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At least 217 records · Page 12

Final Summary of Research Report to the National Aeronautics and Space Administration Cosmochemistry Program

The discovery of presolar grains in meteorites is one of the most exciting recent developments in meteoritics. Six types of presolar grain have been discovered: diamond, Sic, graphite, Si3N4, Al2O3 and MgAl2O4. These grains have been identified as presolar because their isotopic compositions are very different from those of Solar System materials. Comparison of their isotopic compositions with astronomical observations and theoretical models indicates most of the grains formed in the envelopes of highly evolved stars. They are, therefore, a new source of information with which to test astrophysical models of the evolution of these stars. In fact, because several elements can often be measured in the same grain, including elements that are not measurable spectroscopically in stars, the grain data provide some very stringent constraints for these models. Our primary goal is to create large, unbiased, multi-isotope databases of single presolar Sic, Si,N,, oxide and graphite grains in meteorites, as well as any new presolar grain types that are identified in the future. These will be used to: (i) test stellar and nucleosynthetic models, (ii) constrain the galactic chemical evolution (GCE) paths of the isotopes of Si, Ti, O and Mg, (iii) establish how many stellar sources contributed to the Solar System, (iv) constrain relative dust production rates of various stellar types and (v) assess how representative of galactic dust production the record in meteorites is. The primary tool for this project is a highly automated grain analysis system on the Carnegie 6f ion probe.

O'D. Alexander, Conel↗

Research Report to the National Aeronautics and Space Administration Cosmochemistry Program

The discovery of presolar grains in meteorites is one of the most exciting recent developments in meteoritics. Six types of presolar grain have been discovered: diamond, Sic, graphite, Si3N4, Al2O3 and MgAl2O4 (NIITLER, 2003). These grains have been identified as presolar because their isotopic compositions are very different from those of Solar System materials. Comparison of their isotopic compositions with astronomical observations and theoretical models indicates that most of the grains formed in the envelopes of highly evolved stars. They are, therefore, a new source of information with which to test astrophysical models of the evolution of these stars. In fact, because several elements can often be measured in the same grain, including elements that are not measurable spectroscopically in stars, the grain data provide some very stringent constraints for these models. Our primary goal is to create large, unbiased, multi-isotope databases of single presolar Sic, Si3N4, oxide and graphite grains in meteorites, as well as any new presolar grain types that are identified in the future. These will be used to: (i) test stellar and nucleosynthetic models, (ii) constrain the galactic chemical evolution (GCE) paths of the isotopes of Si, Ti, O and Mg, (iii) establish how many stellar sources contributed to the Solar System, (iv) constrain relative dust production rates of various stellar types and (v) assess how representative of galactic dust production the record in meteorites is. The primary tool for this project is a highly automated grain analysis system on the Carnegie 6f ion probe. This proposal was part of a long-standing research effort that is still ongoing.

Alexander, Conel O'D.↗

Tribological Behavior of Nano-Onions in Krytox 143AB Evaluated

Nanoparticles have been developed over the past 10 years and have found several applications. This work presents the use of carbon nano-onions as a potential oil additive for aerospace applications. Researchers at the NASA Glenn Research Center tested lubricant lifetimes in ambient air and ultrahigh vacuum and characterized the breakdown products of the friction and wear. These carbon nanoparticles can provide adequate lubrication very similar to that of graphitic material when run in air. Soot represents one of the very first nanostructured materials, although it has rarely been considered as such. Changes in the carbon nanostructure, resulting in increased graphitic layer plane length, correlate with reactivity loss. Upon heating spherically shaped nanometer-sized carbon black in the absence of oxidant, graphene sheets form, and the initial soot particle templates the growth of a graphitic particle into what is best described as a sphere with many flat sides having a hollow interior. Because there are no edge sites, these polygonal graphitic particles, or nano-onions, are relatively resistant to oxidation. Graphite is used as a solid lubricant because of its stability at moderately high temperatures. However, the temperature at which graphite oxidizes rapidly is strongly influenced by surface area. With the size of particles typically employed in lubrication, a great amount of thermal stability is lost because of size reduction either during preparation or during lubrication of contacting parts. Therefore, we have undertaken a study of the lubricating ability of graphitic nano-onions (ref. 1).

