Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Graphite Characterization”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 487 records · Page 27

Pouch cells with 15% silicon calendar-aged for 4 years

Small amounts of high-capacity silicon-based materials are already used in the anode of commercial Li-ion batteries, helping increase their energy density. Despite their remarkable storage capability, silicon continu-ously reacts with the electrolyte, accelerating time-dependent cell performance fade. Nevertheless, very limited information is available on the specific consequences of this reactivity for the calendar aging of Li-ion cells. Here, we analyze aging effects on 450 mAh pouch cells containing 15 wt% of Si (and 73 wt% graphite) after storage at 21 °C for four years. We show that severe losses of Si capacity occurred due to particle isolation when cells were stored at high states of charge (SOC), but not when cells were fully discharged prior to storage. Impedance rise was also significantly higher when cells were kept at high SOCs and was mostly due to phenomena taking place at the cathode; the continuous electrolyte reduction at the anode did not lead to a major increase in bulk electrode resistance. A series of post-test characterization provided additional information on the effects of time and SOC on the calendar aging of Si-containing cells. In conclusion, our study highlights the many challenges posed by Si during calendar aging and can inform future studies in the field.

25 ENERGY STORAGE↗

Design Rules for Carboborothermic Reduction Synthesis of High Uranium Density UB 4 –UBC Composites

Uranium borides are promising candidate fuel forms for use in advanced nuclear reactors due to their high thermal conductivity and potential for dual use as both fuel and burnable absorber. In this work, uranium tetraboride () and uranium monoboroncarbide (UBC) composite were synthesized by using industrially scalable carboborothermic reduction method. The final uranium boride phase composition is sensitive to the sample holding crucibles ( and graphite) such that graphite supply excess carbon, promoting the formation of a predominant UBC phase. The high‐temperature in situ synchrotron X‐ray diffraction of pristine –UBC show persistence , UBC, and phases while preoxidized –UBC leads to predominant and formation due to progressive oxidation and boron loss at high temperature. The oxidation behavior was further characterized using thermogravimetric analysis, allowing direct comparison with other potential accident tolerant fuels such as , , UC, and UN. The –UBC shows higher uranium loading than monolithic and demonstrates promising oxidation behavior at high temperature, pointing to its potential as an improved uranium boride‐based fuel form.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Performance Testing of Yardney MCMB-LiNiCoAlO2 Lithium-ion Cells Possessing Electrolytes with Improved Safety Characteristics

Many future NASA missions aimed at exploring the Moon and Mars require high specific energy rechargeable batteries that possess enhanced safety characteristics. There is also a strong desire to develop Li-ion batteries with improved safety characteristics for terrestrial applications, most notably for HEV and PHEV automotive applications. In previous work focused upon evaluating various potential flame retardant additives1, triphenyl phosphate (TPP)2 was observed to have the most desirable attributes, including good life characteristics and resilience to high voltage operation. We have employed a number of approaches in the design of promising TPP-based electrolytes with improved safety, including: (a) varying the flame retardant additive (FRA) content (from 5 to 15%), (b) the use of fluorinated co-solvents, (c) the use of additives to improve compatibility, and (c) the use of ester co-solvents to decrease the viscosity and increase the conductivity. In recent work, we have demonstrated a number of these electrolyte formulations to be compatible with a number of chemistries, including: MCMB carbon-LiNi0.8Co0.2O2, graphite-LiNi0.8Co0.15Al0.05O2, Li-Li(Li0.17Ni 0.25 Mn 0.58 )O2, Li-LiNiCoMnO2 and graphite- LiNiCoMnO2.3,4 In the current study, we have demonstrated the performance of a number of TPP-containing electrolytes in 7 Ah prototype MCMB-LiNiCoO2 cells. We will describe the results of a number of performance tests, including: a) 100% DOD cycle life testing at various temperatures, b) discharge rate characterization as a function of temperature, c) charge rate characterization as a function of temperature, and d) impedance as a function of temperature. In addition to displaying good life characteristics, being comparable to baseline chemistries, a number of cells were observed to provide good performance over a wide temperature range.

