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At least 451 records · Page 25

Copper carbon composite wire with a uniform carbon dispersion made by friction extrusion

Copper-carbon composites are a group of materials with excellent mechanical, electrical, thermal, and tribological properties. However, bulk size copper-carbon composites made by the traditional manufacturing processes, like rolling or extrusion, fall short of reaching some of these properties predicted by theory or demonstrated only by samples at centimeter scale or smaller. The two main challenges to the successful scaling-up are: 1) to uniformly disperse carbon in the metal matrix; 2) to avoid degradation due to oxidation or reaction from overheating. In this work, we first demonstrate friction extrusion as a new method to make bulk-size void-free copper-carbon composite wires with homogenized carbon dispersion. Three different carbon varieties, graphite powder, graphene nanopowder, and carbon nanotubes, were added to the copper matrix with the concentration ranging from 0.5 wt% to 15 wt%. Special tooling, processing parameters, and procedures were developed, especially for high carbon content samples. Ten-fold reductions of both copper grain size and carbon particle size were achieved and attributed to the high shear deformation. Energy dispersive X-ray spectrometry indicates the carbon powder was refined to a sub-micron level and uniformly dispersed in the copper matrix. Compared with that of pure copper, the thermal capacity of the composite wire increases by 30 % while density reduces by 29 %.

Friction extrusion, Metal matrix composite, Graphe↗

Examining Performance Loss Mechanisms in Lithium-Ion Batteries with the High-Voltage Mn-Rich Spinel Positive Electrodes

The high-voltage spinel, with the nominal composition of LiNi 0.5-x Mn 1.5+x O 4 (LNMO), could be a sustainable alternative to the layered-oxide positive electrodes used in lithium-ion batteries. However, commercial acceptance has been limited as LNMO cells display rapid performance loss during cycling. To examine reasons for this loss we prepared cells with LNMO-based positive and either graphite or lithium titanate (LTO) based negative electrodes. Our initial cells displayed high impedance and rapid impedance rise during cycling. Adding single walled carbon nanotubes in the positive lowered initial cell impedance but impedance increased during cycling because of coating delamination from the Al foil. Using a primed Al current collector solved the delamination problem: cells with this current collector showed only a small impedance rise. Regarding capacity, cells with the LTO negative showed higher initial capacities and smaller fade. Our data indicate that cell capacity retention is determined by reduction reactions at the negative electrode that lower capacity and oxidation reactions at the positive electrode that increase capacity: both types of reactions deplete the cell electrolyte during extended cycling. All things considered, species generated at high voltages, either in the electrolyte or at the LNMO electrode, drive cell capacity fade.

25 ENERGY STORAGE↗

Experimental Constraints on the Stability of Clinopyroxene (+) Magnesite in Iron Bearing Planetary Mantles: Implications for Nakhlite Formation

Carbon is present in various forms in the Earth s upper mantle (carbonate- or diamond-bearing mantle xenoliths, carbonatite magmas, CO2 emissions from volcanoes...). Moreover, there is enough carbon in chondritic material to stabilize carbonates into the mantles of Mars or Venus as well as in the Earth. However, the interactions with iron have to be constrained, because Fe is commonly thought to buffer oxygen fugacity into planetary mantles. [1] and [2] show evidences of the stability of clinopyroxene Ca(Mg,Fe)Si2O6 + magnesite (Mg,Fe)CO3 in the Earth s mantle around 6GPa (about 180km). The stability of oxidized forms of carbon (like magnesite) depends on the oxygen fugacity of the system. In the Earth s mantle, the maximum carbon content is 10000 ppm [3]. The fO2 parameter varies vertically as a function of pressure, but also laterally because of geodynamic processes like subduction. Thus, carbonates, graphite, diamond, C-rich gases and melts are all stable forms of carbon in the Earth s mantle. [4] show that the fO2 variations observed in SNC meteorites can be explained by polybaric graphite-CO-CO2 equilibria in the Martian mantle. [5] inferred from thermodynamic calculations that the stable form of carbon in the source regions of the Martian basalts should be graphite (and/or diamond). After [6], a metasomatizing agent like a CO2-rich melt may infiltrate the mantle source of nakhlites. However, according to [7] and [8], the FeO wt% value in the Martian bulk mantle is more than twice that of the Earth s mantle (KLB-1 composition by [9]). As iron and carbon are two elements with various oxidation states, Fe/C interaction mechanisms must be considered.

