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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 181 records · Page 10

Performance Testing of Yardney MCMB-LiNiCoAlO2 Lithium-ion Cells Possessing Electrolytes with Improved Safety Characteristics

Many future NASA missions aimed at exploring the Moon and Mars require high specific energy rechargeable batteries that possess enhanced safety characteristics. There is also a strong desire to develop Li-ion batteries with improved safety characteristics for terrestrial applications, most notably for HEV and PHEV automotive applications. In previous work focused upon evaluating various potential flame retardant additives1, triphenyl phosphate (TPP)2 was observed to have the most desirable attributes, including good life characteristics and resilience to high voltage operation. We have employed a number of approaches in the design of promising TPP-based electrolytes with improved safety, including: (a) varying the flame retardant additive (FRA) content (from 5 to 15%), (b) the use of fluorinated co-solvents, (c) the use of additives to improve compatibility, and (c) the use of ester co-solvents to decrease the viscosity and increase the conductivity. In recent work, we have demonstrated a number of these electrolyte formulations to be compatible with a number of chemistries, including: MCMB carbon-LiNi0.8Co0.2O2, graphite-LiNi0.8Co0.15Al0.05O2, Li-Li(Li0.17Ni 0.25 Mn 0.58 )O2, Li-LiNiCoMnO2 and graphite- LiNiCoMnO2.3,4 In the current study, we have demonstrated the performance of a number of TPP-containing electrolytes in 7 Ah prototype MCMB-LiNiCoO2 cells. We will describe the results of a number of performance tests, including: a) 100% DOD cycle life testing at various temperatures, b) discharge rate characterization as a function of temperature, c) charge rate characterization as a function of temperature, and d) impedance as a function of temperature. In addition to displaying good life characteristics, being comparable to baseline chemistries, a number of cells were observed to provide good performance over a wide temperature range.

Li-ion batteries↗

Self assembly properties of primitive organic compounds

A central event in the origin of life was the self-assembly of amphiphilic, lipid-like compounds into closed microenvironments. If a primitive macromolecular replicating system could be encapsulated within a vesicular membrane, the components of the system would share the same microenvironment, and the result would be a step toward true cellular function. The goal of our research has been to determine what amphiphilic molecules might plausibly have been available on the early Earth to participate in the formation of such boundary structures. To this end, we have investigated primitive organic mixtures present in carbonaceous meteorites such as the Murchison meteorite, which contains 1-2 percent of its mass in the form of organic carbon compounds. It is likely that such compounds contributed to the inventory of organic carbon on the prebiotic earth, and were available to participate in chemical evolution leading to the emergence of the first cellular life forms. We found that Murchison components extracted into non-polar solvent systems are surface active, a clear indication of amphiphilic character. One acidic fraction self-assembles into vesicular membranes that provide permeability barriers to polar solutes. Other evidence indicates that the membranes are bimolecular layers similar to those formed by contemporary membrane lipids. We conclude that bilayer membrane formation by primitive amphiphiles on the early Earth is feasible. However, only a minor fraction of acidic amphiphiles assembles into bilayers, and the resulting membranes require narrowly defined conditions of pH and ionic composition to be stable. It seems unlikely, therefore, that meteoritic infall was a direct source of membrane amphiphiles. Instead, the hydrocarbon components and their derivatives more probably would provide an organic stock available for chemical evolution. Our current research is directed at possible reactions which would generate substantial quantities of membranogenic amphiphiles. One possibility is photochemical oxidation of hydrocarbons.