Li-ion batteries↗

Robust Solar Receivers Using MAX Phase Materials

This work was supported by the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy under the Solar Energy Technologies Office Award Number 35928. The objective of the proposed effort was to develop and optimize additive manufacturing technologies for low-cost fabrication of high-temperature receivers using MAX phase-based materials (Ti 3 SiC 2 and Ti 3 AlC 2 ). MAX phase materials are a group of ternary metal carbides and nitrides where M stands for an early transition metal element, A is a group 13–16 element, and X is C and/or N. In Phase 1, the binder jetting additive manufacturing process was used to synthesize and characterize the Ti 3 SiC 2 MAX phase material. The typical process involved first producing a TiC preform using binder jetting followed by infiltration of the preform with silicon melt to form Ti 3 SiC 2 in situ. The reaction-infiltrated samples showed formation of MAX phase in the sample core; however, the surface showed cracking. Various process conditions—cooling rates, hold times, Si proportion, etc.—were varied to minimize the surface cracking. The fabricated MAX phase core was characterized by microstructure analysis and evaluations of mechanical properties such as hardness and thermal shock. In Phase 2, the focus included fabrication of Ti 3 SiC 2 MAX phase materials by spark plasma sintering (SPS) and synthesis of Ti 3 AlC 2 MAX phase materials by the Al melt infiltration process. It is expected that Al infiltration will not cause sample cracking, since Al does not expand during solidification. In addition, other processing approaches were investigated to fabricate the MAX phase materials, such as SPS with a graphite bedding approach for producing short-length Ti 3 AlC 2 MAX phase tubes for demonstration of prototypical Concentrating Solar Power receiver tubes. Fabricated samples underwent thermo-mechanical testing to validate the materials for the solar receiver application at temperatures >1000°C. In Phase 3, the effort focused on the development and optimization of the Ti-Al-C MAX phase composite material using the Al melt infiltration approach. We started with optimization of precursor powders and making preform structures by either pressing them in a die or using the binder jetting additive manufacturing process followed by Al melt infiltration. In addition, we investigated the formation of preform structures by cold isostatic pressing followed by Al melt infiltration for making Ti-Al-C MAX phase composite. Thermo-mechanical characterizations, such as creep, strength, and thermal shock, were conducted to establish the structures’ performance.

36 MATERIALS SCIENCE↗

Structure sensitivity and its effect on methane turnover and carbon co-product selectivity in thermocatalytic decomposition of methane over supported Ni catalysts

We explore how thermocatalytic decomposition of methane (TCD) is a promising approach for producing CO 2 -free hydrogen and solid carbon co-product. In this study, a series of Al 2 O 3 - and MgAl 2 O 4 -based Ni catalysts, prepared with varying synthesis and pretreatment methods, were evaluated for methane TCD performance at 650°C and characterized before and after reaction to elucidate activity-structure relationships. We found that methane TCD turnover increases with Ni particle size. Further, large Ni particle sizes (i.e., >20 nm) are selective toward the formation of carbon nanotubes (CNTs), while small Ni particle sizes (i.e., <10 nm) are selective toward the formation of graphitic carbon layers. The formation of graphitic carbon layers block access to Ni active sites, thus rendering the catalyst inactive more quickly than when CNTs are produced. Additionally, the catalyst deactivation observed with time-on-stream is due to the fragmentation of Ni particles into smaller Ni particles followed by their encapsulation with graphitic carbon layers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Active Learning-driven Quantitative Synthesis-Structure-Property Relations for Improving Performance and Revealing Active Sites of Nitrogen-Doped Carbon for the Hydrogen Evolution Reaction

