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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 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Short O–O separation in layered oxide Na 0.67 CoO 2 enables an ultrafast oxygen evolution reaction

The layered oxide Na 0.67 CoO 2 with Na + occupying trigonal prismatic sites between CoO 2 layers exhibits a remarkably high room temperature oxygen evolution reaction (OER) activity in alkaline solution. The high activity is attributed to an unusually short O–O separation that favors formation of peroxide ions by O - –O – interactions followed by O 2 evolution in preference to the conventional route through surface O–OH – species. The dependence of the onset potential on the pH of the alkaline solution was found to be consistent with the loss of H + ions from the surface oxygen to provide surface O - that may either be attacked by solution OH - or react with another O - ; a short O–O separation favors the latter route. The role of a strong hybridization of the O-2 p and low-spin Co III /Co IV π-bonding d states is also important; the OER on other Co III /Co IV oxides is compared with that on Na 0.67 CoO 2 as well as that on IrO 2 .

Wang, Hao↗
DOE OSTI2017

Major role of nitrite-oxidizing bacteria in dark ocean carbon fixation

Carbon fixation by chemoautotrophic microorganisms in the dark ocean has a major impact on global carbon cycling and ecological relationships in the ocean’s interior, but the relevant taxa and energy sources remain enigmatic. We show evidence that nitrite-oxidizing bacteria affiliated with the Nitrospinae phylum are important in dark ocean chemoautotrophy. Single-cell genomics and community metagenomics revealed that Nitrospinae are the most abundant and globally distributed nitrite-oxidizing bacteria in the ocean. Metaproteomics and metatranscriptomics analyses suggest that nitrite oxidation is the main pathway of energy production in Nitrospinae. Microautoradiography, linked with catalyzed reporter deposition fluorescence in situ hybridization, indicated that Nitrospinae fix 15 to 45% of inorganic carbon in the mesopelagic western North Atlantic. Nitrite oxidation may have a greater impact on the carbon cycle than previously assumed.

Science & Technology - Other Topics↗
DOE OSTI2023

Electro-Oxidative Dehydrogenation of Ethane to Ethylene Using Lanthanum-Strontium-Iron Oxide Perovskite Electrocatalysts

Developing alternative, industrially viable ethylene production routes has received important research attention. One chemical pathway of interest is the oxidative dehydrogenation (ODH) of ethane, although issues such as product selectivity, combustion hazards, and oxidizer supply have hindered the practical scale-up of this technology. The presented work describes the use of a solid oxide fuel cell (SOFC) platform employing lanthanum-strontium-iron oxide perovskite (La 1-x Sr x FeO 3-δ , or LSFx) electrocatalysts to perform electrochemical-ODH (e-ODH), a process design that has the potential to address the challenges of ODH implementation. The effects of La and Sr stoichiometry, operating temperature, and current density are reported. The highest performance was observed using a La:Sr ratio of 0.50 (LSF0.50) at 750 °C and a current density of 0.50 A·cm –2 , achieving an ethane conversion of 18.7 ± 0.3%, ethylene selectivity of 91.4 ± 1.9%, and ethylene yield of 17.1 ± 0.1%. These results demonstrate several potential advantages for utilizing a SOFC platform to perform e-ODH of ethane to ethylene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Electrolytic Oxide Reduction of Plutonium Oxide Surrogates

