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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 73 records · Page 4

High-efficiency catalytic reduction of residual oxygen for purification of carbon dioxide streams from high-pressure oxy-combustion systems

Pressurized oxy-combustion is a promising technology for carbon capture, utilization, and storage. For the captured CO 2 to be used for enhanced oil recovery or stored in geological formations, flue gas impurities, including residual O 2 in the CO 2 stream, must be purified to meet the purity specifications. A catalytic approach to reducing residual O 2 with CH 4 was investigated in this study. Five CoMn- and Cu-based catalysts were synthesized or acquired, and a reverse-flow fixed-bed reactor was used to assess their performance for O 2 removal from a simulated oxy-combustion flue gas at 15 bar. The impacts of the operating parameters on O 2 removal, such as temperature, gas hourly space velocity, O 2 /CH 4 ratio, and gas pressure, were investigated. Among the tested catalysts, the two CoMn catalysts were superior in both activity and selectivity, with the reaction lighting off at about 350 °C and achieving 99% O 2 removal at about 500 °C. Finally, the kinetics of the catalytic reaction is discussed, and the Mars–van Krevelen redox mechanism is deemed valid for describing the reaction pathway for the top-performing CoMn catalysts. The catalytic reaction was determined to be first order in CH 4 and zero order in O 2 under the test conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Raman and infrared spectra of plutonium (IV) oxalate and its thermal degradation products

For over 80 years, plutonium dioxide has been routinely produced via thermal decomposition of hydrated plutonium(IV) oxalate. Despite the longstanding utility of this process, the chemical structures of starting materials and intermediates produced during this thermal conversion remain ill-defined. To help resolve this uncertainty, we measured high-resolution Raman and infrared spectra of Pu(C 2 O 4 ) 2 ·6H 2 O that was heated to 25, 100, 220, 250, 350, and 450 °C in air. Our measurements show that Pu(C 2 O 4 ) 2 ·6H 2 O has a rich vibrational spectrum with at least 15 Raman bands between 180 cm -1 and 1900 cm -1 and 9 infrared bands between 800 cm -1 and 4000 cm -1 . As Pu(C 2 O 4 ) 2 ·6H 2 O is heated, water is liberated, and the oxalate ligand decomposes to produce plutonium oxycarbide species. When heated to 350 °C or higher, vibrational spectra are consistent with PuO 2 with some residual carbon-containing species. Full vibrational spectra, powder X-ray diffraction, and scanning electron microscopy measurements of Pu(C 2 O 4 ) 2 ·6H 2 O and its thermal degradation products are presented herein along with approximate assignments for observed spectral bands. These data can be used to validate and potentially improve existing computational models that describe the chemical structure of compounds produced during thermal degradation of plutonium (IV) oxalate. Given the utility of plutonium (IV) oxalate in synthesizing plutonium dioxide, these results are expected to provide value in the fields of nuclear fuel processing, nuclear nonproliferation, and nuclear forensics.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

N 2 O deconstruction of polycyclooctene to generate carbonyl-functionalized macromonomers

Deconstruction of polyolefins into functionalized macromonomers presents a compelling strategy for polyolefin upcycling by creating macromonomers through dehydrogenation/depolymerization. We show that nitrous oxide (N 2 O), a greenhouse gas waste product from the production of nylon, mediates the deconstruction of polycyclooctene (PCOE) and generates carbonyl-functionalized macromonomers. Carbonyl incorporation and macromonomer molar mass were well controlled by reaction time, and subsequent hydrogenation readily removed residual carbon-carbon double bonds. Here, we also demonstrated that the reaction could progress efficiently with substrates of moderate levels of unsaturation, closely mimicking partially dehydrogenated polyethylene. Such carbonyl-functionalized macromonomers could serve as feedstock for preparing vitrimers and other functional polymers.

