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At least 397 records · Page 22

Evaluation of carbon-carbon for space engine nozzle

An investigation is underway to determine the suitability of carbon-carbon composite materials for lightweight nozzle extensions on the Orbit Transfer Vehicle (OTV). The best combinations of fiber precursor, matrix material, and oxidation protection coatings are being evaluated in a series of hot-fire tests in an O sub 2/H sub 2 rocket nozzle environment. Evaluation criteria include life expectancy (recession), strength to weight, producibility, maturity, and cost. A data base of carbon-carbon performance in the OTV nozzle environment will be established which may be used in designing a full-scale OTV nozzle extension.

Suhoza, J. P.↗

Carbon Electrodes from Powder River Basin Coal Development of Competitive Supercapacitor Electrodes of Diverse Compositions from Coal Extract

Recent demand for coal as a thermal energy source has decreased significantly and will likely continue to decrease as renewable sources of energy become more available and environmental concern and cost from burning coal makes it more costly than renewables. Given that Powder River Basin (PRB) coal in Wyoming has relatively low thermal energy, it is critical for Wyoming to employ coal in other capacities at the current energy transition period in history. Among many potential non-thermal applications, PRB coal can be utilized for membrane and electrode applications through the formation of carbon fibers. Coal-derived membranes can become low-cost, conductive membranes for use in electrodialysis separation processes. Carbon fiber derived electrodes have been shown be a cost-effective alternative to typical electrode materials that can meet or exceed the performance of current carbon electrode materials. In this talk, we demonstrate the manufacture of supercapacitor electrodes from Powder River Basin (PRB) coal-derived precursors. Specifically, PRB coal was treated in cheap solvents, partitioned into liquid extract and solid residue. An electropinning process has been developed that can convert either the liquid extract or the solid residue into carbon fiber mats. The electrospinning process is versatile with many tunable process parameters to achieve desirable physiochemical properties. For example, the coal residue can be manipulated by additional heat treatment, or by adding binders, salts, or surfactants to create a solution that can be electrospun into advanced carbon electrodes with desirable structural and surface properties. Similarly, some of the liquid extract (tar fraction) can be subsequently reacted with toluene diisocyanate to create resinous coal-derived polyurethane (PUs) as a spinnable ink. Carbon nanofiber mats made from our proprietary electrospinning process were further carbonized at temperature ranging from 700°C to 900°C before they are used as electrodes in supercapacitors. Galvanostatic charge-discharge (GCD) results show that the best performing PU fiber mats can deliver a specific capacitance of 604 F g -1 at the current density of 1 A g -1 . A carbon fiber mat from a different solvent extraction residue also delivered the specific capacitance of 508 F g -1 . These specific capacitance values are comparable to or better than commercial activated carbons, demonstrating the viability of manufacturing carbon nanofiber electrodes from coal without the use of a commercial polymer as binder in the spinning ink.

Cincotta, Robert↗

Influence of residual chlorine on Ru/TiO 2 active sites during CO 2 methanation

Titania-supported ruthenium (Ru/TiO 2 ) is an established catalyst for the hydrogenation of carbon dioxide to methane (Sabatier reaction). Chlorine contamination, owed to the RuCl 3 precursor, is demonstrated to have a detrimental impact on methanation activity. After calcination and reduction the catalyst contains residual chlorine, shown by XPS. An aqueous ammonia wash removes Cl without leaching Ru. The washed catalysts exhibit improvements in CH 4 site-time yields. Low Ru loading catalysts encounter the greatest activity enhancements after washing (~4.5-fold). DFT calculations indicate that chlorine and CO 2 directly compete for adsorption on Ru step sites, with Cl impeding the adsorption of CO 2 at under-coordinated sites and at higher Cl coverages. H 2 -chemisorption/TPR show that Cl removal lowers the onset of low temperature H 2 dissociation on Ru. Finally, DRIFTS provide evidence that the removal of Cl facilitates low temperature dissociative binding of CO 2 , indicated by the formation of surface bound linear CO species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Selective Conversion of CO 2 to Methanol on a In 2 O 3– x –TiO 2 (110) Interface: Importance of Oxide–Oxide Interactions