Deamer, D. W.↗

Processing, properties and applications of composites using powder-coated epoxy towpreg technology

Composite manufacturing using the current prepregging technology of impregnating liquid resin into three-dimensionally reinforced textile preforms can be a costly and difficult operation. Alternatively, using polymer in the solid form, grinding it into a powder, and then depositing it onto a carbon fiber tow prior to making a textile preform is a viable method for the production of complex textile shapes. The powder-coated towpreg yarn is stable, needs no refrigeration, contains no solvents and is easy to process into various woven and braided preforms for later consolidation into composite structures. NASA's Advanced Composites Technology (ACT) program has provided an avenue for developing the technology by which advanced resins and their powder-coated preforms may be used in aircraft structures. Two-dimensional braiding and weaving studies using powder-coated towpreg have been conducted to determine the effect of resin content, towpreg size and twist on textile composite properties. Studies have been made to customize the towpreg to reduce friction and bulk factor. Processing parameters have been determined for three epoxy resin systems on eight-harness satin fabric, and on more advanced 3-D preform architectures for the downselected resin system. Processing effects and the resultant mechanical properties of these textile composites will be presented and compared.

Bayha, T. D.↗

Determination of the thermal stability of perfluoropolyalkyl ethers by tensimetry

The thermal decomposition temperatures of several perfluoropolyalkyl ether fluids were determined with a computerized tensimeter. In general, the decomposition temperatures of the commercial fluids were all similar and significantly higher than those for noncommercial fluids. Correlation of the decomposition temperatures with the molecular structures of the primary components of the commercial fluids revealed that the stability of the fluids was not affected by carbon chain length, branching, or adjacent difluoroformal groups. Instead, stability was limited by the presence of small quantities of thermally unstable material and/or chlorine-containing material arising from the use of chlorine containing solvents during synthesis. Finally, correlation of decomposition temperatures with molecular weights for two fluids supports a chain cleavage reaction mechanism for one and an unzipping reaction mechanism for the other.

Helmick, Larry A.↗

Purification of Carbon Nanotubes: Alternative Methods

Traditional carbon nanotube purification process involves nitric acid refluxing and cross flow filtration using surfactant TritonX. This is believed to result in damage to nanotubes and surfactant residue on nanotube surface. Alternative purification procedures involving solvent extraction, thermal zone refining and nitric acid refiuxing are used in the current study. The effect of duration and type of solvent to dissolve impurities including fullerenes and P ACs (polyaromatic compounds) are monitored by nuclear magnetic reasonance, high performance liquid chromatography, and thermogravimetric analysis. Thermal zone refining yielded sample areas rich in nanotubes as seen by scanning electric microscopy. Refluxing in boiling nitric acid seem to improve the nanotube content. Different procedural steps are needed to purify samples produced by laser process compared to arc process. These alternative methods of nanotube purification will be presented along with results from supporting analytical techniques.

Files, Bradley↗

Progress toward Making Epoxy/Carbon-Nanotube Composites

A modicum of progress has been made in an effort to exploit single-walled carbon nanotubes as fibers in epoxy-matrix/fiber composite materials. Two main obstacles to such use of carbon nanotubes are the following: (1) bare nanotubes are not soluble in epoxy resins and so they tend to agglomerate instead of becoming dispersed as desired; and (2) because of lack of affinity between nanotubes and epoxy matrices, there is insufficient transfer of mechanical loads between the nanotubes and the matrices. Part of the effort reported here was oriented toward (1) functionalization of single-walled carbon nanotubes with methyl methacrylate (MMA) to increase their dispersability in epoxy resins and increase transfer of mechanical loads and (2) ultrasonic dispersion of the functionalized nanotubes in tetrahydrofuran, which was used as an auxiliary solvent to aid in dispersing the functionalized nanotubes into a epoxy resin. In another part of this effort, poly(styrene sulfonic acid) was used as the dispersant and water as the auxiliary solvent. In one experiment, the strength of composite of epoxy with MMA-functionalized-nanotubes was found to be 29 percent greater than that of a similar composite of epoxy with the same proportion of untreated nanotubes.