36 MATERIALS SCIENCE↗

Quantification of Uncoupled Spin Domains in Spin-Abundant Disordered Solids

Materials often contain minor heterogeneous phases that are difficult to characterize yet nonetheless significantly influence important properties. Here we describe a solid-state NMR strategy for quantifying minor heterogenous sample regions containing dilute, essentially uncoupled nuclei in materials where the remaining nuclei experience heteronuclear dipolar couplings. NMR signals from the coupled nuclei are dephased while NMR signals from the uncoupled nuclei can be amplified by one or two orders of magnitude using Carr-Meiboom-Purcell-Gill (CPMG) acquisition. The signal amplification by CPMG can be estimated allowing the concentration of the uncoupled spin regions to be determined even when direct observation of the uncoupled spin NMR signal in a single pulse experiment would require an impractically long duration of signal averaging. We use this method to quantify residual graphitic carbon using 13 C CPMG NMR in poly(carbon monofluoride) samples synthesized by direct fluorination of carbon from various sources. Our detection limit for graphitic carbon in these materials is better than 0.05 mol%. The accuracy of the method is discussed and comparisons to other methods are drawn.

36 MATERIALS SCIENCE↗

Nondestructive evaluation of residual stress in low-carbon steel

The effects of the preferred orientation on the temperature dependence of ultrasonic velocity in low carbon steels are investigated. The sensitivity of the acousto-elastic constant to changes in microstructure is assessed as well as the possibility of determining some mechanical properties of a material by measuring the acousto-elastic constant.

Salama, K.↗

Nondestructive evaluation of residual stress in low-carbon steel, introduction

The degree of insensitivity of the temperature dependence method to variations in preferred orientations in A508 low carbon steel specimens was determined. A pulsed phase locked loop was used to measure ultrasonic velocity in these specimens in the temperature range of 50 C below and above room temperature. Results are given in tables and indicate that the temperature dependence of ultrasonic longitudinal velocity in four specimens cut at different angles remains unchanged as a function of orientation within + or -2%. The variation of temperature dependence of ultrasonic shear velocity in the A508 steel as a function of applied stresses was also measured. Results show that values at zero stress are equal regardless of whether the polarization direction is parallel or perpendicular to the direction in which the stress is applied.

Source record↗

Decoupled Rb-Sr and Sm-Nd isotopic evolution of the continental crust

Evidence was presented that the Rb-Sr and Sm-Nd isotopic systems are decoupled in crust-mantle evolution. Rare earth element (including Sm and Nd) residue principally in silicates, and are resistant to mobilization by weathering and metamorphism. In contrast, Rb and Sr are easily fractionated by crustal processes and residue in carbonates as well as in silicates. As a result, continental Sr, but not Nd, can be recycled into the mantle by exchange of seawater with basalt at spreading ridges and by subduction of carbonates associated with ridge processes. These effects result in mean Rb-Sr ages of the continental crust and of the upper mantle that are too young. Crustal growth curves based largely on Rb-Sr data, such that of Hurley and Rand, are therefore incorrect.

Goldstein, S. L.↗

Calculation of residual principal stresses in CVD boron on carbon filaments

A three-dimensional finite element model of the chemical vapor deposition (CVD) of boron on a carbon substrate (B/C) is developed. The model includes an expansion of the boron after deposition due to atomic rearrangement and includes creep of the boron and carbon. Curves are presented to show how the principal residual stresses and the filament elongation vary as the parameters defining deposition strain and creep are varied. The calculated results are compared with experimental axial residual stress and elongation measurements made on B/C filaments. This comparison requires that for good agreement between calculated and experimental results, the deposited boron must continue to expand after deposition, and that the build-up of residual stresses is limited by significant boron and carbon creep rates.