Methanol is a strategic energy vector for the storage and delivery of energy and is a widely used precursor for the synthesis of many high-value chemicals. The hydrogenation of carbon dioxide (CO 2 ) into methanol is a key process in industrial operations. Here, in this study, we show that an oxide-oxide interface generated by a low loading (0.15 ML) of In 2 O 3-x on a TiO 2 (110) substrate has a high activity and selectivity as a catalyst for the CO 2 + 3H 2 → CH 3 OH + H 2 O process. The properties of the In 2 O 3-x -TiO 2 interface under reaction conditions were investigated using a combination of synchrotron-based ambient pressure X-ray photoelectron spectroscopy (AP-XPS), temperature programmed desorption (TPD), and catalytic testing. The In 2 O 3-x overlayer spread out on top of the titania and was rich in defects and O vacancies that activated CO 2 and H 2 as reactants, without destroying CH 3 O and CH 3 OH as reaction products. The In 2 O 3-x /TiO 2 (110) catalyst is at least one order of magnitude more active than bulk indium oxide while maintaining a very high selectivity (~80%) towards methanol production. Under the rich hydrogen environment of methanol synthesis, the oxide-oxide interactions allowed only a partial reduction of the In cations, preventing the formation of metal alloys as seen in the case of catalysts with metal-indium oxide interfaces. Thus, the dispersion of low loadings of In 2 O 3-x on a stable oxide substrate is a valid and low-cost approach for generating efficient catalysts for CO 2 valorization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Mo precursors in Microwave-assisted Methane Dehydroaromatization over Mo/HZSM5 catalysts

Natural gas flaring occurs in remote shale regions due to limited pipeline takeaway capacity. The conversion of the associated natural gas into aromatics in modular microwave reactors is a viable alternative to monetize the wasted gas. Microwaves offer rapid, selective heating in compact reactor systems that can enable on-demand chemical production at the well-site. Mo-HZSM-5 catalysts are widely used for aromatic production, but the location and nature of the active sites are still under debate. This study focuses on the use of 6 different Mo precursors to elucidate insights into the Mo properties that are desirable for BTX production. The catalysts were characterized by different methods (XPS, TPR, Raman, etc) to determine differences in Mo catalytic properties that may affect performance and understand these differences through performance testing under microwave at 700C for methane dehydroaromatization. Metal precursors that enable a better distribution of Mo into the pores and over the surface lead to improved benzene yield, whereas those that limited Mo to primarily the surface suffer rapid deactivation and low benzene yields. Additionally, strong Lewis acidity that arises from the sodium containing precursor drastically shifts the product selectivity towards dehydrogenation, which produces more ethylene and carbon. This catalyst had the highest deactivation constant of all catalysts tested.

gas flaring reduction↗

Viscous effects in rapidly rotating stars with application to white-dwarf models. III - Further numerical results

Improved viscous evolutionary sequences of differentially rotating, axisymmetric, nonmagnetic, zero-temperature white-dwarf models are constructed using the relativistically corrected degenerate electron viscosity. The results support the earlier conclusion that angular momentum transport due to viscosity does not lead to overall uniform rotation in many interesting cases. Qualitatively different behaviors are obtained, depending on how the total mass M and angular momentum J compare with the M and J values for which uniformly rotating models exist. Evolutions roughly determine the region in M and J for which models with a particular initial angular momentum distribution can reach carbon-ignition densities in 10 b.y. Such models may represent Type I supernova precursors.

Durisen, R. H.↗

Mars rover sample return mission utilizing in situ production of the return propellants

This paper presents an unmanned Mars sample return mission that utilizes propellants manufactured in situ from the Martian atmosphere for the return trip. A key goal of the mission is to demonstrate the considerable benefits that can be realized through the use of indigenous resources and to test the viability of this approach as a precursor to manned missions to Mars. Two in situ propellant combinations, methane/oxygen and carbon monoxide/oxygen, are compared to imported terrestrial hydrogen/oxygen within a single mission architecture, using a single Earth launch vehicle. The mission is assumed to be launched from Earth in 2003. Upon reaching Mars, the landing vehicle aerobrakes, deploys a small satellite, and lands on the Martian surface. Once on the ground, the propellant production unit is activated, and the product gases are liquefied and stored in the empty tanks of the Earth Return Vehicle (ERV). Power for these activities is provided by a dynamic isotope power system. A semiautonomous rover, powered by the indigenous propellants, gathers between 25 and 30 kg of soil and rock samples which are loaded aboard the ERV for return to Earth. After a surface stay time of approximately 1.5 years, the ERV leaves Mars for the return voyage to Earth. When the vehicle reaches the vicinity of Earth, the sample return capsule detaches, and is captured and circularized in LEO via aerobraking maneuvers.

