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Solid lubricants that can be used above 300 C in air are discussed, including coatings and self-lubricating composite bearing materials. The lubricants considered are representative dichalcogenides, graphite, graphite fluoride, polyimides, soft oxides, oxidatively stable fluorides, and hard coating materials. A few general design considerations revelant to solid lubrication are interspersed.
This paper will review our current knowledge of circumstellar and interstellar dust from an astronomical point of view. About half of the interstellar dust volume consists of amorphous silicates. The remainder has to be made up of an carbonaceous component such as graphite, amorphous carbon (i.e., soot), Polycyclic Aromatic Hydrocarbon molecules (PAHs), and/or organic grain mantles (i.e., mixed polymers). The observational evidence for these components will be reviewed and their relative importance assessed. The emphasis will be on recent observations using the Infrared Space Observatory. Most of these dust components are formed in the outflows from stars in the late stages of their evolution (i.e., red giants, planetary nebulae, novae, supergiants, Wolf Rayet stars, and supernovae). Indeed, observation of such objects indicate an even richer spectrum of stardust components, including also SiC, MgS, and aluminates and crystalline silicates. These observations will be briefly discussed. The stardust budget of the galaxy will be reviewed and the relative importance of the various birth sites assessed. Finally, in recent years, isotopic composition studies have shown that some circumstellar and interstellar dust grains have been incorporated into solar system bodies such as planetary dust particles and meteorites without totally losing their identity. Among the components identified are SiC, graphite, diamonds, PAHs, aluminum oxides, as well as various trace element carbides. Studies of this kind have opened up a new window on the composition and structure of interstellar dust. These different sources of information on interstellar and circumstellar dust will be briefly contrasted.
A depressurization accident is the one of the design-basis accidents of a Very-High-Temperature Reactor (VHTR). When a depressurization accident occurs, air is expected to enter into the reactor pressure vessel from the breach and oxidize in-core graphite structures. Therefore, it is important to understand the mixing processes of different kinds of gases in the stable and unstable stratified fluid layers. In particular, it is also important to examine the influence of localized natural convection and molecular diffusion on the mixing process from a safety viewpoint. Therefore, in order to predict or analyze the air ingress phenomena during a depressurization accident, it is important to develop a method for the prevention of air ingress during an accident. We carried out experiments and numerical analysis using three-dimensional (3D) CFD code to obtain the mixing process of two-component gases and the flow characteristics of localized natural convection. This study also investigated a control method for the natural circulation of air through the injection of helium gas. The numerical model consists of a storage tank and a reverse U-shaped vertical rectangular passage. They are separated by a horizontal partition plate. One sidewall of the high-temperature side vertical passage is heated and the other sidewall is cooled. The low-temperature vertical passage is cooled by ambient air. The experimental procedures and numerical analysis process are as follows. Firstly, the storage tank is filled with heavy gas and the reverse U-shaped vertical passage is filled with a light gas. In the vertical passage of the high-temperature side, localized natural convection is generated by the temperature difference between the vertical walls. These flow characteristics were obtained from the experiments and steady-state analysis. The experiment and analysis began after the partition plate was opened. The results obtained from the experiments were quantitatively simulated using 3D numerical analysis. The two component gases were mixed via molecular diffusion and natural convection. After some time elapsed, natural circulation occurred through the reverse U-shaped vertical passage. These flow characteristics are the same as those of phenomena generated in the passage between a permanent reflector and a pressure vessel wall of the VHTR. (authors)
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DOE is converting TREAT (Transient Reactor Test) facility from its existing highly enriched uranium (HEU) core to a low-enriched uranium (LEU) core. In order to assess the magnitude of chemical interaction between fuel and cladding materials during physical contact under expected TREAT operational limits, planned transients tests, and reactivity accident scenarios, a combination of experimental testing and thermodynamic modeling was performed to predict the expected chemical interactions among fuel and cladding chemical constituents. Thermodynamic calculations were then validated with empirical data from experiments that emulate TREAT's expected upper operational limits. Pellet samples composed of LEU oxide powder dispersed in a graphite matrix had intimate contact with zirconium-based alloy cladding. The samples were subjected to long-term isothermal heating under high vacuum. Specimen characterization consisted of scanning electron microscopy, x-ray diffraction analysis, and x-ray tomography. ThermoCalc software and Ellingham's diagrams were used for thermodynamic calculations. The X-ray tomography and SEM analysis of the pellets showed a homogeneous distribution of UO{sub 2} particles within the graphite matrix with isolated larger UO{sub 2} agglomerates. The SEM analysis showed the formation of a lamellar structure between the large UO{sub 2} agglomerate and the graphite matrix. This is an indication that diffusion is taking place at a rather moderate temperature and reaction time during the pellet fabrication. Secondary phases, with high Al and Mg content, were detected inside a UO{sub 2} agglomerate using SEM in SE/EBSD mode and chemical analysis with EDS. LEU feedstock impurities, as Al and Mg, seem to promote the chemical reactivity between UO{sub 2} particles and graphite matrix. XRD analysis of a pellet sample showed the presence of UO{sub 2} and graphite, but no other crystalline phases were detected with this technique. Thermodynamic analysis through the use of Ellingham diagrams showed that within TREAT's operational to reactivity accident temperature (278-820 Celsius degrees), UO{sub 2} can be reduced to U metal by Zr due to a more favorable ΔG for the oxidation of Zr.