While quantitative structure-properties relations (QSPRs) have been developed successfully in multiple fields, catalyst synthesis affects structure and in turn performance, making simple QSPRs inadequate. Furthermore, catalysts often have multiple active sites preventing one from obtaining insights into structure-property relations. Here, we develop a data-driven quantitative synthesis-structure-property relation (QS2PRs) methodology to elucidate correlations between catalyst synthesis conditions, structural properties as well as observed performance and to provide fundamental insights into active sites and a systematic way to optimize practical catalysts. Here, we demonstrate the approach to the synthesis of nitrogen-doped catalysts (NDC) made via pyrolysis for the performance of the electrochemical hydrogen evolution reaction (HER), quantified by the onset potential and the current density. We determine crystallinity, nitrogen species type and fraction, surface area, and pore structure of the NDC’s using XRD, XPS, and BET characterization. We demonstrated that an active learning-based optimization combined with various elementary machine learning tools (regression, principal component analysis, partial least squares) can efficiently identify optimum pyrolysis conditions to tune structural characteristics and performance with concomitant savings in materials and experimental time. Unlike previous reports on the importance of pyridinic or graphitic nitrogen, we discover that the electrochemical performance is not driven by a single catalyst property; rather, it arises from a multivariate influence of nitrogen dopants, pore structure and disorder in the NDC materials. Identification of active sites can help mechanistic understanding and further catalyst improvement.

42 ENGINEERING↗

Unusual flat and extended morphology of intercalated Cu under MoS 2

We report a general method was developed to intercalate metals under layered materials through a controlled density of sputtered defects. The method has already been applied to study a range of metals intercalated under graphite, and different types of morphologies were realized. In the current work, we extend the method to the study of intercalation under MoS 2 , noting that work on this system is rather limited. We use Cu as the prototype metal for comparison with Cu intercalation under graphite. Although the growth conditions needed for intercalation under graphite and MoS 2 are similar, the type of intercalated phases is very different. Each Cu island that nucleates on top of MoS 2 during Cu deposition provides material that is transferred below MoS 2 through sputtered defects under the island base; this transfer results in a uniform intercalated Cu “carpet” morphology that extends over the mesoscale. On the contrary, Cu intercalation under graphite results in well separated, compact islands formed by monomer detachment from small Cu islands on top and transfer below through defects far from the islands. The structural techniques (scanning electron microscopy and atomic force microscopy) and spectroscopic techniques (x-ray photoelectron spectroscopy and energy-dispersive spectroscopy) are used for the characterization of the intercalated Cu layer.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Mechanical behavior and fracture characteristics of off-axis fiber composites. 2: Theory and comparisons

The mechanical behavior and stresses inducing fracture modes of unidirectional high-modulus graphite-fiber/epoxy composites subjected to off-axis tensile loads were investigated theoretically. The investigation included the use of composite mechanics, combined-stress failure criteria, and finite-element stress analysis. The results are compared with experimental data and led to the formulation of criteria and convenient plotting procedures for identifying, characterizing, and quantifying these fracture modes.