Our research team has investigated electrolytic oxide reduction (EOR) as an improved metal production process versus the currently employed multiple cycle direct oxide reduction (MCDOR) process for the conversion of plutonium oxide to plutonium metal. Inherent advantages in safety, waste generation, efficiency, and operational ease make EOR an attractive alternative to traditional metal production practices. Phase I of the project consisted of the construction of a prototype electrochemical cell, and proof of concept experiments towards the reduction of SnO 2 and CeO 2 compounds. Phase II of the project was focused on the optimization of the cerium system in preparation for future plutonium EOR experiments. We observed the electrolytic reduction of cerium oxide resulting in mixed degrees of success, and discovered this was a result of parasitic side reactions and partial reduction. We employed cyclic voltammetry (CV) to identify the products of these side reactions and characterize partially reduced species. We also observed that, when metal was successfully produced by EOR, a large amount of passed charge was required. We concluded that this observation was due to several inefficiencies of the process relating to the reduction mechanism (e.g. inefficient use of cathodically produced calcium). We used our CV results to guide our optimization of the EOR of CeO 2 by refining our electrochemical method, cell geometry, and materials of construction. Finally, we developed a next generation cell, worked to establish a new molten salt electrochemical capability in the Plutonium Facility, and completed a strategy for plutonium experiments. Our electrochemical method to produce plutonium metal clearly supports the core mission of the laboratory. Furthermore, this project has allowed for the development of capabilities that will provide valuable data to programs interested in characterization and detection, as well as science of signatures. Additionally, establishing this capability in the plutonium facility will facilitate future safeguard studies that can assist with safeguard development in molten salt reprocessing flowsheets, and molten salt reactor designs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Catalytic Selective Oxidations with Porous Transition Metal Oxides

This final report covers work done concerning oxidation catalysis over the past year. There are three major areas involving synthesis, characterization, and catalysis. The synthetic focus has been on porous metal oxides. Full characterization of these systems using a variety of methods has been done using ex-situ, in situ, and operando conditions. A major goal of the work has been to study the mechanisms of catalytic oxidations including identification of reaction intermediates. Specific applications besides oxidations concern electrocatalytic water splitting, water harvesting, CO 2 capture, and environmental catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Simulating Oxidation of Carbon Surfaces by Atomic Oxygen Coupled with a Finite Rate Oxidation Model

Oxidation is a prominent factor in degradation of carbon based ablative materials at high temperatures, resulting in mass loss and material recession through chemical and mechanical erosion. In this paper, a finite rate carbon oxidation model coupled with surface recession is implemented in the Porous Ablation and Thermal Response (Panther) software to investigate carbon oxidation by atomic oxygen over a range of temperatures and pressures. Panther is utilized to investigate the finite rate oxidation model proposed by Swaminathan-Gopalan et al. at conditions of higher pressure and flux relative to the experiments it was built on.

Kirmanoglu, Kaan K.↗
NASA NTRS1982

Long-term high-velocity oxidation and hot corrosion testing of several NiCrAl and FeCrAl base oxide dispersion strengthened alloys

Several oxide dispersion strengthened (ODS) alloys have been tested for cyclic, long-term, high gas-velocity resistance to oxidation at 1100 C and hot corrosion at 900 C. Both nominally Ni-16Cr-4Al and Fe-20Cr-4.5Al ODS alloys were subjected up to about 2500 cycles, where each cycle consisted of 1 hr in a hot, Mach 0.3 combusted gas stream followed by a 3-min quench in an ambient temperature, Mach 0.3 air blast. For comparison to existing technology, a coated superalloy was simultaneously tested. The ODS iron alloy exhibited clearly superior behavior, surviving 3800 oxidation and 2300 hot corrosion cycles essentially unscathed. While the ODS nickel alloys exhibited adequate oxidation resistance, the long-term hot corrosion resistance could be marginal, since the best life for such alloys under these conditions was only about 1100 cycles. However, the hot corrosion resistance of the ODS Ni-base alloys is excellent in comparison to that of traditional superalloys.

Lowell, C. E.↗
NASA NTRS1989

Predicting minimum Al concentrations for protective scale fromation on Ni-base alloys. I - Isothermal oxidation. II - Cyclic oxidation

Criteria proposed to predict the minimum bulk Al concentration for the formation of protective Al2O3 scales on Ni-based alloys during isothermal oxidation (two criteria proposed by Wagner, 1952 and 1959) and cyclic oxidation (the criteria proposed by Wahl, 1983, and Whittle, 1972/Wahl, 1983) were applied to Ni-Al and Ni-Cr-Al(Zr) alloys, respectively. It is shown that the first Wagner (1952) criterion underpredicted, by a factor of 3, the experimentally observed minimum Al concentration for the formation of an external Al2O3 scale on Ni-Al alloys at 1200 C; the second Wagner criterion predicted a transition from internal oxidation to continuous Al2O3 formation in good agreement with experimentally observed concentrations. It was also found that the two criteria for an Al2O3 scale formation during cyclic oxidation of Ni-Cr-Al(Zr) alloys were inadequate to predict the minimum Al concentration necessary for repeated formation of an Al2O3 scale, regardless of the adherence of the scale.

