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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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Presentation includes slides on Surface Science used to probe LEU-10Mo Spall; Auger highlights graphitic-like inclusions and Mo-deficient oxide on base metal; Higher C concentration detected within spall area Images Courtesy; Depth profiling reveals thick oxide; Mo concentration nears nominal only at depths ~400 nm; and lastly Key Findings.
Materials were studied as candidates for development as potential new aircraft brake lining materials. These families were (1) copper-graphite composites; (2) nickel-graphite composites; (3) copper - rare-earth-oxide (gadolinium oxide (Gd2O3) or lanthanum oxide (La2O3)) composites and copper - rare-earth-oxide (La2O3) - rare-earth-fluoride (lanthanum fluoride (LaF3)) composites; (4) nickel - rare-earth-oxide composites and nickel - rare-earth-oxide - rare-earth-fluoride composites. For comparison purposes, a currently used metal-ceramic composite was also studied. Results showed that the nickel-Gd2O3 and nickel-La2O3-LaF3 composites were comparable or superior in friction and wear performance to the currently used composite and therefore deserve to be considered for further development.
We report here the first use of a new ion-imaging system to locate a rare interstellar aluminum oxide grain in a Murchison acid residue. While several types of carbon-rich interstellar grains, including graphite, diamond, SiC, and TiC, have previously been found, isotopically anomalous interstellar oxide grains have proven more elusive. We have developed an ion imaging system which allows us to map the isotopic composition of large numbers of grains relatively quickly and is, thus, ideally suited to search for isotopically exotic subsets of grains. The system consists of a PHOTOMETRICS CCD camera coupled to the microchannel plate/fluorescent screen of the WU modified CAMECA IMS-3F ion microprobe. Isotopic images of the sample surface are focused on the CCD and digitized. Subsequent image processing identifies individual grains in the images and determines isotopic ratios for each. For the present work, we have imaged in O-16 and O-18; negligible contributions of (17)OH(-) and (16)OH2(-) signals to the O-18 signal allow the use of low mass resolution, simplifying the measurements. Repeated imaging runs on terrestrial corundum particles showed that the system measures isotopic ratios reproducibly to about +/- 40%. Each imaging run took about six minutes to complete, and for this study there were on average 5-15 grains in each image. We have conducted imaging searches in 2-4 micron size separates of both Orgueil and Murchison.
Graphite powder was adopted to prevent AZ91D alloy from oxidizing during melting and casting. The microstructure of the resultant surface films, formed at 933 K, 973 K, 1013 K, and 1053 K (660 °C, 700 °C, 740 °C, and 780 °C) for 30 minutes, was investigated by scanning electron microscopy, energy dispersive spectrometer, and X-ray diffraction, and the phase composition of the surface films was analyzed by the standard Gibbs free energy change of the reactions between the graphite powder, the alloy melt, and the ambient atmosphere. The effect and mechanism of melt temperature on the resultant surface films were also discussed. The results indicated that the surface films, of which the surface morphology comprised folds and wrinkles, were composed of a protective layer and MgF{sub 2} particles. The protective layer was contributive to the prevention of the molten alloy from oxidizing, and consisted of magnesium, oxygen, fluorine, carbon, and a small amount of aluminium existing in the form of MgO, MgF{sub 2}, C, and MgAl{sub 2}O{sub 4}. The layer thickness was 200 to 900 nm. The melt temperature may affect the surface films through the increased interaction between the graphite powder, the melt, and the ambient atmosphere. The oxygen content and thickness of the protective layer decreased and then increased, while the height of the folds increased with melt temperature.
X-ray diffraction, differential thermal analysis, and chemical analysis of sintered nickel electrode at graphitic level and high temperatures
Thermal neutron scattering data is necessary for reactor simulations of thermal reactors, but the data storage required can be unwieldy. This is exacerbated when simulations require a large temperature range, as is the case for accident scenarios and reactor start-up. Previous work conducted at RPI has explored and demonstrated a proof of concept of On-The-Fly (OTF) data storage with light water and crystalline graphite based on ENDF/B-VII.1. This provides an updated data storage paradigm for incoherent inelastic cross-sections that allow the data to be used to generate necessary sampling Cumulative Density Functions (CDFs) for any desired temperature. The work presented in this paper extends the previous work by implementing the proof of concept based on ENDF/B-VIII.0, instead of ENDF/B-VII.1, and to include additional materials, such as beryllium and oxygen in beryllium oxide and the new reactor grades of porous graphite. Completion of this work allows a single thermal data file to represent any thermal scattering event for a given material OTF for the temperature of interest, which greatly reduces the data storage needed with only a marginal cost in the calculation of the CDFs OTF. This paper will review the basic methodologies in generating the OTF data, as well as present the updates and improvements made in the generation process. Application of the methodologies covered in this paper show a significant reduction in the storage requirements for inelastic incoherent scattering events. In which, the evaluated ENDF/B-VIII.0 thermal scattering library can be reduced from 563.1 MB to 10.9 MB for light water and 339.3 MB to 13.6 MB for Be in BeO.