Tiano, Thomas↗

Benzimidazole Based Aerogel Materials

The present invention provides aerogel materials based on imidazoles and polyimidazoles. The polyimidazole based aerogel materials can be thermally stable up to 500 C or more, and can be carbonized to produce a carbon aerogel having a char yield of 60% or more, specifically 70% or more. The present invention also provides methods of producing polyimidazole based aerogel materials by reacting at least one monomer in a suitable solvent to form a polybenzimidazole gel precursor solution, casting the polybenzimidazole gel precursor solution into a fiber reinforcement phase, allowing the at least one gel precursor in the precursor solution to transition into a gel material, and drying the gel materials to remove at least a portion of the solvent, to obtain an polybenzimidazole-based aerogel material.

Rhine, Wendell E.↗

Processing and Characterization of Carbon Nanotube Composites

Recent advances in the synthesis of large-scale quantities of carbon nanotubes (CNT) have provided the opportunity to study the mechanical properties of polymer matrix composites using these novel materials as reinforcement. Nanocomp Technologies, Inc. currently supplies large sheets with dimensions up to 122 cm x 244 cm containing both single-wall and few-wall CNTs. The tubes are approximately 1 mm in length with diameters ranging from 8 to 12 nm. In the present study being conducted at NASA Langley Research Center (LaRC), single and multiple layers of CNT sheets were infused or coated with various polymer solutions that included commercial toughened-epoxies and bismaleimides, as well as a LaRC developed polyimide. The resulting CNT composites were tested in tension using a modified version of ASTM D882-12 to determine their strength and modulus values. The effects of solvent treatment and mechanical elongation/alignment of the CNT sheets on the tensile performance of the composite were determined. Thin composites (around 50 wt% CNT) fabricated from acetone condensed and elongated CNT sheets with either a BMI or polyimide resin solution exhibited specific tensile moduli approaching that of toughened epoxy/ IM7 carbon fiber unidirectional composites.

Can, Roberto J.↗

Phenylated Polyimides With Greater Solubility

In experiments, 3,6-diphenylpyromellitic dianhydride monomer prepared and polymerized with several different diamines. Polyimides with pendent phenyl groups along polymer backbones considerably more soluble than PMDA-based materials. Increased solubility eases processing, providing increased potential use in variety of applications. Because most polymers soluble in organic solvents, usable in microelectronics applications. Excellent thermal stabilities and high transition temperatures make them ideally suited. Many polymers extremely rigid and useful as reinforcing polymers in molecular composites. More flexible compositions useful as matrix resins in carbon-reinforced composites.

Harris, Frank W.↗

Cleaning By Blasting With Pellets Of Dry Ice

Dry process strips protective surface coats from parts to be cleaned, without manual scrubbing. Does not involve use of flammable or toxic solvents. Used to remove coats from variety of materials, including plastics, ceramics, ferrous and nonferrous metals, and composites. Adds no chemical-pollution problem to problem of disposal of residue of coating material. Process consists of blasting solid carbon dioxide (dry ice) pellets at surface to be cleaned. Pellets sublime on impact and pass into atmosphere as carbon dioxide gas. Size, harness, velocity, and quantity of pellets adjusted to suit coating material and substrate.

Fody, Jody↗

Electrochemical Cell for Obtaining Oxygen from Carbon Dioxide Atmospheres

To support human life on the Martian surface, an electrochemical device will be required to obtain oxygen from the carbon dioxide rich atmosphere. The electrolyte employed in such a device must be constructed from extremely thin, dense membranes to efficiently acquire the oxygen necessary to support life. A forming process used industrially in the production of multilayer capacitors and electronic substrates was adapted to form the thin membranes required. The process, known as the tape casting, involves the suspension consisting of solvents and binders. The suspension is passed under a blade, resulting in the production of ceramic membranes between 0.1 and 0.5 mm thick. Once fired, the stabilized zirconia membranes were assembled into the cell design by employing a zirconium phosphate solution as the sealing agent. The resulting ceramic-to-ceramic seals were found to be structurally sound and gas-tight. Furthermore, by using a zirconia-based solution to assemble the cell, the problem of a thermal expansion mismatch was alleviated. By adopting an industrial forming process to produce thin membranes, an electrochemical cell for obtaining oxygen from carbon dioxide was produced. The proposed cell design is unique in that it does not require a complicated manifold system for separating the various gases present in this process, nor does it require a series of complex electrical connections. Thus, the device can reliably obtain the vital oxygen supply from the toxic carbon dioxide atmosphere.