Nesbitt, James A.↗
NASA NTRS1992

A statistical analysis of elevated temperature gravimetric cyclic oxidation data of 36 Ni- and Co-base superalloys based on an oxidation attack parameter

A large body of high temperature cyclic oxidation data generated from tests at NASA Lewis Research Center involving gravimetric/time values for 36 Ni- and Co-base superalloys was reduced to a single attack parameter, K(sub a), for each run. This K(sub a) value was used to rank the cyclic oxidation resistance of each alloy at 1000, 1100, and 1150 C. These K(sub a) values were also used to derive an estimating equation using multiple linear regression involving log(sub 10)K(sub a) as a function of alloy chemistry and test temperature. This estimating equation has a high degree of fit and could be used to predict cyclic oxidation behavior for similar alloys and to design an optimum high strength Ni-base superalloy with maximum high temperature cyclic oxidation resistance. The critical alloy elements found to be beneficial were Al, Cr, and Ta.

Barrett, Charles A.↗
NASA NTRS1951

Some Properties of Beryllium Oxide and Beryllium Oxide - Columbium Ceramals

High-temperature tensile and thermal-shock investigations were conducted on beryllium oxide and beryllium oxide plus columbium metal additions. X-ray diffraction and metallographic results are given. The tensile strength of 6150 pounds per square inch for beryllium oxide at 1800 degrees F compared favorably with the zirconia bodies previously tested. Additions of 2, 5, 8, 10, 12, and 15 percent by weight of columbium metal failed to improve the shock resistance over that of pure beryllium oxide.

Robards, C F↗
NASA NTRS2015

Oxide_Oxide Ceramic Matrix Composite (CMC) Exhaust Mixer Development in the NASA Environmentally Responsible Aviation (ERA) Project

Rolls-Royce North American Technologies, Inc. (LibertyWorksLW) began considering the development of CMC exhaust forced mixers in 2008, as a means of obtaining reduced weight and hotter operating temperature capability, while minimizing shape distortion during operation, which would improve mixing efficiency and reduce fuel burn. Increased component durability, enhanced ability to fabricate complex-shaped components, and engine noise reduction are other potential advantages of CMC mixers (compared to metallic mixers). In 2010, NASA was pursuing the reduction of NOx emissions, fuel burn, and noise from turbine engines in Phase I of the Environmentally Responsible Aviation (ERA) Project. ERA subtasks, including those focused on CMC components, were formulated with the goal of maturing technology from proof of concept validation (TRL 3) to a systemsubsystem or prototype demonstration in a relevant environment (TRL 6). In April 2010, the NASA Glenn Research Center (GRC) and LibertyWorks jointly initiated a CMC Exhaust System Validation Program within the ERA Project, teaming on CMC exhaust mixer development for subsonic jet engines capable of operating with increased performance. Our initial focus was on designing, fabricating, and characterizing the thrust and acoustic performance of a roughly quarter-scale 16-lobe oxide oxide CMC mixer and tail cone along with a conventional low bypass exhaust nozzle. Support Services, LLC (Allendale, MI) and ATK COI Ceramics, Inc. (COIC, in San Diego, CA) supported the design of a subscale nozzle assembly that consisted of an oxide oxide CMC mixer and center body, with each component mounted on a metallic attachment ring. That design was based upon the operating conditions a mixer would experience in a turbofan engine. Validation of the aerodynamic and acoustic performance of the subscale mixer via testing and the achievement of TRL 4 encouraged the NASALWCOIC team to move to the next phase where a full scale CMC mixer sized for a RR AE3007 engine and a compatible attachment flange were designed, followed by CMC component fabrication by COIC, and vibration testing at GRC under conditions simulating the structural and dynamic environment encountered during engine operation. AFRL (WPAFB) supported this testing by performing 3D laser vibrometry to identify the mixer mode shapes and modal frequencies. The successful fabrication and testing of such a component has been achieved. The CMC mixer demonstrated good durability during vibration testing at room and elevated temperature (TRL5). This has cleared the article for a ground-based test on a Rolls-Royce AE3007 engine, where the performance and benefits of the component can be further assessed.