Direct synthesis of thin-film carbon nanomaterials on oxide-coated silicon substrates provides a viable pathway for building a dense array of miniaturized (micron-scale) electrochemical sensors with high performance. However, material synthesis generally involves many parameters, making material engineering based on trial and error highly inefficient. Here, we report a two-pronged strategy for producing engineered thin-film carbon nanomaterials that have a nano-graphitic structure. First, we introduce a variant of the metal-induced graphitization technique that generates micron-scale islands of nano-graphitic carbon materials directly on oxide-coated silicon substrates. A novel feature of our material synthesis is that, through substrate engineering, the orientation of graphitic planes within the film aligns preferentially with the silicon substrate. This feature allows us to use the Raman spectroscopy for quantifying structural properties of the sensor surface, where the electrochemical processes occur. Second, we find phenomenological models for predicting the amplitudes of the redox current and the sensor capacitance from the material structure, quantified by Raman. Our results indicate that the key to achieving high-performance micro-sensors from nano-graphitic carbon is to increase both the density of point defects and the size of the graphitic crystallites. Our study offers a viable strategy for building planar electrochemical micro-sensors with high-performance.
Accurate surface emissivity measurements are integral to the fidelity of the infrared thermography diagnostic evaluation in fusion reactors. The emissivities of ATJ TM graphite, Sigrafine® (R6510) graphite, and TZM alloy were measured as a function of temperature in accordance with the Contact Thermometer Method in the ASTM E1933 standard. Samples were heated resistively in a high-vacuum chamber, and the surface temperature was monitored using a surface thermocouple and a Telops long-wavelength infrared camera. The surfaces of Sigrafine® graphite and TZM alloy samples were coated with 10 nm and 20 nm layers of oxidized boron and were also measured in the uncoated condition. The thickness was assessed from measurement by a quartz crystal microbalance (QCM). ATJ TM graphite was uncoated. The measured emissivity of ATJ TM Graphite ranged from 0.82 to 0.83, uncoated Sigrafine® graphite ranged from 0.76 to 0.98, and uncoated TZM alloy ranged from 0.11 to 0.13. Oxidized boron coatings increased the emissivity of the TZM alloy to 0.18–0.23 but decreased the emissivity of Sigrafine® graphite to 0.56–0.66 for a 10 nm coating and to 0.65–0.74 for a 20 nm coating. In contrast to the expected blackbody radiance, the emissivity of uncoated Sigrafine® graphite and TZM alloy did not monotonically increase with temperature from 100 to 500 ℃.
This study investigated the reasons for the irregular structure of primary graphite nodules that were formed in a hypereutectic cast iron powder during water atomization. The graphite nodules contain a significant amount of micron-sized pores and multiple nanometric voids that formed from silicon oxide bifilms. The bifilms theory is often used to explain the mechanisms responsible for the presence of pores in castings. However, even if many results presented in the literature tend to corroborate the existence of bifilms, to this date, only indirect evidences of their existence were presented. The observations presented in this paper are the first to show the double-sided nature of these defects. These observations support the bifilms theory and give an explanation for the presence of porosities in castings. The bifilms were used as substrate for graphite growth during solidification. The irregular structure of the graphite nodules is a consequence of the rather random structure of the bifilms that were introduced in the melt as a result of turbulences on the surface of the melt during pouring. The confirmation of the existence of bifilms can contribute to the understanding of the mechanical properties of various metallic parts.
Measurements of the oxidation rates of various forms of carbon (soot, graphite, coal char) have often shown an unexplained attenuation with increasing temperatures in the vicinity of 2000 K, even when accounting for diffusional transport limitations and gas-phase chemical effects (e.g. CO 2 dissociation). With the development of oxy-fuel combustion approaches for pulverized coal utilization with carbon capture, high particle temperatures are readily achieved in sufficiently oxygen-enriched environments. Here, in this work, a new semi-global intrinsic kinetics model for high temperature carbon oxidation is created by starting with a previously developed 5-step mechanism that was shown to reproduce all major known trends in carbon oxidation, except for its high temperature kinetic falloff, and incorporating a recently discovered surface oxide decomposition step. The predictions of this new model are benchmarked by deploying the kinetic model in a steady-state reacting particle code (SKIPPY) and comparing the simulated results against a carefully measured set of pulverized coal char combustion temperature measurements over a wide range of oxygen concentrations in N 2 and CO 2 environments. The results show that the inclusion of the spontaneous surface oxide decomposition reaction step significantly improves predictions at high particle temperatures. Furthermore, the simulations reveal that O atoms released from the oxide decomposition step enhance the radical pool in the near-surface region and within the particle interior itself. Incorporation of literature rates for O and OH reactions with the carbon surface results in a reduction in the predicted radical pool concentrations and a very minor enhancement of the overall carbon oxidation rate.
