Demonstration of a Solar Air Separation Process to Produce High-Purity N2 via Ba0.15Sr0.85FeO3-δ Reduction-oxidation Cycles .
Abstract not provided.
Bush, Hagan↗
SEARCH · Engineering Papers
Results for “Oxidation processes”
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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Summary of Gas Generation Behavior Observed in 3013 Surveillance and Monitoring Program Shelf-Life Experiments
Gas generation experiments have been conducted in small- and full-scale test containers at Los Alamos National Laboratory on samples of plutonium oxide material collected from plutonium processes across the DOE complex and tested at the bounding conditions for the Department of Energy 3013 Standard. The gas composition and pressures in the sealed experimental containers were measured over periods of months to years. These experiments have provided results for the formation and consumption of hydrogen and other gases. The conditions supporting the formation of flammable gas mixtures of hydrogen and oxygen in flammable gas mixtures were also determined. Different behaviors were observed between the materials tested based on their compositions, the stabilization performed on the material, and the post stabilization handling of the material. Many of the experiments are still ongoing. This report summarizes the results obtained for the gas generation behavior for high-purity plutonium oxides and salt-bearing impure plutonium oxides in sealed containers.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
High-Performance Matrix Resins
State-of-the-art PMR polyimides provide good strength and light weight in wide variety of critical applications. However, improved processability and elevated temperature thermo-oxidative stability are desired in such polyimide systems. Resins, intended for use in advanced composites, adhesives, and neat resin articles, show improvements in both processability and elevatedtemperature stability over state-of-the-art PMR-15 polymers.
Pater, R. H.↗
The enzymes associated with denitrification
The enzymes involved in the reduction of nitrogenous oxides are thought to be intermediates in denitrification processes. This review examines the roles of nitrate reductase, nitrite reductases, nitric oxide reductase, mechanisms of N-N bond formation, and nitrous oxide reductases.
NASA Discipline Exobiology↗
The Oxidation State of Sulfur in Martian Apatite- Implications for Redox of Surficial Processes
Meteorites from Mars record fO2 values of ∆IW = -1 to +6.5 [1, 2]. This relatively large range in fO2 has been attributed to igneous processes like differentiation and assimilation, or sometimes to alteration [2, 3], modifying the range inherited from the Martian mantle, which is thought to be closer to the values recorded by lunar basalts (~∆IW -1 [e.g., 1]). Trace element compositions reveal that those Martian meteorites that are light Rare Earth Elements (LREE) enriched record higher fO2 values than those that are LREE-depleted [2]. Sulfur (S) has been used to track redox and alteration processes on Mars because it can be present in multiple redox states varying from S2- in magmatic sulfides to S6+ in sedimentary sulfate deposits and alteration products like jarosite [4, 5]. Apatite (Ca5(PO4)3(F,Cl,OH)) is found in many of the Martian meteorites as a late stage crystallizing mineral. It can incorporate both S^(2-) [6] or S^(6+) [7] or mixtures of both [7, 8] in its crystal structure, and it has been hypothesized that the relative proportions of S^(2-) and S^(6+) in apatite will depend on the prevailing fO2 in which it formed (along with P, T, and major element composition). Note: Extended abstract on document.
P. Chowdhury↗
Vanadium oxide for infrared coatings and methods thereof
The present invention relates to vanadium oxide and methods of controlling reaction processes for making such materials (e.g., powders). In particular embodiments, the method includes control of oxygen partial pressure in order to kinetically control the oxidation species of the crystalline vanadium oxide material. Other methods, uses, systems, protocols, and coatings are also described.