exhaust nozzles↗
DOE OSTI2021

Pt Catalysts Modified with Manganese Oxide through Atomic Layer Deposition for CO Oxidation: Establishing a Coating Layer above or below Pt

The effect of atomic layer deposition (ALD) of manganese oxide on CO oxidation over Pt/Al2O3 is investigated. Two types of catalysts with a thin MnOx layer coated on or under the Pt nanoparticles (NPs) are prepared, and a pristine Pt/Al2O3 catalyst is used as a reference sample. The addition of the ALD layers improves the catalyst durability and both catalysts with MnOx exhibit greater stability after thermal aging at 1073-K. Besides, MnOx promotes CO oxidation through active Pt-MnOx interfacial sites, showing a reaction rate up to 35-fold faster than that of unmodified Pt. Interestingly, the CO adsorption ability of the Pt catalysts with MnOx overcoats is greatly suppressed after the high-temperature calcination; however, the reaction rate of CO oxidation is still excellent. This phenomenon is because the uniformly covered MnOx with two atomic layers diminishes the exposed Pt surface, but the reaction near the Pt-MnOx interfacial site still occurs. Our results guide the effective use of ALD, which is actively applied to heterogeneous catalysis, and provide a novel direction to control metal-assisted interactions.

36 MATERIALS SCIENCE↗
DOE OSTI2019

FTIR and Raman Spectroscopy of Reduced Graphene Oxide Carbon Nanoribbons and Graphene Oxide on Copper (Cu)

In the past couple of decades, carbon nanomaterials produced from graphene and graphite have emerged as one of the more important recently discovered substances. These carbon nanomaterials have been found to exhibit high levels of mechanical strength, thermal resistance, and electrical conductivity, thus having a multitude of applications. Therefore, it is important to identify and analyze their traits in order to maximize their effectiveness. Two spectroscopic techniques employed for such analyses of these materials are Fourier-Transform Infrared (FTIR) and Raman Spectroscopy. The advantages of FTIR and Raman include nondestructive analysis, relatively quick measurements under normal atmospheric conditions, and enhanced sensitivity with high resolution capacity. FTIR Spectroscopy was used in this research project to determine the effects of thermal exfoliation and photoreduction on the functionality groups of a carbon nanomaterial. Raman Spectroscopy was used in this research project to determine the effects of thermal exfoliation and photoreduction on the intensity of the disorder peak, which is greater in intensity if the carbon nanomaterial exhibits greater amounts of functionalities or defects in the graphitic material. There were two sample types which were analyzed with both FTIR and Raman Spectroscopy for the research project: graphene nanoribbons and graphene oxide. The m-grade graphene nanoribbons (GNRs) were produced from m-grade carbon nanotubes (CNTs) via Tour's method. The graphene oxide (GO) was produced from graphene via Tour's method, sonicated and centrifuged, dip-coated onto Copper (Cu) foil, and then photoreduced under a UV light source. FTIR measurements and analyses were conducted using a Jasco FTIR Spectrometer. Raman measurements and analyses were conducted using a Jasco Laser Raman Spectrometer. Tasks and techniques for this project included photoreduction, dip-coating, corrosion testing, FTIR and Raman data collection and analysis, and improvement of data collection for the Raman Spectrometer. GNRs exfoliated and reduced (deoxygenation) at 270 deg. C in air showed a significant decrease in O functionalities according to FTIR. However, Raman revealed that a large increase in graphene planar and edge defects are present as indicated by the disorder band at 1340 cm-1. Further optimization could be performed by thermal exfoliation at lower temperatures assuming a need for fewer structural defects. Graphene oxide coatings showed clear reduction with an increase with photoreduction time. Raman revealed that the reduced graphene oxide films had less disruption in the planar phonon lattice vibrations which indicates that the structure is returning to sp2 hybridization of pristine graphene without adding structural defects.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Antiferromagnetic Inverse Spinel Oxide LiCoVO 4 with Spin-Polarized Channels for Water Oxidation