The paper considers different material concepts that can be fabricated of hybridized composites which demonstrate improved graphite fiber retention capability in a severe fire without significant reduction to the composite properties. More than 30 panels were fabricated for mechanical and fire tests, the details and results of which are presented. Methods of composite hybridization investigated included the addition of oxidation resistant fillers to the resin, mechanically interlocking the graphite fibers by the use of woven fabrics, and the addition of glass fibers and glass additives designed to melt and fuse the graphite fibers together. It is concluded that a woven fabric with a serving of glass around each graphite tow is by far the superior of those evaluated: not only is there a coalescing effect in each graphite layer, but there is also a definite adhesion of each layer to its neighbor.
Abstract Developing highly efficient, cost effective, and environmentally friendly electrocatalysts for the oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and hydrogen evolution reaction (HER) is of interest for sustainable and clean energy technologies, including metal–air batteries and fuel cells. In this work, the screening of electrocatalytic activities of a series of single metallic iron, cobalt, and nickel nanoparticles and their binary and ternary alloys encapsulated in a graphitic carbon shell toward the OER, ORR, and HER in alkaline media is reported. Synthesis of these compounds proceeds by a two‐step sol–gel and carbothermal reduction procedure. Various ex situ characterizations show that with harsh electrochemical activation, the graphitic shell undergoes an electrochemical exfoliation. The modified electronic properties of the remaining graphene layers prevent their exfoliation, protect the bulk of the metallic cores, and participate in the electrocatalysis. The amount of near‐surface, higher‐oxidation‐state metals in the as‐prepared samples increases with electrochemical cycling, indicating that some metallic nanoparticles are not adequately encased within the graphite shell. Such surface oxide species provide secondary active sites for the electrocatalytic activities. The Ni–Fe binary system gives the most promising results for the OER, and the Co–Fe binary system shows the most promise for the ORR and HER.
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.
International Research & Development Programs Who is doing what in graphite throughout the world Nuclear graphite components Why is graphite so difficult to develop code rules? Unique features of nuclear grade graphite No nuclear graphite standard Brittle material in a pressure vessel code? General graphite behavior and degradation As-fabricated material properties Irradiation behavior Oxidation behavior Molten salt issues
Sol–gel chemistry, while being extremely established, is to this day not fully understood, and much of the underlying chemistry and mechanisms are yet to be unraveled. Here, in this work, we elaborate on the sol–gel chemistry of Cr 2 GaC, the first layered ternary carbide belonging to the MAX phase family to ever be synthesized using this wet chemical approach. Leveraging a variety of both in- and ex situ characterization techniques, including X-ray and neutron powder diffraction, X-ray absorption fine structure analyses, total scattering analyses, and differential scanning calorimetry coupled with mass spectrometry, in-depth analyses of the local structures and reaction pathways are elucidated. While the metals first form tetrahedrally and octahedrally coordinated oxidic structures, that subsequently grow and crystallize into oxides, the carbon source citric acid sits on a separate reaction pathway, that does not merge with the metals until the very end. In fact, after decomposing it remains nanostructured and disordered graphite until the temperature allows for the reduction of the metal oxides into the layered carbide. Based on this, we hypothesize that the method is mostly applicable to systems where the needed metals are reducible by graphite around the formation temperature of the target phase.
Electrochemical reduction of the dizaonium complex, [Ru II (bda)(NO)(N–N 2 ) 2 ] 3+ , 2 3+ (N–N 2 2+ is 4-(pyridin-4-yl) benzenediazonium and bda 2– is [2,2'-bipyridine]-6,6'-dicarboxylate), in acetone produces the covalent grafting of this molecular complex onto glassy carbon (GC) electrodes. Multiple cycling voltammetric experiments on the GC electrode generates hybrid materials labeled as GC-4, with the corresponding Ru-aqua complex anchored on the graphite surface. GC-4 has been characterized at pH = 7.0 by electrochemical techniques and X-ray absorption spectroscopy (XAS) and has been shown to act as an active catalyst for the oxidation of water to dioxygen. This new hybrid material has a lower catalytic performance than its counterpart in homogeneous phase and progressively decomposes to form RuO 2 at the electrode surface. The resulting metal oxide attached at the GC electrode surface, GC-RuO 2 , is a very fast and rugged heterogeneous water oxidation catalyst with TOF i s of 300 s –1 and TONs >45000. The observed performance is comparable to the best electrocatalysts reported so far, at neutral pH.