Chamis, C. C.↗

AGR-5/6/7 Fuel Fabrication Report

The U.S. Department of Energy Office of Nuclear Energy (DOE NE) and the Idaho National Laboratory (INL) Advanced Reactor Technologies (ART) Advanced Gas Reactor (AGR) Fuel Development and Qualification program (referred to as AGR Fuel program hereafter) are pursuing qualification of tristructural isotropic (TRISO) coated particle fuel for use in high temperature gas cooled reactors (HTGRs). The AGR Fuel program was established to provide a fuel qualification data set in support of the licensing and operation of an HTGR. BWX Technologies Nuclear Operations Group (BWXT-NOG) was subcontracted to fabricate the fuel for the AGR program. Several investments and innovations were realized in preparation to fabricate fuel for the AGR-5/6/7 irradiation experiments that brought fuel fabrication fully out of the laboratory and into engineering-scale operations. These included: • Increased the kernel fabrication line capacity and uniformity • Upgraded ancillary support equipment and processes for the tristructural isotropic (TRISO) coating furnace • Demonstrated efficient production of the matrix precursor powder by dry jet milling of co mingled components • Demonstrated an engineering-scale method for quick and efficient overcoating TRISO particles with the matrix precursor • Demonstrated an automated, multi cavity compacting system with a volumetric feed system • Demonstrated a combined-cycle thermal treatment furnace These changes increased production rates of some of these processes by an order of magnitude or more while eliminating the use of flammable solvents, multiple grinding and sorting operations, and the weighing out of individual die charges. Three fuel kernel lots were fabricated for production of the fuel for AGR-5/6/7. The initial lot (J52R-16-39316) was certified to fuel specifications but was not used because the kernels had a high fraction of internal fissures that caused an unacceptable fraction of the kernels to fragment when charged to the coating furnace where the TRISO coating would be deposited. Fragmented kernels increased the dispersed uranium in the particles and produced a worrisome fraction of dimpled particles with an elevated probability of in-pile failure. After some efforts to identify the cause of the fissure formation, two additional lots were produced with much lower fissure fractions, J52R-16-69317 and 69318. The latter kernel lot was a backup to the first and was not needed. Multiple kernel batches were composited to form each of the lots so as to simulate a commercial-scale operation where kernel batches would also be composited. Multiple TRISO coating runs were performed and the product characterized so that several could be composited into a TRISO lot. TRISO lot J52R-16-98005 conformed to all fuel specifications except the mean outer pyrocarbon (OPyC) layer thickness was thinner than specified. Furthermore, it was determined that the TRISO lot had a dispersed uranium fraction (DUF) that might result in the compacts not meeting the DUF specification. A review of the role of the OPyC layer and consequences of the DUF by the Technical Coordination Team and INL concluded that the fuel was acceptable for use in the AGR-5/6/7 irradiation experiment. The TRISO particles were overcoated with the matrix precursor that had been produced in a jet-milling operation. The overcoating was performed in equipment originally designed to coat pharmaceuticals. The overcoating process performed well; producing highly spherical and uniform overcoats requiring little upgrading and no recycle or rework. TRISO particles were overcoated with the matrix precursor to achieve nominal volumetric packing fractions (PFs) of TRISO particles of 25% and 40% for the irradiation experiments. The 40% PF compacts occupy the first and fifth test capsule in the test train while the inner three capsules are loaded with 25% PF compacts. The resinated graphite matrix precursor powder was a derivative of the German A3-27 matrix formulation, which differs from previous AGR irradiation campaigns that used an A3-3 formulation. Jet milling of the matrix powder precursor produced a finer mean graphite particle size than the milling operations used for the A3-3 matrix powder precursor. Changes made in the matrix formula and equipment yielded compacts with significantly higher matrix density than was attained in previous AGR irradiation campaigns. The changes in the matrix formulation and the means of milling the powders also complicated resolution of the three fuel compact defect fractions, DUF, exposed kernel fraction (EKF), and the silicon carbide defect fraction (SDF). Characterization data from BWXT-NOG had some anomalous results, so samples of the fuel compacts and overcoated TRISO particles were also analyzed by Oak Ridge National Laboratory (ORNL) to ensure that the defect fractions were accurately characterized.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Effect of Si Content on Extreme Fast Charging Behavior in Silicon–Graphite Composite Anodes

Commercial Li-ion batteries typically incorporate a small amount of high-capacity silicon (Si)-based materials in the composite graphite-based anode to increase the energy density of the battery. However, very little is known about the effects of Si on the fast-charging behavior of composite anodes. Herein, we examine the effects of the Si/graphite ratio in the composite anode on the fast-charging behavior of full cells. We show that addition of Si increases the rate capability from 1C to 8C and improves the capacity retention in early cycles at 6C due to reduced overpotential in constant current charging cycles. The impacts of Si content on fast-charging aging were identified by Post-Test characterization. Despite realizing benefits of available capacity and reduced Li plating at 6C, silicon–electrolyte interactions lead the time-dependent cell performance to fade quickly in the long term. The Post-Test analysis also revealed the thickening of the electrode and nonuniform distribution of electrolyte decomposition products on the Si-containing anodes, as well as the organic-rich solid electrolyte interphase (SEI), which are the factors behind cell degradation. Our study sheds insight on the advantages and disadvantages of Si/graphite composite anodes when they are used in fast-charging applications and guides further research in the area by designing an optimized composition of Si incorporated in a mature graphite matrix.