Exploring highly efficient catalysts for the oxygen evolution reaction (OER) is essential for water electrolysis. Cost-effective transition-metal oxides with reasonable activity are raising attention. Recently, OER reactants' and products' differing spin configurations have been thought to cause slow reaction kinetics. Catalysts with magnetically polarized channels could selectively remove electrons with opposite magnetic moment and conserve overall spin during OER, enhancing triplet state oxygen molecule evolution. Herein, antiferromagnetic inverse spinel oxide LiCoVO 4 is found to contain d 7 Co 2+ ions that can be stabilized under active octahedral sites, possessing high spin states S = 3/2 (t 2g 5 e g 2 ). With high spin configuration, each Co 2+ ion has an ideal magnetic moment of 3 µ B , allowing the edge-shared Co 2+ octahedra in spinel to be magnetically polarized. Density functional theory simulation results show that the layered antiferromagnetic LiCoVO 4 studied contains magnetically polarized channels. The average magnetic moment (µ ave ) per transition-metal atom in the spin conduction channel is around 2.66 µ B . Such channels are able to enhance the selective removal of spin-oriented electrons from the reactants during the OER, which facilitates the accumulation of appropriate magnetic moments for triplet oxygen molecule evolution. Finally, the LiCoVO 4 reported has been identified as an oxide catalyst with excellent OER activity.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Oxidation of Cyclopentene with Manganese Oxides Octahedral Molecular Sieves with Layer and Tunnel Structures

We report manganese oxides type octahedral molecular sieves OL-1, OMS-1, and OMS-2 were synthesized, impregnated with sodium tungstate, and evaluated as catalysts for the selective epoxidation of cyclopentene (CPE) to cyclopentene oxide (CPO) in the sodium bicarbonate/hydrogen peroxide (BAP) system. OL-1 was the best catalyst with a conversion of 78.6 % and a selectivity to CPO of 31.4 %. Impregnation with sodium tungstate affected the structure and activity of OL-1 and OMS-1. Mn 2+ is required for the epoxidation of CPE. FTIR spectra provides evidence that tungstate ions react, during impregnation, with Mg 2+ and/or Mn 2+ present in OMS-1 and OL-1 producing an amorphous compound that is not active in the epoxidation reaction. The crystalline and chemical structure of OMS-2 was not affected by tungstate impregnation, since most of the manganese occurs as Mn 3+ and Mn 4+ , which in presence of hydrogen peroxide, tend to form radicals, active in the total oxidation of organic compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Machine learning informed rational design of high entropy double perovskite oxide universal air/steam electrodes for solid oxide electrochemical cells

Due to their high efficiency and versatility, solid oxide electrochemical cells (SOCs) are poised to play a significant role in future energy conversion and storage applications. In recent years, SOCs have bifurcated into two distinct categories: traditional oxygen-ion conducting SOCs that typically operate from ∼650—850 °C and the more recent proton-conducting ceramic (PCC) SOCs that typically operate from ∼400—650 °C. Current performance and lifetime of both oxygen-ion conducting SOCs and PCCs is primarily limited by the air/steam electrode, which facilitates the oxygen reduction reaction (ORR) during fuel cell operation and must also facilitate the oxygen evolution reaction (OER) during electrolysis operation. Here, we present a newly designed high-entropy double perovskite oxide suitable as a universal ORR/OER electrode for both oxygen-ion conducting SOCs and PCCs. Machine learning methods are applied to identify chemical descriptors for highly catalytic high-entropy double perovskite oxides (AA’B 2 O 6 ) across a large compositional space. Based on the machine-learning guidance, we ultimately converge on Ba 0.9 Cs 0.1 (Ca 0.2 Gd 0.2 La 0.2 Pr 0.2 Sr 0.2 )Co 1.5 Fe 0.5 O 6 (CsBaHEO) as a universal air/steam electrode. Structure stabilization is accomplished by an equimolar five-cation high-entropy composition on the A’-site, while cesium substitution on the A-site enhances the electrical conductivity and leads to a higher oxygen vacancy concentration. This material exhibits versatility and high performance in reversible oxygen-ion SOCs, reversible PCCs, and also large-scale tubular PCCs. For example, the CsBaHEO-based PCC reaches 1018 mW∙cm −2 at 600°C, while a large-scale tubular PCC using CsBaHEO for electrolysis achieves a hydrogen production rate of 21.314 ML∙min −1 at 600 °C.