Martin, Audrey M.↗

Polyimide resin composites via in situ polymerization of monomeric reactants

Thermo-oxidatively stable polyimide/graphite-fiber composites were prepared using a unique in situ polymerization of monomeric reactants directly on reinforcing fibers. This was accomplished by using an aromatic diamine and two ester-acids in a methyl alcohol solvent, rather than a previously synthesized prepolymer varnish, as with other A-type polyimides. A die molding procedure was developed and a composite property characterization conducted with high modulus graphite fiber tow. Flexure, tensile, compressive, and shear tests were conducted at temperatures from 72 to 650 F on laminates before and after exposures at the given temperatures in an air environment for times up to 1000 hours. The composite material was determined to be oxidatively, thermally, and hydrolytically stable.

Cavano, P. J.↗

Ultra-Low Amounts of Transition Metals in Carbon-Based Catalysts Improve Their Alkaline OER Performance: A Systematic Study

The pursuit of green hydrogen production highlights a persistent gap in electrocatalyst research: while academic efforts prioritize cost-efficiency via activity enhancement, industrial viability demands greater emphasis on electrochemical stability. Carbon-based electrocatalysts, particularly those incorporating transition metals, have shown promise in alkaline oxygen evolution (OER) due to their high activity, cost-efficiency, and resource-efficiency. However, these catalysts suffer from insufficient stability under oxidizing conditions compared to pure transition metal catalysts due to erosion of the carbon support resulting from carbon corrosion, among other degradation mechanisms. In this systematic study, the influence of ultra-low amounts (<1 wt %) of iron, cobalt, nickel, and their most common combinations on the stability of a hydrothermally derived, N-doped carbon support and the overall catalyst performance during alkaline OER is systematically explored. By identifying critical stability descriptors and correlating them with synthesis conditions and catalyst properties, primary and secondary corrosion pathways are unraveled. Subsequently, through careful adjustment of carbonization temperature and composition of incorporated transition metals, overall catalyst corrosion can be suppressed immensely. Especially, the inclusion of Ni and Fe is paramount for the formation of stable catalyst materials under laboratory conditions (10 mA/cm 2 in 0.1 M KOH), which is surprisingly unconstrained by the degree of graphitization of the carbon support. Mixing this electrochemically stable material with a graphitic carbon powder results in an excellent stability of over 400 h at 100 mA/cm 2 in 1 M KOH, implying great potential for the future improvement of carbon-based electrodes under oxidizing conditions toward industrial application.

N-doped carbon↗

Solar-thermal membrane for dewatering aqueous organic-acid solutions

A thermally conductive porous membrane has been developed to directly absorb solar energy and conduct heat that can effectively evaporate liquid water at the interface between the membrane and the bulk feed solution. Here, black, porous, thermally conductive graphite foam support is employed as an effective photothermal-energy absorber and heat conductor that heats up an aqueous feed solution to produce vapor. Graphite nanoparticle-slurry coating is applied onto the foam surface to reduce the pore size and generate a microporous membrane. Then, application of a dense graphene oxide membrane coating as an active separation layer on the microporous nanoparticle surface of internal foam channels allows vapor permeation of volatile molecules. Acetic acid/water solution was studied as a model feed system to experimentally demonstrate effective separation. This model vapor permeation system demonstrates excellent acetic acid separation, with a separation factor of 8.3, under simulated 0.7 sun irradiation. The membrane hydrophobicity and nanostructure, including pore size and surface chemistry, played a significant role in enabling high permselectivity of water vapor over acetic acid molecules, as well as liquid solution. Pore size reduction from open pores to a nonporous dense layer in the membrane enables effective separation of water vapor from the organic vapor, while it reduces the permeation flux. Also, the hydrophilicity of the membrane surface shows ~3 times higher permeation flux with higher permselectivity, compared with the hydrophobic membrane surface. This work introduces a process of directly using renewable energy instead of conventional heating to drive selective separation of water from organic acids.

14 SOLAR ENERGY↗

Lead leaching and electrowinning in acetic acid for solar module recycling

It is imperative to recover lead (Pb) contained in end-of-life solar modules. In this paper, a two-step leaching and electrowinning process using acetic acid is investigated for Pb recovery. Acetic acid with hydrogen peroxide can dissolve Pb quickly and, under some conditions, in a matter of minutes. Pb electrowinning has been successfully demonstrated from aqueous solutions of 0.009 M lead(II) acetate with 0–10% v/v acetic acid. Pb-containing deposits are found on both the copper cathode and graphite anode. X-ray diffraction, energy-dispersive X-ray spectroscopy, and Fourier transform infrared spectroscopy confirm the presence of metallic Pb and Pb(II) oxide (PbO) co-deposits on the cathode. Further, there is also the formation of lead subacetate on the cathode under certain conditions. On the anode, the deposit consists of lead(IV) oxide and superoxide (PbO 2 and Pb 1–x O 2 ). A Pb recovery rate of 99% is achieved in 0.009 M lead(II) acetate solutions with 10% v/v acetic acid by applying a reduction potential of either –0.8 V or –1.0 V versus the silver/silver chloride reference electrode for 24h. Pb leaching with acetic acid is also demonstrated from milled silicon solar modules.