Bruckner, A. P.↗

Four advances in carbon-carbon materials technology

Carbon-carbon composites are a specialty class of materials having many unique properties making these composites attractive for a variety of demanding engineering applications. Chief among these properties are exceptional retention of mechanical properties at temperatures as high as 4000 F, excellent creep resistance, and low density (1.6 to 1.8 g/cu cm). Although carbon-carbon composites are currently in service in a variety of applications, much development work remains to be accomplished before these materials can be considered to be fully mature, realizing their full potential. Four recent technology advances holding particular promise for overcoming current barriers to the wide-spread commercialization of carbon-carbon composites are described. These advances are: markedly improved interlaminar strengths (more than doubled) of two dimensional composites achieved by whiskerization of the fabric reinforcing plies, simultaneously improved oxidation resistance and mechanical properties achieved by the incorporation of matrix-phase oxidation inhibitors based on carborane chemistry, improved oxidation resistance achieved by compositionally graded oxidation protective coatings, and markedly reduced processing times (hours as opposed to weeks or months) accomplished through a novel process of carbon infiltration and coatings deposition based on the use of liquid-phase precursor materials.

Maahs, Howard G.↗

Formation of Hydrocarbons in the Outflows from Red Giants

The formation of hydrocarbons in the oxygen-rich outflows from red giants was studied. The existence of organic molecules in such outflows has been known for several years; however, their surprisingly high abundances has been a mystery since all of the carbon had been thought to be irretrievably locked up in CO, the most strongly bound molecule. CO is the first molecule to form from the atoms present in the star's extended atmosphere, and as strong stellar winds drive a cooling outflow, dust grains condense out. In oxygen-rich outflows, the dust is thought to be composed mainly of silicates and other metal oxides. Perhaps the noble metals can condense out in metallic form, in particular the relatively abundant transition metals iron and nickel. We proposed that perhaps the carbon reservoir held as CO can be accessed through a catalytic process involving the chemisorption of CO and H2 onto grains rich in metallic iron. CO and H2 are the two most abundant molecules in circumstellar outflows, and they both are known to dissociate on transition metal surfaces at elevated temperatures, freeing carbon to form organic molecules such as methane. We believe methane is a precursor molecule to the organics observed in oxygen-rich red giants. We have developed a nonequilibrium numerical model of a surface chemical (catalytic) process. Based on this model, we believe that methane can be formed under the conditions present in circumstellar outflows. Although the methane formation rates are exceptionally low under these conditions, over dynamical timescales, a significant amount of CO can be converted to methane and driven further out in the envelope, explaining the presence of organics there.

Roberge, Wayne↗

Tractable Chemical Models for CVD of Silicon and Carbon

Tractable chemical models are validated for the CVD of silicon and carbon. Dilute silane (SiH4) and methane (CH4) in hydrogen are chosen as gaseous precursors. The chemical mechanism for each systems Si and C is deliberately reduced to three reactions in the models: one in the gas phase and two at the surface. The axial-flow CVD reactor utilized in this study has well-characterized flow and thermal fields and provides variable deposition rates in the axial direction. Comparisons between the experimental and calculated deposition rates are made at different pressures and temperatures.

Blanquet, E.↗

Synthesis of Amino Acid Precursors with Organic Solids in Planetesimals with Liquid Water

Amino acids are important ingredients of life that would have been delivered to Earth by extraterrestrial sources, e.g., comets and meteorites. Amino acids are found in aqueously altered carbonaceous chondrites in good part in the form of precursors that release amino acids after acid hydrolysis. Meanwhile, most of the organic carbon (greater than 70 weight %) in carbonaceous chondrites exists in the form of solvent insoluble organic matter (IOM) with complex macromolecular structures. Complex macromolecular organic matter can be produced by either photolysis of interstellar ices or aqueous chemistry in planetesimals. We focused on the synthesis of amino acids during aqueous alteration, and demonstrated one-pot synthesis of a complex suite of amino acids simultaneously with IOM via hydrothermal experiments simulating the aqueous processing