Cell↗
DOE OSTI2019

A highly efficient catalyst of palygorskite-supported manganese oxide for formaldehyde oxidation at ambient and low temperature: Performance, mechanism and reaction kinetics

A series of palygorskite-supported manganese oxide (MnO x /PG) catalysts were prepd. by a pptn. method using different manganese precursor. The as-prepared MnO x /PG catalysts were used to evaluate the catalytic oxidn. of HCHO and characterized by BET, XRD, TG, Raman spectroscopy, TEM, H 2 -TPR, XPS, and chemical titration. The results showed that the crystalline phase, distribution and Mn valence states of MnO x on the surface of PG depended on the precursors. Birnessite-type manganese oxide (δ-MnO 2 ) formed and uniformly coated on the surface of PG when potassium permanganate (PP) was used as the precursor. The MnO x /PG-PP catalyst showed the best catalytic activity for HCHO removal at low temp. among these catalysts and achieved complete HCHO conversion at 150 °C. More importantly, the dynamic single-pass removal efficiency of MnO x /PG-PP catalyst for ppm-level HCHO oxidn. was as high as 95% under high GHSV (300 L/g·h) at ambient temp. MnO x /PG-PP catalyst also exhibited excellent cycling stability and long-term activity at low and ambient temp. The kinetic results of MnO x /PG-PP catalyst showed that the oxidn. of HCHO followed the Mars-van Krevelen mechanism. The possible reaction pathway of HCHO oxidn. was proposed based on in situ DRIFTS and TPSR studies. The large sp. surface area, highly distributed active component, a high proportion of Mn 4+ species, and lattice oxygen content are responsible for the high catalytic activity of MnO x /PG-PP for oxidn. of formaldehyde. This work developed a natural mineral supported manganese oxide as an inexpensive and efficient catalyst for the purifn. of HCHO in industrial or indoor air environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Improving bamboo’s fuel and storage properties with a net energy export through torrefaction paired with catalytic oxidation

Using torrefied char, or biocoal, as solid fuel provides an opportunity to introduce a sustainable feedstock into the energy market. The goals of this study were to investigate how torrefaction improves the energy content and the grindability of a Malaysian bamboo along with understanding the potential for integrated energy recovery from torrefaction gases. The feedstock was torrefied at 250–290 °C for 1 h and the combustion characteristics and grindability of the solid products along with the composition of torrefied gas species were measured. The results showed a beneficial increase in elemental carbon increased from 47 to 63 wt% at 290 °C torrefaction, reflecting an increase in higher heating value from 17.8 to 25.6 MJ/kg. The combustion behavior of all the products appeared to show three distinct combustion zones; however, torrefaction severity leading to higher combustion temperature and time as the fixed carbon augmented with the increase of torrefaction temperature. This increase in severity also lead to more friable and grindable material, and the 290 °C condition required a factor of 2.7 less hold-up time in the mill compared to the raw bamboo, and a factor of 8.5 less energy (938 and 111 kWh/tonne respectively). Through analysis of the gas and volatile formation, a case study showed that catalytic oxidation can convert nearly 100% of the embodied chemical energy into usable thermal energy. These experimental findings were scaled to a 100,000 tonne/y capacity torrefaction plant and in the moderate case of 270 °C operating temperature, the plant has 1.25 GJ/tonne excess energy beyond what the process needs.

09 BIOMASS FUELS↗