14 SOLAR ENERGY↗

Graphite Ablation and Thermal Response Simulation Under Arc-Jet Flow Conditions

The Two-dimensional Implicit Thermal Response and Ablation program, TITAN, was developed and integrated with a Navier-Stokes solver, GIANTS, for multidimensional ablation and shape change simulation of thermal protection systems in hypersonic flow environments. The governing equations in both codes are demoralized using the same finite-volume approximation with a general body-fitted coordinate system. Time-dependent solutions are achieved by an implicit time marching technique using Gauess-Siedel line relaxation with alternating sweeps. As the first part of a code validation study, this paper compares TITAN-GIANTS predictions with thermal response and recession data obtained from arc-jet tests recently conducted in the Interaction Heating Facility (IHF) at NASA Ames Research Center. The test models are graphite sphere-cones. Graphite was selected as a test material to minimize the uncertainties from material properties. Recession and thermal response data were obtained from two separate arc-jet test series. The first series was at a heat flux where graphite ablation is mainly due to sublimation, and the second series was at a relatively low heat flux where recession is the result of diffusion-controlled oxidation. Ablation and thermal response solutions for both sets of conditions, as calculated by TITAN-GIANTS, are presented and discussed in detail. Predicted shape change and temperature histories generally agree well with the data obtained from the arc-jet tests.

Chen, Y.-K.↗

Solubility, stability, and electrochemical studies of sulfur-sulfide solutions in organic solvents

A preliminary study of the sulfur electrode in organic solvents suggests that the system warrants further investigation for use in a low temperature (100 deg to 120 C) Na-S secondary battery. A qualitative screening was undertaken at 120 C to determine the solubilities and stabilities of Na2S and Na2S2 in representatives of many classes of organic solvents. From the screening and quantitative studies, two classes of solvents were selected for work; amides and cyclic polyalcohols. Voltammetric and Na-S cell charge discharge studies of sulfide solutions in organic solvents (e.g., N, N-dimethylformamide) at 120 C suggested that the reversibilities of the reactions on Pt or high density graphite were moderately poor. However, the sulfur electrode was indeed reducible (and oxidizable) through the range of elemental sulfur to Na2S. Reactions and mechanisms are proposed for the oxidation reduction processes occurring at the sulfur electrode.

Fielder, W. L.↗

High Temperature Chemistry in the Columbia Accident Investigation

Initial estimates on the temperature and conditions of the breach in Columbia's wing focused on analyses of the slag deposits. These deposits are complex mixtures of the reinforced carbon/carbon (RCC) constituents, insulation material, and wing structural materials. However it was possible to clearly discern melted/solidified Cerachrome(R) insulation, indicating the temperatures had exceeded 1760 C. Current research focuses on the carbon/carbon in the path from the breach. Carbon morphology indicates heavy oxidation and erosion. Raman spectroscopy yielded further temperature estimates. A technique developed at Sandia National Laboratories is based on crystallite size in carbon chars. Lower temperatures yield nanocrystalline graphite; whereas higher temperatures yield larger graphite crystals. By comparison to standards the temperatures on the recovered RCC fragments were estimated to have been greater than 2700 C.

Jacobson, Nathan↗

Pt-Ni and Pt-Co Catalyst Synthesis Route for Fuel Cell Applications

Oxygen reduction reactions (ORRs) at the cathode are the rate-limiting step in fuel cell performance. The ORR is 100 times slower than the corresponding hydrogen oxidation at the anode. Speeding up the reaction at the cathode will improve fuel cell efficiency. The cathode material is generally Pt powder painted onto a substrate (e.g., graphite paper). Recent efforts in the fuel cell area have focused on replacing Pt with Pt-X alloys (where X = Co, Ni, Zr, etc.) in order to (a) reduce cost, and (b) increase ORR rates. One of these strategies is to increase ORR rates by reducing the powder size, which would result in an increase in the surface area, thereby facilitating faster reaction rates. In this work, a process has been developed that creates Pt-Ni or Pt-Co alloys that are finely divided (on the nano scale) and provide equivalent performance at lower Pt loadings. Lower Pt loadings will translate to lower cost. Precursor salts of the metals are dissolved in water and mixed. Next, the salt mixtures are dried on a hot plate. Finally, the dried salt mixture is heattreated in a furnace under flowing reducing gas. The catalyst powder is then used to fabricate a membrane electrode assembly (MEA) for electrochemical performance testing. The Pt- Co catalyst-based MEA showed comparable performance to an MEA fabri cated using a standard Pt black fuel cell catalyst. The main objective of this program has been to increase the overall efficiencies of fuel cell systems to support power for manned lunar bases. This work may also have an impact on terrestrial programs, possibly to support the effort to develop a carbon-free energy source. This catalyst can be used to fabricate high-efficiency fuel cell units that can be used in space as regenerative fuel cell systems, and terrestrially as primary fuel cells. Terrestrially, this technology will become increasingly important when transition to a hydrogen economy occurs.