Behrendt, D. R.↗

Calculation of residual principal stresses in CVD boron on carbon filaments

A three-dimensional finite element model of the chemical vapor deposition of boron on a carbon substrate (B/C) is developed. The model includes an expansion of the boron after deposition due to atomic rearrangement and includes creep of the boron and carbon. Curves are presented showing the variation of the principal residual stresses and the filament elongation with the parameters defining deposition strain and creep. The calculated results are compared with experimental axial residual stress and elongation measurements made on B/C filaments. For good agreement between calculated and experimental results, the deposited boron must continue to expand after deposition, and the build up of residual stresses must be limited by significant boron and carbon creep rates.

Behrendt, D. R.↗

Carbon Nanotube Purification

A method for cleaning or otherwise removing amorphous carbon and other residues that arise in growth of a carbon nanotube (CNT) array. The CNT array is exposed to a plurality of hydroxyls or hydrogen, produced from a selected vapor or liquid source such as H2O or H2O2. and the hydroxyls or hydrogen (neutral or electrically charged) react with the residues to produce partly or fully dissolved or hydrogenated or hydroxylizated products that can be removed or separated from the CNT array. The hydroxyls or hydrogen can be produced by heating the CNT array, residue and selected vapor or liquid source or by application of an electromagnetic excitation signal with a selected frequency or range of frequencies to dissociate the selected vapor or liquid. The excitation frequency can be chirped to cover a selected range of frequencies corresponding to dissociation of the selected vapor or liquid. Sonication may be uscd to supplement dissociation of the H2O and/or H2O2.

Delzeit, Lance D.↗

Development of sulfonated carbon-based solid-acid catalysts derived from biorefinery residues and biomass ash for xylan hydrolysis

In this study, biorefinery residues and biomass ash were used to develop sulfonated carbon-based solid-acid catalysts to enhance xylan hydrolysis. Here, metals extracted from the biomass ash were impregnated into a carbon support prepared from biorefinery residues to synthesize sulfonated ash-impregnated carbon-based catalyst. Metals present in the ash most probably are responsible for the increased acid density in the catalyst. Using this catalyst, 11.4 % xylose yield was produced, an increase of 171 % over the yield obtained from a catalyst without ash impregnation. Using a xylan-to-catalyst ratio of 1:2, 72.9 % xylose yield was obtained, comparable to using 0.5 wt% sulfuric acid under the same reaction condition. Moreover, this catalyst significantly inhibited xylose dehydration, only forming 11.3 % furfural compared to that generated using dilute acid. Hence, these results show the potential for using biomass ash as a metal source to increase the number of acid sites in solid-acid catalysts used for biomass pretreatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct Air Capture and Sequestration of CO 2 by Accelerated Indirect Aqueous Mineral Carbonation under Ambient Conditions

Mineralization of gaseous carbon dioxide into solid carbonates using alkaline industrial residues such as coal fly ash has a dual advantage of reducing the carbon dioxide footprint of coal power plants and improving ash utilization. However, the slow mineral carbonation rate under atmospheric conditions is a major challenge, especially when using natural minerals or industrial residues for direct air capture (DAC) of CO 2 . In this study, using coal fly ash samples and concentrated alkali carbonate aqueous solutions as a recyclable solvent, we show the feasibility of coupling mineral carbonation with DAC under atmospheric conditions. Findings show that carbonation efficiency is best under alkaline conditions, achieving as high as ~80% conversion to calcium carbonates within 1 h in a 1.9 M sodium carbonate solution. Based on the experimental results, a process coupling DAC and mineral carbonation that operates entirely under ambient conditions is proposed. Here, the techno-economic and life cycle assessments for the proposed process project a levelized cost of $\$116$–133/t-CO 2 -sequestered (US $\$2019$) and process carbon emissions (GWP) in the range of 0.03–0.25 t-CO 2 e/t-CO 2 -sequestered. Considering the low cost, simplicity, and gigaton-scale sequestration potential, we believe that DAC based on alkaline industrial residue carbonation can be considered a “low-hanging fruit” in the pursuit of negative emissions to combat climate change.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalytic Reduction of Residual Oxygen for the Purification of Carbon Dioxide Streams from Pressurized Oxy-Combustors