Street, Kenneth W.↗

Molecular dynamics simulations reveal that water diffusion between graphene oxide layers is slow

Membranes made of stacked layers of graphene oxide (GO) hold the tantalizing promise of revolutionizing desalination and water filtration if selective transport of molecules can be controlled. We present the findings of a molecular dynamics simulation study of water intercalated between GO layers that have a C/O ratio of 4. We simulated a range of hydration levels from 1 wt.% to 23.3 wt.% water. The interlayer spacing increased upon hydration from 0.8 nm to 1.1 nm. We also synthesized GO membranes that showed an increase in spacing from about 0.7 nm to 0.8 nm and an increase in mass of about 14% on hydration. Water diffusion through GO layers is an order of magnitude slower than that in bulk water, because of strong hydrogen bonded interactions. Most of the water molecules are bound to OH groups even at the highest hydration level. We observed large water clusters that could span graphitic regions, oxidized regions and holes that have been experimentally observed in GO. As a result, slow interlayer diffusion can be consistent with experimentally observed water transport in GO if holes lead to a shorter path length than previously assumed and sorption serves as a key rate-limiting step.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scanning transmission electron microscopy analysis of Ge(O)/(graphitic carbon nitride) nanocomposite powder

Analytical electron microscopy has revealed the structure of particles that were synthesized by chemical reaction of GeO{sub 2} with NaBH{sub 4} in the basic solution including graphitic carbon nitride (g-C{sub 3}N{sub 4}) powders. The g-C{sub 3}N{sub 4} was arranged by recrystallization of melamine at 600 °C under N{sub 2} gas atmosphere. The samples were dried at 60 °C or 180 °C for 4 h. The g-C{sub 3}N{sub 4} was observed as lamellae of several ten nm or less in size and had an amorphous-like structure with a distorted lattice in an area as small as a few hundred pm in size. The reaction product was Ge(O) particles as fine as several nm in size and composed of Ge and O atoms. Most of the particles must be of GeO{sub 2−x} with the amorphous-like structure that has also a distorted lattice in an area of a few hundred pm in size. In the sample dried at 60 °C, the particles were found to be dispersed in a wide area on the g-C{sub 3}N{sub 4} lamella. It is hard to recognize those particles in TEM images. The particles in the sample dried at 180 °C became larger and were easily observed as isolated lumps. Hence, these powders can be regarded as GeO{sub 2}/g-C{sub 3}N{sub 4} or Ge/GeO{sub 2}/g-C{sub 3}N{sub 4} nanocomposites, and expected to be applicable to anode materials for high energy Li-ion batteries due to Ge catalysis effect, accordingly. - Graphical abstract: STEM analysis of Ge(O)/(graphitic carbon nitride) nanocomposite powder. - Highlights: • Graphitic (g)-C{sub 3}N{sub 4} powder was prepared at 600 °C by recrystallization of melamine. • Ge(O) was prepared by chemical reaction in a solution including the g-C{sub 3}N{sub 4} powders. • The products can be regarded as GeO{sub 2}/g-C{sub 3}N{sub 4} or Ge/GeO{sub 2}/g-C{sub 3}N{sub 4} nanocomposites. • GeO{sub 2} was amorphous several-nm particles and g-C{sub 3}N{sub 4} was amorphous lamella of several 10 nm in size. • We expect them to be applicable for high energy Li-ion battery anode materials.

36 MATERIALS SCIENCE↗

Two-dimensional van der Waals heterojunctions for functional materials and devices

Two-dimensional (2D) materials, such as graphene, phosphorene, graphitic carbon nitride (g-C3N4), graphitic zinc oxide (g-ZnO) and transition metal dichalcogenides (TMDs, e.g., MoS2), have already attracted extensive attention due to their outstanding properties and wide range of applications in electronic and optoelectronic devices. In particular, 2D van der Waals heterojunctions combining the electronic structures of such 2D materials have also been predicted theoretically and synthesized experimentally to expect more new properties (e.g., bandgap opening in graphene, semiconductor band alignment, charge transfer and new optical absorption) and potential applications (e.g., solar cells, field-effect transistors (FFTs), PN junctions, PN diodes and photodetectors) far beyond corresponding 2D materials. This review focuses on recent theoretical works about 2D van der Waals heterojunctions especially for functional materials and devices such as photovoltaic solar cells (phosphorene/MoS2 and edge-modified phosphorene nanoflake based heterojunctions), Schottky and Ohmic contacts (graphene/MoS2 based heterojunctions), PN junctions (graphene/g-ZnO based heterojunctions) and supercapacitors (graphene/h-BN based heterojunctions). These theoretical simulations and designs of 2D van der Waals heterojunctions provide a promising direction for high-performance electronic and optoelectronic devices in experiments.