Hooker, Matthew↗

Carbon Nanotube Synthesis in a Flame with Independently Prepared Laser-Ablated Catalyst Particles

Laser ablation has been used ex situ to create metal nanoparticles for introduction into a reactive pyrolysis flame. By prior synthesis of the metal nanoparticles, the effects of the reactive gases can be clearly separated from the pyrolysis chemistry of a solvent carrier, as when nebulized solutions are used. Moreover, varying reactivity issues associated with particle growth and size are bypassed. Our results show that Fe selectively reacts with CO to produce nanotubes, whereas Ni selectively reacts with C2H2 to produce nanofibers. These observations are interpreted through the donation and withdrawal of electron density between the adsorbate's molecular orbitals and surface atoms of the metal nanoparticle. The rate of reaction of Ni with only C2H2 is found to be greater than the rate with C2H2 and CO. This suggests that CO inhibits the Ni-catalyzed reaction.

Nanotubes, Carbon/chemistry/ultrastructure↗

Polyimides Containing Carbonyl and Ether Connecting Groups

Semicrystallinity gives rise to tough, solvent-resistant polymers. New polyimides prepared from reaction of aromatic dianhydrides with new diamines containing carbonyl and ether connecting groups between aromatic rings. Damines prepared from reaction of 4-aminophenol with activated aromatic difluoro compounds in presence of potassium carbonate. These types of polymers have potential applications in molded products, films, adhesives, and composites.

Hergenrother, Paul M.↗

Lithium Dinitramide as an Additive in Lithium Power Cells

Lithium dinitramide, LiN(NO2)2 has shown promise as an additive to nonaqueous electrolytes in rechargeable and non-rechargeable lithium-ion-based electrochemical power cells. Such non-aqueous electrolytes consist of lithium salts dissolved in mixtures of organic ethers, esters, carbonates, or acetals. The benefits of adding lithium dinitramide (which is also a lithium salt) include lower irreversible loss of capacity on the first charge/discharge cycle, higher cycle life, lower self-discharge, greater flexibility in selection of electrolyte solvents, and greater charge capacity. The need for a suitable electrolyte additive arises as follows: The metallic lithium in the anode of a lithium-ion-based power cell is so highly reactive that in addition to the desired main electrochemical reaction, it engages in side reactions that cause formation of resistive films and dendrites, which degrade performance as quantified in terms of charge capacity, cycle life, shelf life, first-cycle irreversible capacity loss, specific power, and specific energy. The incidence of side reactions can be reduced through the formation of a solid-electrolyte interface (SEI) a thin film that prevents direct contact between the lithium anode material and the electrolyte. Ideally, an SEI should chemically protect the anode and the electrolyte from each other while exhibiting high conductivity for lithium ions and little or no conductivity for electrons. A suitable additive can act as an SEI promoter. Heretofore, most SEI promotion was thought to derive from organic molecules in electrolyte solutions. In contrast, lithium dinitramide is inorganic. Dinitramide compounds are known as oxidizers in rocket-fuel chemistry and until now, were not known as SEI promoters in battery chemistry. Although the exact reason for the improvement afforded by the addition of lithium dinitramide is not clear, it has been hypothesized that lithium dinitramide competes with other electrolyte constituents to react with lithium on the surface of the anode to form a beneficial SEI. Apparently, nitrides and oxides that result from reduction of lithium dinitramide on the anode produce a thin, robust SEI different from the SEIs formed from organic SEI promoters. The SEI formed from lithium dinitramide is more electronically insulating than is the film formed in the presence of an otherwise identical electrolyte that does not include lithium dinitramide. SEI promotion with lithium dinitramide is useful in batteries with metallic lithium and lithium alloy anodes.