Pressurized oxy-combustion (OC) is regarded as an energy-efficient alternative to atmospheric OC. To utilize the captured carbon dioxide (CO2) from pressurized OC for enhanced oil recovery or carbon storage in geological formations, the CO2 product stream must meet the required purity specifications. One major impurity in OC flue gases is residual O2 (e.g., 3 vol%). In this study, a catalytic approach has been investigated to remove the residual O2 through a reduction reaction with injected methane (CH4) in a reverse-flow fixed-bed (RFFB) reactor. The performance was tested for a supported copper (Cu)-based catalyst synthesized by incipient wetness impregnation and a cobalt-manganese (CoMn) oxide catalyst synthesized by a coprecipitation method. A commercial Cu-based catalyst was also studied as the reference. Experimental results revealed that under the reverse-flow operation, the temperature profiles in the reactor were symmetrical on both sides of the catalyst zone and were more homogenous than those under the conventional one-direction-flow operation. Among the tested catalysts, the CoMn catalyst was the most reactive for promoting the reduction of O2 with CH4, able to attain >95% O2 removal at 475 °C and a gas hourly space velocity (GHSV) of 18,000 h-1 with a feed gas containing 3 vol% O2. Under all experiments, the concentrations of carbon monoxide (CO) were lower than 30 ppmv in the effluent gas streams. The reaction between O2 and CH4 could be depicted by using the Mars–van Krevelen redox mechanism based on a two-step reduction–oxidation reaction pathway.

36 MATERIALS SCIENCE↗

Carbon in the Allende meteorite - Evidence for poorly graphitized carbon rather than carbyne

A carbon-rich acid residue from the Allende carbonaceous chondrite was examined by high-resolution transmission electron microscopy (HRTEM) and also by analytical electron microscopy. A TEM mount of this residue that has previously been reported to contain carbyne forms of carbon was shown to contain sheet silicate contaminants. These sheet silicate grains give electron diffraction patterns similar to those reported for carbynes, thus raising questions about the previous report of carbynes in this residue. Furthermore, two crystals from a glacier microspherule, which had previously been identified as carbyne VIII, were shown by microanalysis to be talc. In view of these observations it is suggested that identifications of carbyne by electron diffraction should be supported by microanalyses of the individual grains. HRTEM investigations of the Allende carbon indicate that it is a poorly crystalline graphite, structurally similar to 'glassy' carbon

Smith, P. P. K.↗

Carbon and sulfur distributions and abundances in lunar fines

Total sulfur abundances have been determined for 20 Apollo 14, 15, and 16 soil samples and one Apollo 14 breccia. Sulfur concentrations range from 474 to 844 microg S/g. Volatilization experiments on selected samples have been carried out using step-wise heating. Sample residues have been analyzed for their total carbon and sulfur abundances to establish the material balance in lunar fines for these two elements. Volatilization experiments have established that between 31 to 54 microg C/g remains in soils which have been heated at 1100 C for 24 hours under vacuum. The residual carbon is believed to be indigenous lunar carbon whereas all forms of carbon lost from samples below 1100 C is extralunar carbon. Total carbon and sulfur abundances taken from the literature have been used to show the depletion of volatile elements with increasing grade for the Apollo 14 breccias.

Gibson, E. K., Jr.↗

A carbonate-rich, hydrated, interplanetary dust particle Possible residue from protostellar clouds

Transmission electron microscopy of a hydrated interplanetary dust particle (IDP) indicates that it contains abundant magnesium-iron carbonates, primarily breunnerite and magnesian siderite. This IDP displays a strong absorption band at 6.8 micrometers in its infrared spectrum, similar to that in certain protostellar spectra. The carbonates probably account for the 6.8-micrometer band in the IDP spectrum, suggesting that carbonate also may occur in interstellar dust and be the source of the controversial 6.8-micrometer feature from the protostellar spectra.

Tomeoka, K.↗