36 MATERIALS SCIENCE↗
Optical vibrational spectroscopic signatures related to U 3 O 8 production processes
Uranium ore concentrates are materials found early within the nuclear fuel cycle and contain high concentrations of uranium in an easily transported form, making the concentrates a likely target for illegal diversion. These concentrates are typically converted to U 3 O 8 for further processing and, therefore, may lose specific physicochemical characteristics in determining the materials’ source and processing history. In this work, we explore the Raman spectra of eight oxide samples produced from various uranium ore concentrates and processing pathways to examine the presence of spectroscopic signatures relating to each sample's process history. Samples produced from amine extraction and dialkylphosphoric acid extraction processes show unique characteristics due to high concentrations of α-UO 3 , whereas samples calcinated from metallic diuranates do not form pure α-U 3 O 8 because of metallic ion inclusions. Pure α-U 3 O 8 oxide samples are obtained through calcination of ammonium diuranate, ammonium uranyl carbonate, and metastudtite intermediates. The Raman spectra of these oxide samples show close agreement with pristine α-U 3 O 8 spectra. However, deviations from the pristine spectra are observed in the 300–460 cm -1 spectral range. In conclusion, these deviations are unique identifying signatures that were likely created by lasting effects from the process history. Spectral center of mass calculations indicate grouping of samples based on processing history.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Advanced Diagnostics for Megahertz Imaging of Mixing, Fuel Spray, and Combustion Processes for Rotating Detonation Combustors
Recent advancements in megahertz rate, high-power, burst-mode laser technology are leveraged to perform and explore imaging measurements that spatially and temporally resolve the mixing, combustion, and detonation flow field in two laboratory-scale rotating detonation combustors (RDCs). In a non-premixed annular RDC, multiple imaging diagnostics are explored to investigate gaseous and liquid injector behavior, the detonation wave structure, and the propellant refill. In one instance, OH planar laser-induced fluorescence (OH-PLIF) imaging is performed up to a 2 MHz repetition rate to track the combustion products and reaction zone locations. In the same annular RDC, a single liquid fuel jet is injected, and laser-based 355-nm imaging of the fuel spray is performed up to a 1 MHz repetition rate. For this configuration, the annular RDC is used as a detonation driver to impose periodic detonation waves to interact with the fuel spray. Moreover, in this annular RDC, a range of tracer-based laser imaging measurements are explored to time-resolve the unsteady oxidizer air recovery and refill process. In a non-premixed linear RDC, planar imaging measurements of the fuel mixing are performed up to a 200 kHz repetition rate using PLIF of a tracer in the fuel supply. The fuel mixing imaging helps explain the origin of the observed pre and post wave burning, detonation structure, and enables quantifying injector recovery timescales. This paper will provide a high-level broad survey of diagnostics applied in these RDCs, lessons learned, and interesting observations.
Combustion↗
Advanced Diagnostics For Megahertz Imaging Of Mixing, Fuel Spray, And Combustion Processes For Rotating Detonation Combustors
Recent advancements in megahertz rate, high-power, burst-mode laser technology are leveraged to perform and explore imaging measurements that spatially and temporally resolve the mixing, combustion, and detonation flow field in two laboratory-scale rotating detonation combustors (RDCs). In a non-premixed annular RDC, multiple imaging diagnostics are explored to investigate gaseous and liquid injector behavior, the detonation wave structure, and the propellant refill. In one instance, OH planar laser-induced fluorescence (OH-PLIF) imaging is performed up to a 2 MHz repetition rate to track the combustion products and reaction zone locations. In the same annular RDC, a single liquid fuel jet is injected, and laser-based 355-nm imaging of the fuel spray is performed up to a 1 MHz repetition rate. For this configuration, the annular RDC is used as a detonation driver to impose periodic detonation waves to interact with the fuel spray. Moreover, in this annular RDC, a range of tracer-based laser imaging measurements are explored to time-resolve the unsteady oxidizer air recovery and refill process. In a non-premixed linear RDC, planar imaging measurements of the fuel mixing are performed up to a 200 kHz repetition rate using PLIF of a tracer in the fuel supply. The fuel mixing imaging helps explain the origin of the observed pre and post wave burning, detonation structure, and enables quantifying injector recovery timescales. This paper will provide a high-level broad survey of diagnostics applied in these RDCs, lessons learned, and interesting observations.
