SEARCH · Engineering Papers
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.
Structure of the program Graphite material issues of interest How do things fit together Status of the program Baseline AGC Experiment Update AGC-4 and HDG-1 Irradiation Oxidation Modeling ASME Code development Discussion of how the data can be used Modeling behavior of core components Licensing/code development Interaction with vendors Collaborations (domestic and international)
Carbon fibers and carbon fiber composites are applied in high-performance applications, but a key consideration for application is their relative sensitivity to oxidative environments. To enable in-situ characterization of carbon fibers exposed to oxidative conditions, the Raman spectral response of T700 carbon fibers that have been exposed to a variety of dwell temperatures is reported herein with dwell times reaching up to 1 month. Here, we evaluate the spectra holistically by using integrated absolute difference analysis. By combining this analysis with straightforward kinetic models, we connect the total Raman spectral response to the temperature-time curve that could yield such a shift in spectral parameters. Our work connects the Raman spectral response of carbon fibers to their thermal history and can easily be extended to other graphitic materials, such as nuclear graphite.
The function of nanomaterials and biomaterials greatly depends on understanding nanoscale recognition mechanisms, crystal growth and surface reactions. The Interface Force Field (IFF) and surface model database are the first collection of transferable parameters for inorganic and organic compounds that can be universally applied to all materials. IFF uses common energy expressions and achieves best accuracy among classical force fields due to rigorous validation of structural and energetic properties of all compounds in comparison to perpetually valid experimental data. This paper summarises key aspects of parameterisation, including atomic charges and transferability of parameters and current coverage. Examples of biomolecular recognition at metal and mineral interfaces, surface reactions of alloys, as well as new models for graphitic materials and pi-conjugated molecules are described. For several metal–organic interfaces, a match in accuracy of computed binding energies between of IFF and DFT results is demonstrated at ten million times lower computational cost. Predictive simulations of biomolecular recognition of peptides on phosphate and silicate surfaces are described as a function of pH. The use of IFF for reactive molecular dynamics is illustrated for the oxidation of Mo3Si alloys at high temperature, showing the development of specific porous silica protective layers. The introduction of virtual pi electrons in graphite and pi-conjugated molecules enables improvements in property predictions by orders of magnitude. The inclusion of such molecule-internal polarity in IFF can reproduce cation–pi interactions, pi-stacking in graphite, DNA bases, organic semiconductors and the dynamics of aqueous and biological interfaces for the first time.
Ultrahigh-Ni layered oxides hold great promise as high-energy-density cathodes at an affordable cost for lithium-ion batteries, yet their practical application is greatly hampered by the poor cyclability. Herein, by employing LiNi 0.94 Co 0.06 O 2 as a model cathode in a full-cell configuration, the interphasial and structural evolution processes of ultrahigh-Ni layered oxides are systematically investigated over the course of their service life (1500 cycles). By applying advanced analytic techniques (e.g., Li-isotope labeling, region-of-interest method), the dynamic chemical evolution on the cathode surface is revealed with spatial resolution, and the correlation between lattice distortion and cathode surface reactivity is established. Benefiting from in situ X-ray diffraction (XRD) analysis, the ultrahigh-Ni layered oxide is demonstrated to undergo dual-phase reaction mechanisms with huge lattice variation, which leads to a decrease in crystallinity and secondary particle pulverization. Furthermore, the critical impact of cathode surface reaction on the graphite anode–electrolyte interphase (AEI) is revealed at nanometer scale, and a universal chemical/physical evolution process of the AEI is illustrated, for the first time. Finally, the practical viability of ultrahigh-Ni layered oxides is demonstrated through Al-doping strategy. Finally, this work presents a comprehensive understanding of the structural and interphasial degradation of ultrahigh-Ni layered oxide cathodes for developing high-energy-density lithium-ion batteries.