Navitas Advanced Solutions Group proposes a novel, commercially scalable approach to supply microporous silicon (μpSi) to lithium ion battery manufacturers. If successful, this project will result in a significant reduction in the cost and environmental impact of high capacity anodes that are needed to meet the EV Everywhere battery goals. Silicon nanocomposite materials have been identified as a viable anode technology for EV batteries. Presently, high capacity silicon-based anodes rely either on materials that are expensive (e. g., silane or nano-silicon powder) or on processes that are limited by low yield methods (e.g., chemical vapor deposition). Microporous silicon potentially avoids these limitations and is attracting increasing attention as a lower cost alternative for the manufacture of high capacity silicon-based anodes. Microporous silicon suitable for EV batteries is not currently available as a commodity material. Microporous silicon can be produced at lab scale through a metal catalyzed hydrofluoric acid etching process. However, this process is expensive and hazardous. Our proposed production route will facilitate the availability of μpSi to lithium ion battery producers and developers at a scale and cost able to support EV battery production. Under the Vehicle Technologies FOA AOI 4 seeks Advances in Existing and Next-Generation Battery Material Manufacturing to reduce the cost of EV batteries. The EV Everywhere initiative establishes a goal of $100/kWh system level cost for an EV battery. This cost target can be met with moderate risk through pairing silicon-based high capacity anodes with lithium metal-rich nickel manganese cobalt oxide 'LMR-NMC' cathodes. For this set of assumptions, the silicon anode active material cost would need to be <$25/kg. The Navitas µpSi powder manufacturing process will reach this target through a combination of low-cost commodity raw materials and reactants with scalable and low environmental impact processes. Processing will involve mechanical milling and thermal reduction operations that are in wide application at industrial scale. The goal of this program is to reach most or all of the MRL 6 criteria in a pilot scale demonstration for the manufacturing of porous silicon powder, while minimizing raw material added cost and limiting hazardous and environmental impact and using scalable industrial processing (i.e. mechanical milling, thermal reduction). The Navitas μpSi fabrication process represents a novel approach to reduce the cost of silicon anode material manufacturing. This process has been shown to be more efficient (higher yield) and economical on scaling up than conventional metal-assisted etching. The process significantly reduces the cost on $/mAh basis versus existing anode materials. The μpSi powders can be modified to form nanocomposite structures through blending with graphite or coating with carbon or a metal oxide to decrease initial capacity loss (ICL) and improve cell cycle life, a key barrier to adoption of silicon anodes into EV batteries. The impact of this technology will be driven by the projected rate of EV adoption and market share. By reducing battery cost, the proposed technology will stimulate EV adoption rate. Assuming this technology enables capturing an additional 6% of the present PHEV + EV market the reduction in petroleum consumption would be 90,000 gallons of gasoline per day, or 1.6M barrels per year. The carbon emissions from a gallon of gasoline = 2.4 kg/gallon. Thus, if the proposed technology was incorporated into just 0.1% of all new vehicles produced and if all the electricity to power those electric-drive vehicles was produced from clean, renewable sources such as wind and solar, it would result in 15K metric tons/yr reduction of CO2 emissions.
Polyethylene is notoriously difficult to upcycle because it decomposes into light gases at approximately 350-400 °C which prevents processing it at higher temperatures to convert it into high-value carbon materials, such as graphene or graphite. We address this challenge by using an air-based, thermo-oxidation process, which heats polyethylene (PE) just below the decomposition point to initiate oxidation and cross-linking of PE alkyl chains. These molecular transformations allow PE to be further graphenized or graphitized at higher temperatures without decomposing. The PE-derived graphene has a specific surface area up to 1,800 m 2/g and Raman ID/IG ratio of 0.85, which enables it to be used as an electrode material for a symmetric supercapacitor with the 1 M H2SO4 electrolyte. The PE-derived graphene material has a comparable electrochemical capacitive performance, such as power density, specific capacitance, and long cycle stability, to the commercial state of art porous carbon electrode. The stabilized PE could also be converted into highly crystalline flake graphite via low-temperature catalytic graphitization. The PE-derived graphite is used for the lithium-ion battery anode, which showed comparable electrochemical battery performance, such as reversible rate performance and long-term cyclic stability, to the current use battery-grade graphite, thus providing a scalable method to upcycle PE plastic waste into high-value carbon material.