Firdosy, Samad A.↗

In-situ Nanoscale Ablation

An understanding of the ablation of carbon-based materials is crucial to modeling the behavior of atmospheric entry spacecrafts equipped with thermal protection systems (TPS).Carbon is the backbone of TPS systems such as PICA (phenolic-impregnated carbon ablator).Therefore in the present work we study ablation of highly oriented pyrolytic graphite (HOPG)in oxygen at temperatures up to 1000°C done within a gas reaction cell housed in a scanning transmission electron microscope (STEM). Observation of the HOPG oxidation on specimens sectioned parallel and normal to the carbon basal planes in the presence of oxygen are reported.Pitting caused by residual oxygen and/or platinum particles from the sectioning process was observed before oxygen gas flow was established at 750°C in the specimen sectioned with the carbon basal planes parallel to the beam direction. Introduction of oxygen flow caused rapid oxidation moving in a uniform front that completely consumed the HOPG in approximately 1.5minutes. The specimen sectioned with the carbon basal planes normal to the beam direction did not show the same pitting phenomenon but exhibited rapid oxidation at 1000°C that proceeded in a uniform front and completed in approximately 1 minute. All specimens tested had a husk resembling the original specimen shape left over after oxidation. It is concluded that this husk is most likely ash impurity from the HOPG or impurities from the sectioning process or E-chip. A residual gas analyszer (RGA) was successfully used to monitor gas flows during the experiments but was yet unsuccessful in monitoring oxidation gas products produced during the experiment.Future studies will optimize the RGA setup in order to maximize the potential for detecting these species. These in-situ studies successfully show how this highly ordered carbon ablates on a nano- and micro-scopic length scale and can be used to provide fundamental understanding of carbon ablation that can be used to design the next-generation of TPS systems.

Nanoscale Ablation↗

Functionalized Embedded Monometallic Nickel Catalysts for Enhanced Hydrogen Evolution: Performance and Stability

Viable anionic exchange membrane (AEM) electrolysis for H 2 production requires highly active hydrogen evolution reaction (HER) catalysts that are also robust and cost-effective. Traditionally juxtaposition of two transition metals with one being more oxophilic is necessary for easier access to water in the inner Helmholtz plane as a source of protons in the crucial Volmer step for enhanced HER activity. However, they are prone to passivation at anodic potentials or deactivation via the formation of sub-surface metal hydrides at high cathodic overpotentials. Here we report a method of enabling close juxtaposition of Ni-Ni-oxide surfaces by functionalizing Ni-based catalysts via the careful thermal treatment of carbon-supported Ni nano-particles chelated with a select organic chelating compound referred to as cupferron. This functionalization results in an embedded Ni surface with a clear graphitic coating engendering long-term stability for passivation and subsurface hydride formation. The stability and activity of the functionalized Ni catalyst are demonstrated in half-cell RDE and full-cell AEM membrane-based hydrogen pump experiments. In the case of the latter, the functionalized Ni outperforms carbon-supported Pt.

25 ENERGY STORAGE↗

Replacement of MDA with more oxidatively stable diamines in PMR-polyimides

Studies are performed to investigate the effect of substituting 4,4'-oxydianiline and 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane for the 4,4'-methylenedianiline in PMR polyimide matrix resin. Graphite fiber reinforced composites are fabricated from unsized Celion 6000 and PMR-polyimide matrix resins having formulated molecular weights in the range of 1500 to 2400. The composite processing characteristics are investigated and the initial room temperature and 316 C (600 F) composite mechanical properties are determined. Comparative 316 C composite weight losses and 316 C mechanical properties retention after prolonged 316 C air exposure are also determined.