Composites of intercalated graphite fibers show promise to significantly reduce the weight of electromagnetic interference shielding in spacecraft and aircraft. Bromine intercalated pitch-based fibers have been among the most heavily studied systems because of their attractive electrical and thermal conductivities and their stability over a wide range of environmental conditions. Previous studies found that the resistivity of bromineintercalated graphite fibers began to increase when the fibers were exposed to temperatures in excess of about 200 C in air for long periods of time. If the temperature was as high as 450 C, the resistivity increased dramatically within a few hours. It remained unclear, however, whether the increase was due to deintercalation of the bromine or to air oxidation of the fibers. Studies were initially directed toward determining the temperature at which bromine would deintercalate from the fibers, and perhaps become a hazard to both personnel and equipment. So the mass of bromine-intercalated graphite fibers was carefully monitored as it was heated in an inert atmosphere, since the fibers are known to oxidize at a lower temperature than they deintercalate. What was found was that the fibers, which are about 18-wt% bromine, did not lose any appreciable mass even at temperatures approaching 1000 C. X-ray diffraction studies showed that there were also no changes in the overall structure of the compound. Resistivity measurements indicated that there is some slight degradation in the electronic structure, in that the resistivity increased by a few percent. Overall, the results show that these materials may be suitable for applications at temperatures at least this high, provided oxygen is excluded. This may enable their use in carbon-ceramic, and perhaps even carbon-carbon composites.
Carbon-graphite seal ring bodies for operation at air temperatures to 1300 F(704 C) were manufactured from three select formulations. Mechanical and thermal properties, porosities, and oxidation rates were measured. The results have shown that: (1) Major property improvements anticipated from the screening studies were not realized because of processing problems associated with the scale-up in material size and probable deterioration of a phenolic resin binder; (2) the mechanical properties of a phenolic resin-bonded, carbon-graphite material can be improved by applying high pressure during carbonization; and (3) the textile form of graphite fiber used as the minor filler component in a carbon-graphite material can beneficially affect mechanical properties.
Not Available
Highlights: • SiO{sub 2}@SiO{sub 2}/RF resin composite nanospheres are prepared via a dual-templating method. • Hollow carbon nanospheres with large surface area are obtained after carbonization. • Hollow C/SiC composite nanospheres are produced after magnesiothermic reduction. • The carbonaceous nanospheres show superior electrochemical performance. • SiC nanomaterials can serve as candidate for LIBs anode materials. - Abstract: This paper presents a facile method for preparing hollow carbonaceous nanospheres for use in advanced Li-ion batteries (LIBs). Core–shell-structured silica@resin/silica nanosphere composites were used as the starting material. Hollow carbon nanospheres with a high specific surface area, i.e., 1389 m{sup 2} g{sup −1}, and C/SiC composite nanospheres composed of 24.4 wt.% amorphous carbon and 75.6 wt.% cubic β-SiC were obtained. Electrochemical measurements showed that the hollow carbon nanospheres delivered a reversible capacity of 553.5 mA h g{sup −1} after 100 cycles, which is higher than the theoretical capacity of graphite. A C/SiC composite nanosphere electrode gave a reversible capacity of 296 mA h g{sup −1} after 500 cycles. The results show that these nanospheres are promising candidates for use in LIB anodes.
The catalytic activity of a colloidal nanoparticle is typically inhibited by the very capping agents that are required to maintain colloidal stability and catalyst dispersion. Yet, the relative importance of steric contributions to the observed attenuation in catalytic activity is poorly understood. In this work, we prepare colloidal graphitic carbon nanoparticles featuring covalent amide linkages to aliphatic surface capping agents of varying length. Using aerobic benzylamine oxidation as a test reaction, we find that the steric profile of the ligand shell plays a negligible role in suppressing catalytic activity relative to chemisorption interactions that alter the surface chemistry of the catalyst. The work indicates that heterostructured nanoparticles that provide distinct surface sites for ligand binding and substrate activation should allow for high colloidal stability and robust catalytic activity.
PEM fuel cells and redox flow batteries are two very similar technologies which share common component materials and device design. Electrocatalysts are the key components in these two devices. In this Review, we discuss recent progress of electrocatalytic materials for these two technologies with a focus on our research activities at Pacific Northwest National Laboratory (PNNL) in the past years. This includes (1) nondestructive functionalization of graphitic carbon as Pt support to improve its electrocatalytic performance, (2) triple-junction of metal–carbon–metal oxides to promote Pt performance, (3) nitrogen-doped carbon and metal-doped carbon (i.e., metal oxides) to improve redox reactions in flow batteries. A perspective on future research and the synergy between the two technologies are also discussed.
