesis and characterization of a series of pyridylamido–Hf complexes and their corresponding surface catalysts chemisorbed on sulfated alumina (AlS) and zirconia (ZrS). Comparative ethylene homo- and 1-octene copolymerizations reveal similar activity and 1-octene selectivity trends in the homogeneous and heterogeneous systems. For the surface pyridylamido–Hf catalyst series, large variations in activity (up to 10×) and 1-octene incorporation (up to 28×) are achieved by ligand and support manipulation. Interestingly, while the homogeneous catalysts exhibit positive comonomer effects in ethylene/1-octene copolymerization, the surface catalysts behave oppositely. Extended X-ray absorption fine structure (EXAFS) reveals significantly elongated Hf···O bond distances vs typical Hf–O covalent bonds (2.06 vs 1.97 Å). Furthermore, density functional theory (DFT) analysis of the heterolytic ion pair separation enthalpies, olefin insertion energetics, and NBO/Bader charges also suggest electrostatic Hf cation–anionic support binding and catalytic patterns, which are modulated by the ion-pairing energetics and ligand architecture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1974

A chondrule - Evidence of energetic impact unlikely

It had been concluded by Lange and Larimer (1973) that the morphology and mineralogy of an unusual chondrule from the Ngawi meteorite are the results of a highly energetic impact within the solar nebula. The evidence for this conclusion is examined. It is found that the chondrule does not show evidence of high relative velocities in the solar nebula. It is pointed out that arguments against chondrule production by impact on planetary surfaces on the basis of ejection velocities are not supported by laboratory experiments.

Vedder, J. F.↗
NASA NTRS1982

The cometary atmosphere and its interaction with the solar wind

The present state of knowledge of cometary atmospheres and their interaction with the solar winds is assessed. Current models of the magnetospheres and ionospheres of comets are based on either an atmospheric chemistry approach, minimizing the effects of atmospheric dynamics and thermodynamics, while the other method takes the exact opposite viewpoint and roles and significance are reversed. A major difficulty in completing the models is a lack of data on the chemical composition of the cometary nucleus, although UV observations have revealed the H, C, O, and S elemental abundance ratios. It is suggested that further studies of collisional ionization by energetic electrons be performed to characterize processes in the cometary atmosphere. Hydronium may be the dominat molecule in the inner coma, if the assumption that the ionosphere is a magnetic field-free cavity separated from the solar wind by an unyielding tangential discontinuity surface is accurate. Particular observations and theoretical attention are recommended for the solar wind interaction in the intermediate range, i.e., 2.5-5 AU, when the cometary atmosphere develops.

Mendis, D. A.↗
NASA NTRS1984

Dust-magnetosphere interactions

Many different interactions have been proposed among the magnetospheric particles, fields, and dust grains in the rings of the outer planets. Attention is presently given to the energetic particle absorption signatures obtained by Pioneer 11 and Voyagers 1 and 2, which trace the mass concentrations of particulates in the magnetospheres of Jupiter and Saturn. Particulates immersed in the magnetospheric plasma and exposed to solar UV radiation will charge up to a surface potential that depends on the density and electron energy of the plasma, as well as on the concentration of dust particles. Kinetic effects of charged dust particles arise from the interaction with the planetary magnetic field. Electromagnetic effects are noted which lead to the halo of Jupiter's ring, the dust distribution in Saturn's E ring, and the levitated dust in the Saturn B ring spokes.

Gruen, E.↗
NASA NTRS2003

Atomistic Modeling of Nanostructures via the BFS Quantum Approximate Method

Ideally, computational modeling techniques for nanoscopic physics would be able to perform free of limitations on the type and number of elements, while providing comparable accuracy when dealing with bulk or surface problems. Computational efficiency is also desirable, if not mandatory, for properly dealing with the complexity of typical nano-strucured systems. A quantum approximate technique, the BFS method for alloys, which attempts to meet these demands, is introduced for the calculation of the energetics of nanostructures. The versatility of the technique is demonstrated through analysis of diverse systems, including multi-phase precipitation in a five element Ni-Al-Ti-Cr-Cu alloy and the formation of mixed composition Co-Cu islands on a metallic Cu(III) substrate.