Gorkovenko, Alexander A.↗

Method of synthesizing small-diameter carbon nanotubes with electron field emission properties

Carbon nanotube material having an outer diameter less than 10 nm and a number of walls less than ten are disclosed. Also disclosed are an electron field emission device including a substrate, an optionally layer of adhesion-promoting layer, and a layer of electron field emission material. The electron field emission material includes a carbon nanotube having a number of concentric graphene shells per tube of from two to ten, an outer diameter from 2 to 8 nm, and a nanotube length greater than 0.1 microns. One method to fabricate carbon nanotubes includes the steps of (a) producing a catalyst containing Fe and Mo supported on MgO powder, (b) using a mixture of hydrogen and carbon containing gas as precursors, and (c) heating the catalyst to a temperature above 950.degree. C. to produce a carbon nanotube. Another method of fabricating an electron field emission cathode includes the steps of (a) synthesizing electron field emission materials containing carbon nanotubes with a number of concentric graphene shells per tube from two to ten, an outer diameter of from 2 to 8 nm, and a length greater than 0.1 microns, (b) dispersing the electron field emission material in a suitable solvent, (c) depositing the electron field emission materials onto a substrate, and (d) annealing the substrate.

Liu, Jie↗

Development of an impact- and solvent-resistant thermoplastic composite matrix, phase 3

The polyimide from BTDA 1,6-hexanediamine and m-phenylenediamine was selected from a prior study for the present study. Methods to prepare prepreg which would provide low void composites at low molding pressures from the thermoplastic polyimide were studied. Cresol solutions of the polyimide were applied to a balanced weave carbon fabric and the cresol removed prior to composite molding. Low void composites were prepared from smoothed prepregs at high pressures (34.5 MPa) and temperatures as low as 260 C. Lower molding pressures lead to higher void composites. Need for a lower melt viscosity in the neat resin is suggested as a requirement to achieve low void composites at low pressures. Some mechanical properties are included.

Delano, C. B.↗

Thermodynamic Properties of Uranium-Zirconium Carbide Solid Solutions with Oxygen

Uranium-zirconium carbide solid solutions are potential candidates for fuel in space nuclear reactors. To support development of advanced robust fuels for space applications, (U y Zr 1-y )C x O z solid solutions were synthesized via carbothermic reduction with uranium, carbon, and oxygen contents raging from y=0.05 – 0.3, x=0.95 – 0.98, and z = 0.02 – 0.07. These solid solutions were subsequently characterized by X-ray diffraction and elemental combustion analysis. High-temperature oxidative drop solution calorimetry in molten sodium molybdate solvent at 1073 K was employed to determine the formation, oxidation, and mixing enthalpies of (U y Zr 1-y )C x O z solid solutions, and thereby for evaluating their thermodynamic stability. The solid solutions are enthalpically less stable than the UC and ZrC end members. They also become less stable and more reactive towards oxidation with increasing uranium content. Incorporation of oxygen into solid solutions increases their solid solution-stability and improves their oxidation resistance.

Calorimetry↗

Lunar carbon chemistry - Relations to and implications for terrestrial organic geochemistry.

Survey of the various ways in which studies of lunar carbon chemistry have beneficially affected terrestrial organic geochemistry. A lunar organic gas-analysis operating system is cited as the most important instrumental development in relation to terrestrial organic geochemistry. Improved methods of analysis and handling of organic samples are cited as another benefit derived from studies of lunar carbon chemistry. The problem of controlling contamination and minimizing organic vapors is considered, as well as the possibility of analyzing terrestrial samples by the techniques developed for lunar samples. A need for new methods of analyzing carbonaceous material which is insoluble in organic solvents is indicated.

Eglinton, G.↗