25 ENERGY STORAGE↗

Optimizing dicyandiamide pretreatment conditions for enhanced structure and electronic properties of polymeric graphitic carbon nitride

Graphitic carbon nitride, a polymeric semiconductor, possesses a distinctive electronic band structure and exceptional chemical stability, making it a highly promising material for various catalytic applications such as electrocatalysis, photocatalysis, and photo-electrocatalysis. However, its practical applications remain limited due to its low active site density and poor electrical conductivity. In this study, to overcome such limitations, we have conducted a thorough investigation to explore the impact of dicyandiamide (DCDA) precursor pretreatment prior to thermal polymerization to graphitic carbon nitride. The DCDA precursor was subjected to various pretreatment methods including grinding using mortar and pestle, recrystallization through stirring or probe sonication after dissolving in deionized water, and freeze drying, prior to thermal polymerization at 550 °C for 2 hours. The structural and morphological properties of the catalysts prepared were compared and characterized by X-ray diffraction (XRD), attenuated total reflectance–Fourier transform infrared (ATR-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) analysis while the electronic band gap properties were determined based on density functional theory (DFT) calculations for a set of crystalline systems having C/N ratios similar to those identified experimentally. In comparison to direct thermal polymerization, pretreated samples rendered the same product yield, diverse morphologies with flat or wrinkle structures, and reduced electrochemical resistance, making them suitable for use in various catalytic processes.

36 MATERIALS SCIENCE↗

Fracture modes of high modulus graphite/epoxy angleplied laminates subjected to off-axis tensile loads

Angelplied laminates of high modulus graphite fiber/epoxy were studied in several ply configurations at various tensile loading angles to the zero ply direction in order to determine the effects of ply orientations on tensile properties, fracture modes, and fracture surface characteristics of the various plies. It was found that fracture modes in the plies of angleplied laminates can be characterized by scanning electron microscope observation. The characteristics for a given fracture mode are similar to those for the same fracture mode in unidirectional specimens. However, no simple load angle range can be associated with a given fracture mode.

Sinclair, J. H.↗

A ceramic matrix composite based on polymerization and pyrolysis of ethynylated aromatics

A number of ethynylated aromatic monomers recently have been synthesized which thermally homopolymerize and copolymerize to produce rigid, highly cross-linked polymers with high thermal stability (Tg of about 450 C). On pyrolysis, these polymers lose few volatiles (more than 85 percent char yield) to yield carbon bodies of relatively low porosity. These properties render the ethynylated aromatics of significant interest as matrices for high temperature composites. Incorporation of a SiC particle filler in the matrix improves the rheology of the system and minimizes shrinkage during pyrolysis. Several unidirectional composites have been fabricated combining a graphite or boria-alumina-silica continuous reinforcement with an ethynylated aromatic polymer matrix and SiC filler. Thermogravimetric analysis of composite pyrolysis behavior was used to determine reaction kinetics and to establish a composite fabrication cycle. Composites retained 95 percent of their green weight on pyrolysis. Microstructure of the green and pyrolyzed composites is characterized for materials pyrolyzed at 600 C in vacuum and argon as well as for laminates heated at 1200 C in argon following pyrolysis.

Hurwitz, F. I.↗

Space Environment Stability and Physical Properties of New Materials for Space Power and Commercial Applications

Useful and informative results were obtained on virtually all materials investigated. For example, the stability of ITO-based arc-proof transparent coatings was greatly improved by substitution of silicon oxide for magnesium fluoride as a dopant. Research on 'air-doped' ITO films has yielded new insight into their conduction mechanism which will help in further development of these coatings. Some air-doped films were found to be extremely pressure sensitive. This work may lead to improved, low-cost gas sensors and vacuum gauges. Work on another promising transparent arc-proof coating (titanium oxide) was initiated in collaboration with industry. Graphite oxide-like materials were synthesized and tested for possible use in high energy-density batteries and other applications. We also started a high-priority project to find the cause of unexpected environmental damage to the exterior of the Hubble Space Telescope (HST) discovered on a recent Shuttle mission. Materials were characterized before and after exposure to soft x-rays and other threats in ground-based simulators.