Graphitic matrix material encapsulates tristructural isotropic (TRISO) coated fuel particles and is a structural component for both pebble and cylindrical fuel compacts in high temperature gas reactor (HTGR) designs. In an off-normal event involving steam exposure, the matrix material is exposed to oxidants, leading to degradation of the fuel compact and subsequent exposure of the TRISO particle fuel to oxidizing species. This study presents microstructural characterization of matrix material after exposure to high temperature (1200°C), 48 kPa steam in which the evolved microstructure demonstrated nonuniform degradation. Subsequent Raman spectroscopy determined the nature of the remaining material post-exposure. Finally, the electron microscopy characterization suggests and Raman spectroscopic analysis confirms, under off-normal conditions, the carbonized phenolic resin binder is preferentially oxidized ahead of the graphite flake filler and is responsible for the nonuniform degradation and enhanced depth of attack.
High levels of mechanical performance in tension, flexure, fatigue, and creep loading situations of graphite fiber reinforced glass matrix composites are discussed. At test temperatures of up to 813 K it was found that the major limiting factor was the oxidative instability of the reinforcing graphite fibers. Particular points to note include the following: (1) a wide variety of graphite fibers were found to be comparable with the glass matrix composite fabrication process; (2) choice of fiber, to a large extent, controlled resultant composite performance; (3) composite fatigue performance was found to be excellent at both 300 K and 703 K; (4) composite creep and stress rupture at temperatures of up to 813 K was limited by the oxidative stability of the fiber; (5) exceptionally low values of composite thermal expansion coefficient were attributable to the dimensional stability of both matrix and fiber; and (6) component fabricability was demonstrated through the hot pressing of hot sections and brazing using glass and metal joining phases.
A screening study was conducted to develop improved carbon-graphite materials for use in self-acting seals at air temperatures to 1300 F (704 C). Property measurements on materials prepared during this study have shown that: (1) The mechanical properties of a carbon-graphite material were significantly improved by using a fine milled artificial graphite filler material and including intensive mixing, warm molding, and pitch impregnation in the processing; and (2) the oxidation resistance of a carbon-graphite material was improved by including fine milled boron carbide as an oxidation-inhibiting additive. These techniques were employed to develop a material that has 10 times more oxidation resistance than that of a widely used commercial grade and mechanical properties that approach those of the commercial grade.
The effects of carbon structure and surface oxygen on the carbon's performance as the anode in lithium-ion battery were studied. Two carbon materials were used for the electrochemical tests: soft carbon made from defluorination of graphite fluoride, and the carbon precursor from which the graphite fluoride was made. In this research the precursor was graphitized carbon fiber P-100. It was first fluorinated to form CF(0.68), then defluorinated slowly at 350 to 450 C in bromoform, and finally heated in 1000 C nitrogen before exposed to room temperature air, producing disordered soft carbon having basic surface oxides. This process caused very little carbon loss. The electrochemical test involved cycles of lithium intercalation and deintercalation using C/saturated LiI-50/50 (vol %) EC and DMC/Li half cell. The cycling test had four major results. (1) The presence of a basic oxide surface may prevent solvent from entering the carbon structure and therefore prolong the carbon's cycle life for lithium intercalation-deintercalation. (2) The disordered soft carbon can store lithium through two different mechanisms. One of them is lithium intercalation. which gives the disordered carbon an electrochemical behavior similar to its more ordered graphitic precursor. The other is unknown in its chemistry, but is responsible for the high-N,oltage portion (less than 0.3V) of the charge-discharge curve. (3) Under certain conditions, the disordered carbon can store more lithium than its precursor. (4) These sample and its precursor can intercalate at 200 mA/g. and deintercalate at a rate of 2000 mA/g without significant capacity loss.