Bozzolo, Guillermo↗
NASA NTRS2005

Effects of Cutoffs on Galactic Cosmic-Ray Interactions in Solar-System Matter

The energetic particles in the galactic cosmic rays (GCR) induce many interactions in a variety of solar-system matter. Cosmogenic nuclides are used to study the histories of meteorites and lunar samples. Gamma rays and neutrons are used to map the compositions of planetary surfaces, such as Mars, the Moon, and asteroids. In almost all of these cases, the spectra of incident GCR particles are fairly similar, with only some modulation by the Sun over an 11-year cycle. Strong magnetic fields can seriously affect the energy spectrum of GCR particles hitting the surface of objects inside the magnetic fields. The Earth s geomagnetic field is strong enough that only GCR particles with magnetic rigidities above approx. 17 GV (a proton energy of approx. 17 GeV) reach the atmosphere over certain regions near the equator. This effect of removing lower-energy GCR particles is called a cutoff. The jovian magnetic fields are so strong that the fluxes of GCR particles hitting the 4 large Galilean satellites are similarly affected. The cutoff at Europa is estimated to be similar to or a little higher than at the Earth s equator.

Kim, K. J.↗
NASA NTRS2007

Seeking to Improve Low Energy Neutral Atom Detection in Space

The detection of energetic neutral atoms allows for the remote examination of the interactions between plasmas and neutral populations in space. Before these neutral atoms can be measured, they must first be converted to ions. For the low energy end of this spectrum, interaction with a conversion surface is often the most efficient method to convert neutrals into ions. It is generally thought that the most efficient surfaces are low work functions materials. However, by their very nature, these surfaces are highly reactive and unstable, and therefore are not suitable for space missions where conditions cannot be controlled as they are in a laboratory. We therefore are looking to optimize a stable surface for conversion efficiency. Conversion efficiency can be increased either by changing the incident angle of the neutral particles to be grazing incidence and using stable surfaces with high conversion efficiencies. We have examined how to increase the angle of incidence from -80 degrees to -89 degrees, while maintaining or improving the total active conversion surface area without increasing the overall volume of the instrument. We are developing a method to micro-machine silicon, which will reduce the volume to surface area ratio by a factor of 60. We have also examined the material properties that affect the conversion efficiency of the surface for stable surfaces. Some of the parameters we have examined are work function, smoothness, and bond structure. We find that for stable surfaces, the most important property is the smoothness of the surface.

Shappirio, M.↗
NASA NTRS2016

Solar Array at Very High Temperatures: Ground Tests

Solar array design for any spacecraft is determined by the orbit parameters. For example, operational voltage for spacecraft in Low Earth Orbit (LEO) is limited by significant differential charging due to interactions with low temperature plasma. In order to avoid arcing in LEO, solar array is designed to generate electrical power at comparatively low voltages (below 100 volts) or to operate at higher voltages with encapsulation of all suspected discharge locations. In Geosynchronous Orbit (GEO) differential charging is caused by energetic electrons that produce differential potential between the coverglass and the conductive spacecraft body in a kilovolt range. In such a case, the weakly conductive layer over coverglass, indium tin oxide (ITO) is one of the possible measures to eliminate dangerous discharges on array surface. Temperature variations for solar arrays in both orbits are measured and documented within the range of minus150 degrees Centigrade to plus 1100 degrees Centigrade. This wide interval of operational temperatures is regularly reproduced in ground tests with radiative heating and cooling inside a shroud with flowing liquid nitrogen. The requirements to solar array design and tests turn out to be more complicated when planned trajectory crosses these two orbits and goes closer to the Sun. The conductive layer over coverglass causes a sharp increase in parasitic current collected from LEO plasma, high temperature may cause cracks in encapsulating (Room Temperature Vulcanizing (RTV) material; radiative heating of a coupon in vacuum chamber becomes practically impossible above 1500 degrees Centigrade; conductivities of glass and adhesive go up with temperature that decrease array efficiency; and mechanical stresses grow up to critical magnitudes. A few test arrangements and respective results are presented in current paper. Coupons were tested against arcing in simulated LEO and GEO environments under elevated temperatures up to 2000 degrees Centigrade. The dependence of leakage current on temperature was measured, and electrostatic cleanness was verified for coupons with antireflection (AR) coating over the indium tin oxide (ITO) layer.

differential charging↗
NASA NTRSDate not supplied

Identifying Neutron Irradiation in Space to Mitigate Bio-Medical Effects

Ubiquitous GCR high energy particles >1 GeV is primary concern • Medical effects compounded by ionizing dose of radiation from energetic particles- cancer, mutations, microbiome changes • Cancer induction and effects are irreversible after initiation • Long term space radiation exposure is cancer promoting but reversible Secondary GCR and Solar induced neutron spallation is a concern • Produced by interactions with space craft materials, EVA and planetary surfaces • Neutron Quality Factor is 10x that of beta, x-ray or gamma rays Space isn’t friendly to life or electronics! Real-time charged particle and EARLY neutron detection are required. Traveling fast or digging deep are the best protection. Nuclear space propulsion through LENR/LCF/Solid-State Fusion is a good bet!