The recent discovery of ferromagnetism in two-dimensional van der Waals crystals has provoked a surge of interest in the exploration of fundamental spin interaction in reduced dimensions. However, existing material candidates have several limitations, notably lacking intrinsic room-temperature ferromagnetic order and air stability. Here, motivated by the anomalously high Curie temperature observed in bulk diluted magnetic oxides, we demonstrate room-temperature ferromagnetism in Co-doped graphene-like Zinc Oxide, a chemically stable layered material in air, down to single atom thickness. Through the magneto-optic Kerr effect, superconducting quantum interference device and X-ray magnetic circular dichroism measurements, we observe clear evidences of spontaneous magnetization in such exotic material systems at room temperature and above. Transmission electron microscopy and atomic force microscopy results explicitly exclude the existence of metallic Co or cobalt oxides clusters. X-ray characterizations reveal that the substitutional Co atoms form Co 2+ states in the graphitic lattice of ZnO. By varying the Co doping level, we observe transitions between paramagnetic, ferromagnetic and less ordered phases due to the interplay between impurity-band-exchange and super-exchange interactions. Our discovery opens another path to 2D ferromagnetism at room temperature with the advantage of exceptional tunability and robustness.
The energetics involved in the bonding fluctuations between nanometer-sized silicon dioxide (SiO{sub 2}) probes and highly oriented pyrolytic graphite (HOPG) and molybdenum disulfide (MoS{sub 2}) could be quantified directly and locally on the submicron scale via a time-temperature superposition analysis of the lateral forces between scanning force microscopy silicon dioxide probes and inorganic sample surfaces. The so-called “intrinsic friction analysis” (IFA) provided direct access to the Hamaker constants for HOPG and MoS{sub 2}, as well as the control sample, calcium fluoride (CaF{sub 2}). The use of scanning probe enables nanoscopic analysis of bonding fluctuations, thereby overcoming challenges associated with larger scale inhomogeneity and surface roughness common to conventional techniques used to determine surface free energies and dielectric properties. A complementary numerical analysis based on optical and electron energy loss spectroscopy and the Lifshitz quantum electrodynamic theory of van der Waals interactions is provided and confirms quantitatively the IFA results.
PMR polyimides are safe, easy to handle, can be processed with relatively wide process controls, and offer excellent mechanical properties, with thermo-oxidative stability. Procedures, staging and cure schedules fully dense, crackfree, dimensionally controlled, complex structure: high tip speed fan blades 1.27 cm (0.5 in) thick.
Approximately 275 mineral species have been identified in meteorites, reflecting diverse redox environments, and, in some cases, unusual nebular formation conditions. Anhydrous ordinary, carbonaceous and R chondrites contain major olivine, pyroxene and plagioclase; major opaque phases include metallic Fe-Ni, troilite and chromite. Primitive achondrites are mineralogically similar. The highly reduced enstatite chondrites and achondrites contain major enstatite, plagioclase, free silica and kamacite as well as nitrides, a silicide and Ca-, Mg-, Mn-, Na-, Cr-, K- and Ti-rich sulfides. Aqueously altered carbonaceous chondrites contain major amounts of hydrous phyllosilicates, complex organic compounds, magnetite, various sulfates and sulfides, and carbonates. In addition to kamacite and taenite, iron meteorites contain carbides, elemental C, nitrides, phosphates, phosphides, chromite and sulfides. Silicate inclusions in IAB/IIICD and lIE iron meteorites consist of mafic silicates, plagioclase and various sulfides, oxides and phosphates. Eucrites, howardites and diogenites have basaltic to orthopyroxenitic compositions and consist of major pyroxene and calcic plagioclase and several accessory oxides. Ureilttes .are made up mainly of calcic, chromian olivine and low-Ca clinopyroxene embedded in a carbonaceous matrix; accessory phases include the C polymorphs graphite, diamond, lonsdaleite and chaoite as well as metallic Fe-Ni, troilite and halides. Angrites are achondrites rich in fassaitic pyroxene (i.e. , AI-Ti diopside); minor olivine with included magnesian kirschsteinite is also present. Martian meteorites comprise basalts, Iherzolites, a