Several approaches for applying high resistance coatings continuously to graphite yarn were investigated. Two of the most promising approaches involved (1) chemically vapor depositing (CVD) SiC coatings on the surface of the fiber followed by oxidation, and (2) drawing the graphite yarn through an organo-silicone solution followed by heat treatments. In both methods, coated fibers were obtained which exhibited increased electrical resistances over untreated fibers and which were not degraded. This work was conducted in a previous program. In this program, the continuous CVD SiC coating process used on HTS fiber was extended to the coating of HMS, Celion 6000, Celion 12000 and T-300 graphite fiber. Electrical resistances three order of magnitude greater than the uncoated fiber were measured with no significant degradation of the fiber strength. Graphite fibers coated with CVD Si3N4 and BN had resistances greater than 10(exp 6) ohm/cm. Lower pyrolysis temperatures were used in preparing the silica-like coatings also resulting in resistances as high as three orders of magnitude higher than the uncoated fiber. The epoxy matrix composites prepared using these coated fibers had low shear strengths indicating that the coatings were weak.
A number of thermo-oxidative stability studies addressing the effects of fiber reinforcement on composite thermal stability and influence of geometry on the results of aging studies were performed at NASA-Lewis. The information presented herein, a compilation of some results from these studies, shows the influence of the reinforcement fibers on the oxidative degradation of various PMR-15 composites. Reinforcement of graphite and ceramics were studied and three composite oxidation mechanisms were observed. One was a dominant attack of the reinforcement fiber, the second was the aggressive oxidation of the matrix material, and the third was interfacial degradation.
We explore the incorporation of the cosmically abundant species O, C, N, Mg, Si, Fe, and S into interstellar dust. Column densities based on Goddard High Resolution Spectrograph 3.5 km/s resolution measurements from the literature for eight individual absorbing regions toward five lines of sight are used. Corrections are applied as needed in order to account for recent improvements in oscillator strengths. In order to acquire the most accurate column densities, and check on the accuracy of the oscillator strengths, we compare column densities based on the very strong Lorentzian damped lines of C II, O I, N I, and Mg II with results for the weak lines of these species, and confirm the previously determined f-values for O I lambda 1335, C II lambda 2325, and N I lambda lambda 1159, 1160. New empirical f-values of 1.25 x 10(exp -3) and 6.25 x 10(exp -4), respectively, are derived for the Mg II weak doublet at 1239 and 1240 A. Assuming a cosmic reference abundance based on solar and B star values, we derive depletions and dust-phase abundances which suggest that more than 70% of the available Mg and Fe is incorporated into dust-grain cores, whereas only 35% of the silicon is. This implies that oxides are important constituents of the grain core population. Mg and Fe atoms are mantled onto grain cores in a ratio of 1.8 to 1, whereas approximately 4.0 Si atoms are in the mantle per Fe atom. Since Si is not expected to accrete onto silicate or graphite grains, other grain cores, perhaps oxides and/or metallic Fe, may provide mantling sites for this species. The abundances of Fe and Mg in mantles would imply that graphite grains must have a substantial coating unless oxides provide significant mantling sites for these species. The abundance of O and N in the dust phase as implied by the solar reference abundance values are difficult to reconcile with the fact that these elements are not expected to participate in mantle formation, and the 3.1 micrometer H2O ice feature is not seen in absorption toward stars similar to those studied. The B star reference abundances for O and N, however, imply that no mantling of these species has occurred. The dust-phase abundance for C implied by solar reference abundances agrees with predictions for the number of graphite grains needed to produce the 2175 A bump. B star reference abundances, however, suggest that the abundance of C in the dust phase is not always sufficient to produce the bump.
Highlights: • Novel mpg-C{sub 3}N{sub 4}/rod-like CuO nanocomposites were synthesized via a facile precipitation method for the first time. • The BET surface area of as-synthesized mpg-C{sub 3}N{sub 4}/CuO is 111.33 m{sup 2} g{sup −1}, which is beneficial for catalyzing the thermal decomposition process of ammonium perchlorate (AP). • The synergistic effect between mpg-C{sub 3}N{sub 4} and CuO was the origin of the high catalytic activity. • The mpg-C{sub 3}N{sub 4}/CuO nanocomposites were applied in catalyzing the thermal decomposition of AP and the proposed catalytic mechanism was also proposed. - Abstract: Aiming at enhancing the catalytic activity of mpg-C{sub 3}N{sub 4} on thermal decomposition of ammonium perchlorate, mpg-C{sub 3}N{sub 4} was successfully modified by CuO nanorods, via a facile precipitation method. The structure, morphology and composition of mpg-C{sub 3}N{sub 4} and mpg-C{sub 3}N{sub 4}/CuO nanocomposites were characterized by nitrogen adsorption-desorption measurements, transmission electron microscopy, scanning electron microscope, X-ray power diffraction, fourier transform infrared spectroscopy, as well as X-ray photoelectron spectroscopy. The results demonstrated that CuO nanorods (length of 200–300 nm, diameter of 10–15 nm) were uniformly dispersed throughout mpg-C{sub 3}N{sub 4}, efficiently avoiding the agglomeration. Finally, it was demonstrated that the high weight-loss decomposition temperature of AP was decreased up to 118.5 °C in the presence of 2 wt% mpg-C{sub 3}N{sub 4}/CuO nanocomposites, which was higher than that of pure mpg-C{sub 3}N{sub 4} and CuO, respectively, demonstrating the catalytic performances of the nanocomposites was enhanced via the synergistic catalysis between mpg-C{sub 3}N{sub 4} and CuO.