Kebukawa, Y↗

Triton Hopper: Exploring Neptune's Captured Kuiper Belt Object

Neptune's moon Triton is a fascinating object, a dynamic moon with an atmosphere, and geysers. Triton is unique in the outer solar system in that it is most likely a captured Kuiper belt object (KBO), a leftover building block of the solar system. When Voyager flew by it was the coldest body yet found in our solar system (33 degrees Kelvin) and had volcanic activity, geysers, and a thin atmosphere. It is covered in ices made from nitrogen, water, and carbon-dioxide, and shows surface deposits of tholins, organic compounds that may be precursor chemicals to the origin of life. Exploring Triton will be a challenge well beyond anything done in previous missions; but the unique environment of Triton also allows some new possibilities for mobility. We developed a conceptual design of a Triton Hopping probe that both analyzes the surface and collects it for use to propel its hops. The Hopper would land near the South Pole in 2040 where geysers have been detected. Depending the details of propulsion chosen the Hopper should be able to jump over 300 kilometers in 60 hops or less, exploring the surface and thin atmosphere on its way. This craft will autonomously carry out detailed scientific investigations on the surface, below the surface (drilling) and in the upper atmosphere to provide unprecedented knowledge of a KBO-turned moon and expanding NASA's existing capabilities in deep space planetary exploration to include Hoppers using different ices for propellant. Triton is roughly 2700 kilometers in diameter with a surface of mostly frozen nitrogen, mostly water ice crust and core of metal and rock. Its gravity is half that of Earth's Moon and its atmosphere is 170,000th of Earth's or 0.3 of Mars.The mission concept studied investigated the full surface and atmospheric phenomenon: chemical composition of surface and near subsurface materials, the thin atmosphere, volcanic and geyser activity. Measurements of all these aspects of Triton's unique environment can only be made through focused in-situ exploration with a well-instrumented craft. And this craft will be provided revolutionary mobility, nearly global, using in-situ ices as propellants. While other concepts have looked at gathering gases at Mars to propel a hopper, long periods of time are needed to gather the thin CO2 atmosphere. Several gases, mainly nitrogen are on the surface in a readily dense ice form and just need to be picked up, vaporized and used for propellant.

low conductivity materials↗

BETO 2021 Peer Review - Waste Carbon Gas Upgrading via Acetogens 2.3.2.106

Waste carbon gas represents a large and diverse set of feedstocks that could be captured and turned into useful products. This includes waste gas emitted from industrial activity, syngas from burned plant biomass or processed municipal waste, and electrochemical reduction of CO2. Currently, carbon gas is being microbially converted to ethanol as a main product. However, ethanol is a lower value product with a limited market size. While these microbes can make other higher value products, there are no commercial processes for generating these other products, leaving a gap in understanding potential implementation for commercialization. Expanding the products microbially produced from waste carbon gas requires several steps before commercial implementation. We are studying the acetogen Clostridium ljungdahlii as a biocatalyst to convert waste carbon gas to the chemical 3-hydroxybutyrate (3HB), a plastic monomer and fuel precursor. For that, we are studying and engineering microbial characteristics for novel 3HB product formation from waste gas streams. This includes metabolic characterization, genetic engineering, gas fermentation scaling, as well as technoeconomic and life cycle analysis.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Unidirectional growth of graphene nano-islands from carbon cluster seeds on Ge(1 1 0)

The anisotropic twofold symmetry of Ge(1 1 0) makes it a unique substrate for the growth of single-crystalline graphene. However, the underlying mechanism during the initial stage of growth of graphene on Ge(1 1 0) surface is not well understood. Here, we use in-situ cryogenic scanning tunneling microscopy (STM) and spectroscopy (STS), to study the initial growth properties of graphene synthesized on Ge(1 1 0) surface with ethylene precursor gases. The STM results reveal that the unidirectional growth of the graphene nanoribbons (GNRs) initiates from carbon cluster seeds on terraces during the early stage of the growth. The orientations of the GNRs show the same directions which are nearly parallel to the direction of the Ge(1 1 0) surface. This orientation is the same as that of the wafer-scale graphene grown on Ge(1 1 0). Subsequent growth, transformed the GNRs to graphene nanoislands (GNIs), which eventually coalesced to form single crystalline monolayer graphene. STS measurements demonstrated that the GNRs have small bandgaps induced by the confinement effect of graphene. Furthermore, this study provides an in-depth understanding of the growth mechanism of graphene on Ge(1 1 0) surface in various synthesis conditions.