Hu, Wei↗

Dynamic sampling of laser-induced vapor plumes by mass spectrometry

Mass spectrometric techniques and instrumentation for the dynamic sampling of laser-induced vapor clouds during their submillisecond expansion periods are discussed. Illustrations are drawn primarily from the results of pulsed-laser heating of some oxides and graphites; these include comparisons of incident laser beam pulses with the resultant pulses of positive ions and selected neutral species. Observed characteristics of vapor pulses from graphite are shown to correlate with calculated surface temperature response. Dynamic velocity measurements of individual vapor species are described and, from these velocities, vaporization temperatures are derived and compared using four gas dynamic models for vapor expansion into vacuum. Additional measurements indicate that the laser beam may interact directly with the neutral vapors to produce ions.

Lincoln, K. A.↗

Origins of interstellar and solar system: Carbonaceous materials

Carbon is a crucial atom in cosmochemistry. It is well-established that carbon is synthesized in stellar interiors after the main sequence, is ejected by red giants as small carbonaceous grains during their 'carbon star' phase, resides in the interstellar medium, and was later incorporated into the solar system. The mechanisms of carbon grain formation and later chemical processing are complex because, with only small thermodynamic differences, carbon can take on a bewildering variety of forms: diamond; oxides; carbides; graphite; aliphatic hydrocarbons; polycyclic aromatic hydrocarbons (PAH's); fullerenes; amorphous carbon; and other compounds. These are evidence for many of the forms of carbon found in astronomical observations. We seek to understand the possible astrophysical sites and conditions of the origins of different forms of carbon by combining state-of-the-art capabilities of carbon chemistry with astrophysical modeling. The work is a collaboration between Prof. Frenklach, a leading carbon materials scientist with both laboratory and computer modeling expertise and Prof. Feigelson, an astrophysicist with interests in star formation. The largest effort under this grant was devoted to developing this concept into a comprehensive quantitative model. In addition to explaining the astronomical properties of red giants producing carbonaceous grains, our model also can incorporate recent meteoritic findings. Finally, our induced nucleation grain formation model provides a natural explanation for the widespread presence of PAH emission bands in the Galactic interstellar medium. A brief synopsis of other activities sponsored under this grant and a list of publications from this grant is included.

Feigelson, Eric D.↗

"CHON" particles: The interstellar component of cometary dust

Interstellar dust is characterized by strong absorption in the ultraviolet and the mid-IR. Current models of interstellar dust are based on three chemically distinct components: a form of carbon (usually graphite), a silicate, and a blend of polycyclic aromatic hydrocarbons or other carbonaceous material. Previous work using effective medium theories to understand the optical properties of cometary dust suggested that an amalgam of materials could reproduce the observed interstellar and cometary dust features. Recently, Lawler and Brownlee (1992) re-analyzed the PIA and PUMA-1 data sets from the Giotto flyby of P/Halley and discovered that the so-called "CHON" particles were actually composed of a blend of carbon-bearing and silicon-bearing materials. Based on effective medium theories, the absorption spectrum of such a material would display the spectral features of each of the components - strong UV absorption from the carbonaceous component and strong absorption in the IR from the silicate component. To test this idea, vapor-deposited samples were created using two different deposition techniques: sputtering with an argon RF magnetron and deposition from an argon plasma torch. Two different compositions were tested: a blend of graphite and silica in a 7:1 ratio and an amalgam of materials whose approximate composition matches the "CHON"-silicate abundances for the uncompressed PIA data set of Lawler and Brownlee: graphite, iron oxide, magnesium oxide, ammonium sulfate, calcium carbonate, and silica in mass ratios of 6:4.3:4:2.2:1:9. The samples were finely ground and pressed into 2" diameter disks using a 40 ton press. In all, four different experiments were performed: one with each of the compositions (C:SiO and "CHON") in both the RF magnetron and the plasma torch chambers. The RF magnetron created a uniform dark thin film on the substrate surface, and the plasma torch created a coating of small (<100 micron) diameter grey particles. The spectra of all four samples show a strong, broad absorption feature at around 220 nm as well as a strong but narrower absorption peak near 10 microns. The RF magnetron sputtered samples showed some sub-structure in the UV, and the peak of the absorption was shifted toward longer wavelengths. The UV absorption in the plasma torch deposited samples have no sub-structure, and the peak absorption is very near 220 nm. Strong absorption near 9 microns is seen in the spectra from both sample preparation techniques, and is consistent with the IR spectra of some terrestrial silicates. Other features, particularly at 6.2 and 8.6 microns, are seen in the interstellar medium. A strong feature near 2 microns is due to absorbed water in the sample. Based on the results of these experiments, there is evidence that a material with a composition similar to that detected in "CHON" particles in the coma of P/Halley have a spectral signature which reproduces the main absorption features of interstellar dust. This suggests that the "CHON" particles could be the interstellar component of cometary dust.