This work investigates 14 C release behaviour from UK Magnox reactor sourced irradiated graphite under relatively low temperature oxidation conditions: a 1% oxygen in argon atmosphere at temperatures ranging from 600°C to 700°C, and durations from 4 to 120 hours. A method is used for construction of a detailed 14 C release profile with mass loss. The 14 C release profile is predictable between samples, and an empirical release profile is derived to predict releases to higher mass losses than in this work. An accelerated 14 C release rate at small mass losses is observed, indicative of a 14 C-enriched surface region with a depleting concentration gradient into the material, and the source terms and complexities associated with predicting where the 14 C arose from are discussed. Selective decontamination of a fraction of the 14 C is possible, with the limitation of a reducing efficiency with mass loss and time. This work demonstrates a method for determining the distribution of 14 C between near-surface regions and the bulk material in differing sources of irradiated graphite, and provides data in support of making an informed assessment for the adoption of low temperature thermal treatment and isotopic reduction of irradiated graphite wastes.
The Advanced Gas Reactor (AGR) program has a need to perform high-temperature oxidation testing of tristructural isotropic (TRISO)-coated particle fuel and reactor core materials to evaluate their performance under conditions relevant to air- and moisture-ingress events in high-temperature gas-cooled reactors (HTGRs). The objectives of these tests are to assess the impact of oxidizing environments on fission product release from exposed fuel kernels, compact matrix, and nuclear grade graphite, and to determine the impact of oxidizing environments on TRISO coating integrity. The program is currently developing a capability for testing irradiated fuel, matrix, and graphite specimens inside a hot cell. The Air/Moisture Ingress Experiment (AMIX) system will be capable of temperatures up to 1650°C in atmospheres containing oxygen or moisture with varying concentrations. The system will be capable of collecting fission gases as well as condensable fission products, in order to quantify total released inventory from the heated specimens. A basis for establishing experimental test matrices, and the test matrices themselves, are presented in this document. This includes considerations on specific objectives for the tests, types of oxidizing environments that should be tested, and the expected availability of irradiated specimens from the various AGR program irradiation experiments. This document only briefly discusses post-test analysis of the heated specimens, and it is recognized that in many cases the post-test analysis may be extensive. It is expected that this will be a “living” document, subject to revision as data are collected and scoping calculations are performed.
The results of a study on the production of cubic titanium carbide in direct-current arc discharge plasma initiated in open air are presented. A feature of the method is its implementation without the use of gas or liquid protective media preventing the oxidation of products and initial reagents with air oxygen. According to the X-ray diffraction data, graphite gC, hexagonal titanium α-Ti, and cubic titanium carbide TiC are identified in the composition of the powder product. The TiC particles are represented by objects with a regular characteristic cut and sizes from units to tens of micrometers.
Mixed bandgap and bandgap tunability in semiconductors is critical in expanding their use. Composition altera-tions through single-crystal epitaxial growth and formation of multi-layer tandem structures are often employed to achieve mixed bandgaps albeit with limited tunability. In this study, self-assembled one-dimensional coordination polymers provide a fac-ile synthon and template for graphitic C-doped mesoporous oxides, gC-β-Ga 2 O 3 or gC-In 2 O 3 via controlled oxidative ligand ablation. These materials have mixed bandgaps, and colors, depending on amount of gC present. The carbon-oxide interface leads to induced gap states, hence, a stoichiometrically tunable band structure. Structurally, a multi-scale porous network percolating throughout the material is realized. The nature of heat-treatment and top-down process allows for facile tunabil-ity and formation of mixed bandgap metal oxides through controlled carbon deposition. As a proof of concept, gC-β-Ga 2 O 3 was utilized as a photocatalyst for CO 2 reduction, which demonstrated excellent selectivity and conversion rates into CH 4 and CO.
A graphite component in a nuclear reactor core is subjected to variety of stresses and can experience degradation during normal and off-normal operation. Understanding how a graphite component will behave in service is essential to ensuring core structural stability and safe reactor operation. This report summarizes a graphite modeling tool currently under development at Idaho National Laboratory. The model incorporates several of the anticipated stresses during service and includes the effects of oxidation and irradiation prior to turnaround. This tool is intended to be used to help assess the design of graphite components by utilizing design code rules found in Section III, Division 5 of the American Society of Mechanical Engineering Boiler and Pressure Vessel Code. Specifically, the tool uses the methodologies found within the Full and Simplified assessments from Article HHA-3000 to verify that a graphite component has an acceptably low probability of failure.