36 MATERIALS SCIENCE↗

Base-catalyzed sol-gel inks for direct ink writing of high resolution hierarchically porous carbon aerogels

According to one aspect of an inventive concept, an ink includes a base catalyst, a sol gel precursor composition, and a block copolymer. According to another aspect of an inventive concept, an aerogel includes a three-dimensional printed structure having printed ligaments geometrically arranged, where an average diameter of the printed ligaments is in a range of greater than 0 microns and less than 50 microns. In addition, an average distance between a center of a first of the printed ligaments and a center of a second of the printed ligaments is at least equal to the average diameter of the printed ligaments, where the first and the second of the printed ligaments are adjacent. Each printed ligament includes of a plurality of random pores, where an average diameter of the random pores is less than 50 nanometers.

Zhu, Cheng↗

Precursor-mediated in situ growth of hierarchical N-doped graphene nanofibers confining nickel single atoms for CO 2 electroreduction

Despite the various strategies for achieving metal–nitrogen–carbon (M–N–C) single-atom catalysts (SACs) with different microenvironments for electrochemical carbon dioxide reduction reaction (CO 2 RR), the synthesis–structure–performance correlation remains elusive due to the lack of well-controlled synthetic approaches. Here, we employed Ni nanoparticles as starting materials for the direct synthesis of nickel (Ni) SACs in one spot through harvesting the interaction between metallic Ni and N atoms in the precursor during the chemical vapor deposition growth of hierarchical N-doped graphene fibers. By combining with first-principle calculations, we found that the Ni-N configuration is closely correlated to the N contents in the precursor, in which the acetonitrile with a high N/C ratio favors the formation of Ni-N 3 , while the pyridine with a low N/C ratio is more likely to promote the evolution of Ni-N 2 . Moreover, we revealed that the presence of N favors the formation of H-terminated edge of sp 2 carbon and consequently leads to the formation of graphene fibers consisting of vertically stacked graphene flakes, instead of the traditional growth of carbon nanotubes on Ni nanoparticles. With a high capability in balancing the *COOH formation and *CO desorption, the as-prepared hierarchical N-doped graphene nanofibers with Ni-N 3 sites exhibit a superior CO2RR performance compared to that with Ni-N 2 and Ni-N 4 ones.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Capturing Carbonation: Understanding Kinetic Complexities through a New Era of Electron Microscopy

Cryogenic plasma focused ion beam (PFIB) electron microscopy analysis is applied to visualizing ex situ (surface industrial) and in situ (subsurface geologic) carbonation products, to advance understanding of carbonation kinetics. Ex situ carbonation is investigated using NIST fly ash standard #2689 exposed to aqueous sodium bicarbonate solutions for brief periods of time. In situ carbonation pathways are investigated using volcanic flood basalt samples from Schaef et al. (2010) exposed to aqueous CO 2 solutions by them. The fly ash reaction products at room temperature show small amounts of incipient carbonation, with calcite apparently forming via surface nucleation. Reaction products at 75° C show beginning stages of an iron carbonate phase, e.g., siderite or ankerite, common phases in subsurface carbon sequestration environments. This may suggest an alternative to calcite in carbonation low calcium-bearing fly ashes. Flood basalt carbonation reactions show distinct zonation with high calcium and calcium-magnesium bearing zones alternating with high iron-bearing zones. The calcium-magnesium zones are notable with occurrence of localized pore space. Oscillatory zoning in carbonate minerals is distinctly associated with far-from-equilibrium conditions where local chemical environments fluctuate via a coupling of reaction with transport. The high porosity zones may reflect a precursor phase (e.g., aragonite) with higher molar volume that then “ripens” to the high-Mg calcite phase-plus-porosity. These observations reveal that carbonation can proceed with evolving local chemical environments, formation and disappearance of metastable phases, and evolving reactive surface areas. Together this work shows that future application of cryo-PFIB in carbonation studies would provide advanced understanding of kinetic mechanisms for optimizing industrial-scale and commercial-scale applications.

36 MATERIALS SCIENCE↗