Combustion↗
Production of Carbon Nanomaterials and Sorbents from Domestic U.S. Coal (Final Report)
The main goal of this project was to produce high-value carbon nanomaterials and carbon sorbents from domestic coal resources in a cost-effective manner. Four types of domestic coal samples were processed through a combination of deashing, devolatilization, oxidation, reduction, and activation treatments to produce graphene oxide (GO), reduced graphene oxide (RGO), and activated carbon (AC). The precursors and developed materials were extensively characterized by various methods to investigate the impact of the coal feedstock type on the yield and quality of each product. A commercial graphite-based GO sample was included in the experimental work as the baseline material for comparison with the coal-based materials developed in this work. The performed work also included a technoeconomic analysis and cost estimation for a plant processing 20 tons/day coal, a market evaluation for the graphene materials, and a technology gap analysis. A simple process by concentrated nitric acid oxidation is used to oxidize coal precursors for the production of GO. Fine oxidized coal particles that were separated from larger oxidized coal particles had significantly higher oxygen contents and were identified as coal-based GO samples. Coarse oxidized coal particles were used as precursors for production of AC. Based on the Raman spectroscopy results, coal-based GO samples exhibited G and D bands similar to those of graphite-based GO samples. X-ray photoelectron spectroscopy revealed that coal-based GO samples had surface oxygen contents of ~26-35% that were higher than the oxygen contents of graphite-based GO samples. Larger particles of oxidized coal samples were activated under different conditions to produce high surface area functionalized AC. Prepared materials had surface areas exceeding 1,500 m 2 /g and pore volumes more than 1 cm 3 /g with different pore size distributions. Reduced graphene oxide samples were prepared by thermal reduction of both coal-based and graphite-based GO samples at 170-2800 ºC. Coal-based and graphite-based RGO samples exhibited similar carbon contents, Raman spectra, and XRD profiles. Heat treatment above 1500 ºC shifted RGO to synthetic graphite. Among anthracite, bituminous, subbituminous, and lignite coals tested, anthracite was the best precursor to produce carbon nanomaterials exhibiting properties similar to those of graphite-based materials. Anthracite-based carbon nanomaterials also had the highest production yields. Technoeconomic analysis estimated the production cost of GO and RGO for anthracite-based samples at about 2,600 and 4,200 $/ton, respectively, which is about two orders of magnitude lower than the current estimated price of graphite-based materials. Several gaps to further develop the proposed technology were identified and discussed that include process and equipment optimization, process integration, need for additional bench- and pilot-scale experiments, and other items to reduce the scale up risk. Market analysis reports suggested a compound annual growth rate of 40% for graphene and related materials. Short-term applications include composites, inks, and coatings. However, energy storage applications appear to be the dominant potential long-term applications. Different applications of coal-based GO and RGO need to be explored and clear metrics and standards for each application need to be developed.
01 COAL, LIGNITE, AND PEAT↗
The influences of fluorine and process variations on polysilicon film stress and MOSFET hot carrier effects
The use of fluorinated gate oxides may provide an improvement in nMOSFET reliability by enhancing hot carrier resistance. In order to clarify the mechanisms by which polysilicon processing and fluorination influence the oxide behavior, a matrix of nMOSFET structures was prepared using various processing, doping, and implantation strategies. These structures were evaluated for crystalline morphology and chemical element distribution. Mechanical stress measurements were taken on the polysilicon films from room temperature to cryogenic temperature. These examinations showed that fluorination of a structure with randomly oriented polysilicon can reduce residual mechanical stress and improve hot carrier resistance at room temperature.
Lowry, Lynn E.↗
Containerless measurements on liquids at high temperatures
The application of containerless techniques for measurements of the thermophysical properties of high temperature liquids is reviewed. Recent results obtained in the materials research laboratories at Intersonics are also presented. Work to measure high temperature liquid properties is motivated by both the need for reliable property data for modeling of industrial processes involving molten materials and generation of data form basic modeling of materials behavior. The motivation for this work and examples of variations in thermophysical property values from the literature are presented. The variations may be attributed to changes in the specimen properties caused by chemical changes in the specimen and/or to measurement errors. The two methods used to achieve containerless conditions were aeroacoustic levitation and electromagnetic levitation. Their qualities are presented. The accompanying slides show the layout of levitation equipment and present examples of levitated metallic and ceramic specimens. Containerless techniques provide a high degree of control over specimen chemistry, nucleation and allow precise control of liquid composition to be achieved. Effects of minor additions can thus be measured in a systematic way. Operation in reduced gravity enables enhanced control of liquid motion which can allow measurement of liquid transport properties. Examples of nucleation control, the thermodynamics of oxide contamination removal, and control of the chromium content of liquid aluminum oxide by high temperature containerless processes are presented. The feasibility of measuring temperature, emissivity, liquidus temperature, enthalpy, surface tension, density, viscosity, and thermal diffusivity are discussed in the final section of the paper.