dunite and an orthopyroxenite. Major phases include various pyroxenes and olivine; minor to accessory phases include various sulfides, magnetite, chromite and Ca-phosphates. Lunar meteorites comprise mare basalts with major augite and calcic plagioclase and anorthositic breccias with major calcic plagioclase. Several meteoritic phases were formed by shock metamorphism. Martensite (a2-fe,Ni) has a distorted body-centered-cubic structure and formed by a shear transformation from taenite during shock reheating and rapid cooling. The C polymorphs diamond, lonsdaleite and chaoite formed by shock from graphite. Suessite formed in the North Haig ureilite by reduction of Fe and Si (possibly from olivine) via reaction with carbonaceous matrix material. Ringwoodite, the spinel form of (Mg,Fe)2Si04, and majorite, a polymorph of (Mg,Fe)Si03 with the garnet structure, formed inside shock veins in highly shocked ordinary chondrites. Secondary minerals in meteorite finds that formed during terrestrial weathering include oxides and hy-. droxides formed directly from metallic Fe-Ni by oxidation, phosphates formed by the alteration of schreibersite, and sulfates formed by alteration of troilite.
The Thermionic Energy Converter (TEC) development program includes theoretical and experimental surface studies, diode evaluation, enhanced mode converter investigations and system studies, as well as materials fabrication and testing. The primary effort has been concentrated on increasing converter performance via improved electrodes. Diodes with oxide collectors (i.e., tungsten oxide, titanium oxide, zinc oxide and barium oxide) have provided the best performance. Emitters requiring reduced cesium pressure (such as oxygenated tungsten, lanthanum hexaboride, platinum and graphite) are being tested. Converter configurations using particle spacing are under investigation. Experiments with auxiliary electrode thermionic converters are in progress. Both silicon carbide and alloy hot shells (i.e., barriers to isolate the converter from the combustion environment) have been fabricated and tested.
The purposes of this study were to evaluate the growth of the surface damage layer in polymer matrix composites (PMC's) fabricated with graphite fabric reinforcement and to determine the effects of the cut-surface degradation on the overall thermo-oxidative (TOS) stability of these materials. Four important conclusions were made about the TOS behavior of T650-35/PNIR- 15 fabric-reinforced composites: (1) Three stages of composite weight loss were seen on the plot of weight loss versus aging time; (2) the depth of the cut-edge damage is related to the composite thickness; (3) the actual weight loss realized by a mechanical test specimen that has had all the aging-induced cut-edge damage removed during the preparation process is significantly less than the weight loss measured using specimens with a high percentage of cut edges exposed to the damaging environment; and (4) an extrapolation of a section of the weight loss curve can be used to obtain a more correct estimate of the actual weight loss after extended periods of aging at elevated temperatures.
With the recent start (October 2011) of the joint National Aeronautics and Space Administration (NASA) and Department of Energy (DOE) Advanced Exploration Systems (AES) Nuclear Cryogenic Propulsion Stage (NCPS) Program, there is renewed interest in developing advanced ceramics for use as fuel element materials in nuclear thermal propulsion (NTP) systems. Three classes of fuel element materials are being considered under the NCPS Program: (a) graphite composites - consisting of coated graphite elements containing uranium carbide (or mixed carbide), (b) cermets (ceramic/metallic composites) - consisting of refractory metal elements containing uranium oxide, and (c) advanced carbides consisting of ceramic elements fabricated from uranium carbide and one or more refractory metal carbides [1]. The current development effort aims to advance the technology originally developed and demonstrated under Project Rover (1955-1973) for the NERVA (Nuclear Engine for Rocket Vehicle Application) [2].
A reactor unit cell is disclosed including a graphite moderator structure, a heat pipe positioned in the graphite moderator structure, and a fuel assembly positioned in the graphite moderator structure. The fuel assembly comprises at least one fuel rod. Each fuel rod comprises a beryllium-oxide sleeve and nuclear fuel positioned in the beryllium-oxide sleeve.