Alston, W. B.↗

Graphene Transparent Conductive Electrodes for Next- Generation Microshutter Arrays

Graphene is a single atomic layer of graphite. It is optically transparent and has high electron mobility, and thus has great potential to make transparent conductive electrodes. This invention contributes towards the development of graphene transparent conductive electrodes for next-generation microshutter arrays. The original design for the electrodes of the next generation of microshutters uses indium-tin-oxide (ITO) as the electrode material. ITO is widely used in NASA flight missions. The optical transparency of ITO is limited, and the material is brittle. Also, ITO has been getting more expensive in recent years. The objective of the invention is to develop a graphene transparent conductive electrode that will replace ITO. An exfoliation procedure was developed to make graphene out of graphite crystals. In addition, large areas of single-layer graphene were produced using low-pressure chemical vapor deposition (LPCVD) with high optical transparency. A special graphene transport procedure was developed for transferring graphene from copper substrates to arbitrary substrates. The concept is to grow large-size graphene sheets using the LPCVD system through chemical reaction, transfer the graphene film to a substrate, dope graphene to reduce the sheet resistance, and pattern the film to the dimension of the electrodes in the microshutter array. Graphene transparent conductive electrodes are expected to have a transparency of 97.7%. This covers the electromagnetic spectrum from UV to IR. In comparison, ITO electrodes currently used in microshutter arrays have 85% transparency in mid-IR, and suffer from dramatic transparency drop at a wavelength of near-IR or shorter. Thus, graphene also has potential application as transparent conductive electrodes for Schottky photodiodes in the UV region.

Li, Mary↗

A search for noble-gas evidence for presolar oxide grains

Early results from an ongoing search for isotopically distinctive noble gases as evidence for presolar oxide grains are presented. With some qualifications, we do not see such evidence in spinel rich acid residue fractions from the Allende meteorite. We remain hopeful that less abundant mineral separates may yet be fruitful. Presolar grains, micro-diamonds, silicon carbide, and graphite, were found in primitive meteorites. While the abundances of these three refractory C rich grains are low, a few hundred ppm, a few ppm, & less than 1 ppm, respectively in primitive meteorites, they are tagged with high concentrations of isotopically anomalous noble gas components, Xe-HL, KR & Xe-s and Ne-E(H), and Ne-E(L). These tags have served as tracers and allowed the development of techniques for their purification and eventual identification. One might expect similar amounts of refractory presolar oxides to have survived, but so far only three cases exist for their identification. The first two cases are individual corundum oxide grains. Huss et al. found one such grain from an Orgueil residue with an Al-26/Al-27 ratio of 8.9 x 10(exp -5), about 18 times higher than the canonical initial solar system value. The second corundum grain, from Murchison, was found by Nittler et al. to have unusual oxygen in addition to a similar Al-26/Al-27 ratio of 8.7 x 10(exp -4). The oxygen was depleted in O-18 by 22 percent and enriched in O-17 by a factor of 2. The third case is a measurement by Zinner et al. on an aggregate of fine grained spinels from a Murray residue with an O-17 enrichment and a possible O-18 depletion similar to the second grain, but much subdued. This is consistent with a few such presolar grains diluted by a much larger population of isotopically normal corundum grains and an even larger number of normal spinel grains.

Lewis, Roy S.↗

Bismaleimides and related maleimido polymers as matrix resins

Significant processing and property improvements can be achieved by copolymerization of state-of-the-art bisimides with various vinyl stilbazole derivatives to give both fire resistance and high-temperature properties from hot-melt compositions. Significant improvement in mechanical properties is achieved through these modifications, which may make these new matrix resins ideal candidates for fireworthy secondary graphite composite structures. Phosphorous modifications of maleimido polymers through phosphonate structure and tricyclophosphazene derivatives provide families of new matrix resins for short-time applications in severe thermo-oxidative environments. With further research these may provide matrix resins for long-term thermo-oxidative stability of advanced composites at temperatures up to 400 to 500 C.

Parker, J. A.↗

Thermo-oxidative stability studies of PMR-15 polymer matrix composites reinforced with various fibers

An experimental study was conducted to measure the thermo-oxidative stability of PMR-15 polymer matrix composites reinforced with various fibers and to observe differences in the way they degrade in air. The fibers that were studied included graphite and the thermally stable Nicalon and Nextel ceramic fibers. Weight loss rates for the different composites were assessed as a function of mechanical properties, specimen geometry, fiber sizing, and interfacial bond strength. Differences were observed in rates of weight loss, matrix cracking, geometry dependency, and fiber-sizing effects. It was shown that Celion 6000 fiber-reinforced composites do not exhibit a straight-line Arrhenius relationship at temperatures above 316 C.

Bowles, Kenneth J.↗