Weber, Richard↗
Thermochemical processes for CO 2 hydrogenation to fuels and chemicals: Challenges and opportunities
This manuscript discusses the potential use of CO 2 as a carbon and oxygen carrier to return it to the carbon life cycle in the form of fuels or chemicals via thermochemical catalytic pathways. Theoretically, CO 2 hydrogenation can form a variety of fuels and chemicals. Practically, however, the selectivity, conversion, operating range, and kinetic limitations and operational cost determine the end product. Because of their high value and versatility as a chemical or fuel, small olefins (i.e., C 2 H 4 ) and methanol are often considered as target species. Whether alcohol or olefin formation, CH 4 and CO are the nature’s primary choices of CO 2 conversion. They can be formed over a wide operating temperature, pressure, and CO 2 :H 2 ratios. They are often competitive carbon species in olefin or methanol formation steps. Although they are less valuable as end products, they can be used as intermediate species. Secondary processes of CO and CH 4 to form chemicals and fuels can increase the overall CO 2 hydrogenation yield. Independent of the choice of end product, CO 2 hydrogenation requires hydrogen. Pure hydrogen derived mostly from fossil fuels adds to the overall process cost and also increases the CO 2 emissions. Hydrogen produced from water electrolysis is a renewable green pathway but is limited by the process efficiency and cost. As an alternative to pure hydrogen, low-value, small chain paraffins are suggested as the hydrogen carriers. Carbon dioxide–assisted oxidative dehydrogenation of paraffins to olefins process is a direct pathway to olefin formation. The paper discusses these potential pathways for CO 2 utilization based on theoretical analysis and recent advances in academia and industry.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Containerless Processing of Molten Tin Samples in a Controlled Oxygen Environment
Contamination due to oxygen or oxide layer formation is a major concern in containerless processing of metallic melts.
tin samples gas environment copper zeolite outgass↗
Chemical kinetic models for combustion of hydrocarbons and formation of nitric oxide
The formation of nitrogen oxides NOx during combustion of methane, propane, and a jet fuel, JP-4, was investigated in a jet stirred combustor. The results of the experiments were interpreted using reaction models in which the nitric oxide (NO) forming reactions were coupled to the appropriate hydrocarbon combustion reaction mechanisms. Comparison between the experimental data and the model predictions reveals that the CH + N2 reaction process has a significant effect on NO formation especially in stoichiometric and fuel rich mixtures. Reaction models were assembled that predicted nitric oxide levels that were in reasonable agreement with the jet stirred combustor data and with data obtained from a high pressure (5.9 atm (0.6 MPa)), prevaporized, premixed, flame tube type combustor. The results also suggested that the behavior of hydrocarbon mixtures, like JP-4, may not be significantly different from that of pure hydrocarbons. Application of the propane combustion and nitric oxide formation model to the analysis of NOx emission data reported for various aircraft gas turbines showed the contribution of the various nitric oxide forming processes to the total NOx formed.
Jachimowski, C. J.↗
Investigation of Oxidation Mechanisms in HfS 2 and ZrS 2 via In Situ Electron Microscopy
Transition metal dichalcogenides (TMD) combine semiconducting properties with stability and are therefore widely studied for future microelectronic devices. However, applications require integration with a suitable dielectric at a planar, defect-free interface. For Hf- and Zr-based TMDs, the good dielectric properties of hafnia and zirconia imply that direct oxidation is a promising strategy, provided that a high-quality interface and suitable oxide morphology can be formed. Here, in this study, we investigate HfS 2 and ZrS 2 oxidation, aiming to understand pathways toward planar oxide layer formation and the mechanisms that determine the characteristics of the semiconductor/dielectric interface. We use conventional and environmental transmission electron microscopy to reveal changes in morphology and composition of the TMDs under different gaseous environments. We show that oxidation at ambient conditions causes compositional heterogeneities, with local replacement of S by O in both materials. Thermal oxidation causes desulfurization and formation of a smooth but defective oxide layer. In contrast, plasma oxidation appears the best-suited to forming a controlled TMD/dielectric interface with a smooth oxide layer and without major defects. These results provide insight into the opportunities available from HfS 2 and ZrS 2 through oxidation and suggest a materials processing strategy for electronic device fabrication.