Lien, David J.↗

Tomographic Location of Potential Melt-Bearing Phenocrysts in Lunar Glass Spherules

In 1971, Apollo 17 astronauts collected a 10 cm soil sample (74220) comprised almost entirely of orange glass spherules. Below this, a double drive-tube core sampled a 68 cm thick horizon comprised of orange glass and black beads (crystallized equivalents of orange glass). Primitive lunar glass spherules (e.g.-A17 orange glasses) are thought to represent ejecta from lunar mare fire fountains [1, 2]. The fire-fountains were apparently driven by a combination of C-O gas ex-solution from orange glass melt and the oxidation of graphite [3, 4]. Upon eruption, magmas lost their volatiles (e.g., S, CO, CO2) to space. Evidence for volatile escape remains as volatile-rich coatings on the exteriors of many spherules [e.g., 5,6]. Moreover, [7] showed that Type I and II Fe-Ni-rich metal particles found within orange glass olivine phenocrysts, or free-floating in the glass itself, are powerful evidence for the volatile driving force for lunar fire fountains.

Ebel, D. S.↗

Direct reuse of graphite and lithium nickel manganese cobalt oxide (NMC) recovered from ultrafast-laser ablation debris in Li-ion battery electrodes

Here we demonstrate that debris collected from the ultrafast-laser ablation of graphite anodes can be directly reused in a lithium-ion battery with little to no negative effects on electrochemical performance. Further, we show that while post-ablation NMC (LiNi 0.33 Mn 0.33 Co 0.33 O) cathode debris will require additional processing before being incorporated into an electrode, its critical materials (nickel, manganese, and cobalt) are not lost during ablation and can be recovered for recycling. Pre- and post-ablation materials are characterized with a suite of diagnostics, including SEM, TEM, X-ray CT, EDS, and XRD, to study changes in material morphology, composition and crystal structure. Graphite exhibited little to no morphological or compositional changes and a slight annealing of its crystal structure. NMC underwent profound morphological and crystallographic changes, but retained its elemental composition. Finally, post-ablation materials were re-manufactured into electrodes and cycled vs lithium metal. Graphite showed equal or better capacity and Coulombic efficiency compared to pre-ablation electrodes, while the post-ablation NMC exhibited severely reduced electrochemical performance. Furthermore, we discuss the outlook for application of this work to advanced manufacturing lines that produce next-generation, laser-patterned electrodes.

25 ENERGY STORAGE↗

Advanced High-Temperature Sodium-Cooled Thermal Reactors Using Less Than 10% Enriched UO 2 Fuel

Here, this paper presents a 1200-MW(thermal) advanced sodium-cooled thermal reactor concept that uses online refueling of 3.5% to 9.95% enriched UO2 fuel pin bundles; uses either graphite or beryllium oxide (BeO) as a neutron moderator; reaches outlet temperatures of 650°C enabling a thermal efficiency of at least 45%; has a high specific power of 133 W/g U; has average power densities of 16.4 and 43.2 W/cm 3 with graphite and BeO, respectively; reaches an average discharge burnup of 100 MWd/kg U; and generates 52% less spent fuel volume, 28% less fission products, and 47% to 64% less transuranics than a typical large pressurized water reactor for the same amount of electricity produced.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Understanding the reaction of nuclear graphite with molecular oxygen: Kinetics, transport, and structural evolution

A thorough understanding of oxidation is important when considering the health and integrity of graphite components in graphite reactors. For the next generation of graphite reactors, HTGRs specifically, an unlikely air ingress has been deemed significant enough to have made its way into the licensing applications of many international licensing bodies. While a substantial body of literature exists on nuclear graphite oxidation in the presence of molecular oxygen and significant efforts have been made to characterize oxidation kinetics of various grades, the value of existing information is somewhat limited. Often, multiple competing processes, including reaction kinetics, mass transfer, and microstructural evolution, are lumped together into a single rate expression that limits the ability to translate this information to different conditions. This article reviews the reaction of graphite with molecular oxygen in terms of the reaction kinetics, gas transport, and microstructural evolution of graphite. It also presents the foundations of a model for the graphite-molecular oxygen reaction system that is kinetically independent of graphite grade, and is capable of describing both the bulk and local oxidation rates under a wide range of conditions applicable to air-ingress.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