space medicine↗
DOE OSTI2022

Leaching Model of Radionuclides in Metal-Organic Framework Particles

Metal-organic frameworks (MOFs) have been used to sequester radionuclides and seal them inside of porous scaffolds using postsynthetic modification procedures. Experiments show that certain Zr-MOF with different capping linkers significantly affects the radionuclide release kinetics. In this work, we developed a leaching model of radionuclides in Zr-MOF particles. The model assumes that uranyl species occupy two energetically favored sites: the metal node and the MOF pores. For a given overall concentration of uranyl species, the partitions of uranyl species at the metal nodes and within the pores are determined by their chemical potentials. The model also considers the effect of particle surface and concentration on chemical potentials and diffusivity. The effects of spatial and structural dependent chemical potentials and diffusivity as well as particle sizes on leaching kinetics are investigated with the model. Predicted and measured uranyl leaching kinetics in Zr-MOF particles under batch experiments are compared. The results demonstrate the model’s capability for exploring the mechanisms of leaching and provide guidance for material design.

Metal-Organic Framework, Diffusion, uranyl, Leachi↗
DOE OSTI2025

Imaging the Acceptor Wave Function Anisotropy in Silicon

We present the first scanning tunneling microscopy (STM) image of hydrogenic acceptor wave functions in silicon. These acceptor states appear as square-ring-like features in STM images and originate from near-surface defects introduced by high-energy bismuth implantation into a silicon (001) wafer. Scanning tunneling spectroscopy confirms the formation of a p-type surface. Effective-mass and tight-binding calculations provide an excellent description of the observed square-ring-like features, confirming their acceptor character and attributing their symmetry to the light- and heavy-hole band degeneracy in silicon. A detailed understanding of the energetic and spatial properties of acceptor wave functions in silicon is essential for engineering large-scale acceptor-based quantum devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Bespoke Liquid/Liquid Interfaces (Final Technical Report)

The goal of DE-SC0001815 was to advance the basic science of liquid:liquid interface formation, to develop a deeper understanding of the mechanisms of phase separation and the essential relationships between solution composition, organization and dynamics that underlie the kinetic regime of solvent extraction. This included learning how interfacial organization and dynamics alters the properties of the primary coordination sphere of ions and the free energy of transport of ions complexes across a phase boundary. We relied primarily upon classical molecular dynamics studies to determine the equilibrium ensembles of these complex systems, but also utilized ab-initio MD and cluster-based density functional theory (DFT) calculations when more detailed investigation of the electronic structure was needed. We continued development of graph-theory based analyses to elucidate hierarchical correlations and expanded into geometric topology methods to quantify the collectively organized structures that can organize at a liquid/liquid interface during solute transport. One of the main conclusions was from the observation of two distinct mechanisms for solute transport - those that derive from amplifications of interfacial heterogeneity and surface roughness, and those wherein surface roughness has been dampened and instead collectively organized macrostructures work to bring solutes into the organic phase. It was our aim to create a concrete chemical model of the underlying driving forces behind interfacial primary and secondary structure formation and to map out the energetic features of solute transport so that tailored liquid/liquid can be developed that have characteristic kinetic features associated with mass transport.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1972

Suprathermal ion detector results from Apollo missions.

This paper reviews briefly the knowledge of the ion environment of the moon as obtained from the Apollo Lunar Surface Experiments Package, Suprathermal Ion Detector Experiment. Topics to be discussed include: an interplanetary shock as seen from the lunar surface; bow shock and magnetosheath ions; magnetotail plasma seen during a magnetic disturbance; suprathermal ions seen during passage of the sunset and sunrise terminators; and ions associated with neutral gas clouds in the vicinity of the moon, and in particular the low energy mono-energetic spectrum of these ions. It is believed that these low energy spectra and some terminator ions can be explained by ion acceleration by the interplanetary electric field. This paper serves as catalog to references to these and other related phenomena.

Freeman, J. W., Jr.↗
NASA NTRS1991

Thin, Lightweight Solar Cell

Improved design for thin, lightweight solar photovoltaic cells with front contacts reduces degradation of electrical output under exposure to energetic charged particles (protons and electrons). Increases ability of cells to maintain structural integrity under exposure to ultraviolet radiation by eliminating ultraviolet-degradable adhesives used to retain cover glasses. Interdigitated front contacts and front junctions formed on semiconductor substrate. Mating contacts formed on back surface of cover glass. Cover glass and substrate electrostatically bonded together.

Brandhorst, Henry W., Jr.↗