HfS2↗
Light-Promoted C(sp 3 )–C(sp 3 ) Reductive Elimination from Dialkyl NiII Complexes
Ni-catalyzed cross-coupling is a powerful strategy to forge C(sp 3 )–C(sp 3 ) bonds. Typically, to do so requires overcoming a challenging C–C bond-forming reductive elimination, often enabled by the intermediacy of highly oxidized Ni species or outer-sphere processes. While direct C(sp 3 )–C(sp 3 ) reductive elimination from the Ni II base oxidation state is normally thermally inaccessible, light-activation provides an avenue to affect such transformations. Here, we investigate the mechanism of light-induced C(sp 3 )–C(sp 3 ) bond formation from dialkyl bipyridine Ni II complexes through a variety of organometallic, spectroscopic, and computational studies. Wavelength-dependent quantum yields, ligand electronics–reactivity relationships, excited-state lifetimes, computed barriers, and product distributions from crossover studies support a photolysis/radical rebound mechanism. Furthermore, this reactivity paradigm complements existing strategies in the literature to promote reductive elimination from Ni II , such as the use of destabilizing, sterically hindered ligands and reduction of electron density at Ni through the binding of electron-deficient olefins. Hence, we envision that light-induced reductive elimination may enable the development of challenging C(sp 3 )–C(sp 3 ) couplings.
Alkyls↗
Catalyst and reactor design considerations for selective production of acids by oxidative cleavage of alkenes and unsaturated fatty acids with H 2 O 2
Oxidative cleavage of alkenes and unsaturated fatty acids with hydrogen peroxide gives an efficient and sustainable process to obtain mono- and di-acids for polymers and lubricants with fewer safety risks and less environmental impact than processes that utilize ozone or other inorganic oxidizers (e.g., permanganate, dichromate, etc.). Guided by insight into the mechanisms for competing reaction pathways (i.e., epoxidation of alkene on W–(η 2 -O 2 ) complexes vs. H 2 O 2 decomposition) and the apparent kinetics derived from kinetic experiments, here, we postulate that W-based heterogeneous catalysts can provide high performance and stable operations at low H 2 O 2 concentrations. Semi-batch reactors with continuous introduction of H 2 O 2 solutions offer the means to maintain low H 2 O 2 concentrations while providing sufficient quantities of H 2 O 2 to satisfy the reaction stoichiometry. We derived simple kinetic model equations for the epoxidation, ring-opening, oxidative cleavage, and oxidation steps and fit theses equations to batch experimental data to obtain kinetic parameters. Furthermore, this kinetic model describes the concentration profiles of reactant, oxidant, and products well as shown by agreement with experimental data. Further predictions of the optimal H 2 O 2 feed rate for semi-batch operation utilized by the proposed rate expressions and the reactor design equations suggest that low H 2 O 2 feed rate increases selectivity towards oxidative cleavage products and selective use of H 2 O 2 for oxidative cleavage pathway. Comparisons of oxidative cleavage of 4-octene in batch and semi-batch reactors show that semibatch reactors with optimized molar feed rates of H 2 O 2 increased oxidative cleavage product selectivities (76% to 99%; with an increase in butyric acid selectivity from 1% to 55%) and H 2 O 2 selectivity (3% to 30%). In addition, semibatch reaction conditions used avoid H 2 O 2 -mediated dissolution of W-atoms from the catalyst. Analysis of these findings suggest that solid oxide catalysts will be effective for continuous oxidative cleavage reactions if deployed within fixed-bed reactors that allow for distributed introduction of reactants and therefore low in situ concentrations of H 2 O 2 .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