Hambourger, Paul D.↗

Lunar and Planetary Science XXXVI, Part 12

Topics discussed include: The Ancient Lakes in Hellas Basin Region as Seen Through the First Year of Mars Express HRSC-Camera; DISR Observations of Craters at Titan at the Huygens Landing Site: Insights Anticipated; The Sun s Dust Disk - Discovery Potential of the New Horizons Mission During Interplanetary Cruise; Evidence for Aqueously Precipitated Sulfates in Northeast Meridiani Using THEMIS and TES Data; Integrated Spectroscopic Studies of Anhydrous Sulfate Minerals; Venusian Channel Formation as a Subsurface Process; Reexamination of Quartz Grains from the Permian-Triassic Boundary Section at Graphite Peak, Antarctica; Observations of Calcium Sulfate Deposits at High Latitudes by OMEGA/Mex at Km/Pixel Resolutions; Observations of the North Permanent Cap of Mars in Mid-Summer by OMEGA/MEX at km per Pixel Resolutions; Classification and Distribution of Patterned Ground in the Southern Hemisphere of Mars Genesis: Removing Contamination from Sample Collectors; Thermal Characterization of Fe3O4 Nanoparticles Formed from Poorly Crystalline Siderite; Hydrogen Abundances in Metal Grains from the Hammadah Al Hamra (HaH) 237 Metal-rich Chondrite: A Test of the Nebular-Formation Theory; REE and Some Other Trace Elements Distributions of Mineral Separates in Atlanta (EL6); The Composition and Origin of the Dewar Geochemical Anomaly; Asteroid Modal Mineralogy Using Hapke Mixing Models: Testing the Utility of Spectral Lookup Tables; and The Huygens Mission at Titan: Results Highlights. (sup 182)Hf-(sup 182)W Chronometry and an Early Differentiation in the Parent Body of Ureilites Ground Penetrating Radar in Sedimentary Rocks Mars, Always Cold, Sometimes Wet: New Constraints on Mars Denudation Rates and Climate Evolution from Analog Studies at Haughton Crater, Devon Island, High Arctic Europa s Porous Ice Rheology and Implications for Ice-penetrating Radar Scattering Loss Surface Generated Cracks on Europa

Source record↗

Structural Response of Compression-Loaded, Tow-Placed, Variable Stiffness Panels

Results of an analytical and experimental study to characterize the structural response of two compression-loaded variable stiffness composite panels are presented and discussed. These variable stiffness panels are advanced composite structures, in which tows are laid down along precise curvilinear paths within each ply and the fiber orientation angle varies continuously throughout each ply. The panels are manufactured from AS4/977-3 graphite-epoxy pre-preg material using an advanced tow placement system. Both variable stiffness panels have the same layup, but one panel has overlapping tow bands and the other panel has a constant-thickness laminate. A baseline cross-ply panel is also analyzed and tested for comparative purposes. Tests performed on the variable stiffness panels show a linear prebuckling load-deflection response, followed by a nonlinear response to failure at loads between 4 and 53 percent greater than the baseline panel failure load. The structural response of the variable stiffness panels is also evaluated using finite element analyses. Nonlinear analyses of the variable stiffness panels are performed which include mechanical and thermal prestresses. Results from analyses that include thermal prestress conditions correlate well with measured variable stiffness panel results. The predicted response of the baseline panel also correlates well with measured results.

Wu, K. Chauncey↗

Purification Procedures for Single-Wall Carbon Nanotubes

This report summarizes the comparison of a variety of procedures used to purify carbon nanotubes. Carbon nanotube material is produced by the arc process and laser oven process. Most of the procedures are tested using laser-grown, single-wall nanotube (SWNT) material. The material is characterized at each step of the purification procedures by using different techniques including scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), Raman, X-ray diffractometry (XRD), thermogravimetric analysis (TGA), nuclear magnetic resonance (NMR), and high-performance liquid chromatography (HPLC). The identified impurities are amorphous and graphitic carbon, catalyst particle aggregates, fullerenes, and hydrocarbons. Solvent extraction and low-temperature annealing are used to reduce the amount of volatile hydrocarbons and dissolve fullerenes. Metal catalysts and amorphous as well as graphitic carbon are oxidized by reflux in acids including HCl, HNO3 and HF and other oxidizers such as H2O2. High-temperature annealing in vacuum and in inert atmosphere helps to improve the quality of SWNTs by increasing crystallinity and reducing intercalation.

Gorelik, Olga P.↗