Oxidation Resistant Graphite
Oxidation Resistant Graphite, current and prior research.
SEARCH · Search NASA
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.
Oxidation Resistant Graphite, current and prior research.
Status of Graphite Oxidation Research Chronic Oxidation Oxidation of Irradiated Graphite Oxidation Resistant Graphite Material Property Changes with Oxidation
Introduction of ART Graphite R&D to include oxidation activities, oxidation resistant graphite, model development, ASME component failure, ASME code development (design rules), ceramic composites, AGC update, molten salt intrusion, split-disk studies, wear testing, and concluding remarks.
Slides for Oxidation Activities, oxidation rate, penetration/lathing, and strength after oxidation work. Also includes recent and current oxidation studies, background for rate behavior, strength behavior, density profile, and penetration measurements, oxidation resistant graphite coating development, and irradiated and unirradiated graphite oxidation rate behavior.
Carbon/graphite fibers were chemically oxidized in the liquid phase to fibers of graphite oxide. Resistivity increases as high as 10,000 times were obtained, the oxidized fiber decomposed on exposure to atmosphere. A factor of 1,000 remained as a stable increment. The largest change observed was 1,000,000 times. Best results were obtained on the most highly graphitized fibers. Electrochemical oxidation yielded a lower increase--about 10 times, but provided a controllable method of synthesis and insight to the mechanism of reaction. Tensile tests indicated that the strength of the fiber on oxidation was decreased by no more than 25 percent.
A variety of silicon-carbide treated carbon and graphite products were prepared, and oxidation and strength properties determined. Carbon and graphite materials used in the preliminary study include fiber, tape, felt, foam, bulk, and laminar configurations. The silicon-carbide treatment used in preparing the oxidation resistant specimens employs either vacuum or ultrasonic impregnation of various silicone-silicon mixtures into the matrix material. The impregnation phase is followed by controlled thermal reaction at which time the silicon carbide is synthesized and takes the form of an integral protective boundary layer. Thickness of the layer ranges from a fraction of a mil to 10 mils, depending on the matrix material and processing parameters. Oxidation resistance of all the silicon-carbide-treated specimens investigated was found to be significantly improved. Mechanical strengths of the laminar composites were also found to be somewhat improved. At room temperature the specific strength of the silicon-carbide treated fibers and tapes was degraded to some extent; however, their relative strengths were significantly increased at elevated temperatures in oxidizing atmosphere.
A number of leading-edge specimens of ATJ graphite and 0.5-percent titanium-molybdenum alloy were tested in a 6-inch subsonic low-pressure arc-powered tunnel and a 1,500-kw subsonic arc jet to determine the effectiveness of several refractory coatings in preventing the oxidation of these materials. The results indicate that the siliconized coating for the ATJ graphite and the W-2 and Durak MG coatings for the titanium-molybdenum alloy provide adequate protection at temperatures up to 3,000 F for the durations of the tests in these facilities, approximately 70 seconds in the arc tunnel and approximately 10 minutes in the arc jet. Weight losses (less than one-half of 1 percent) experienced by a few of the coated specimens indicate that tests of longer duration in these environments may prove deleterious and that the stability of these coatings may be depreciated under the low-pressure environmental conditions encountered during reentry.
Studies were conducted to determine the friction and wear properties of experimental carbon-graphites. Hemispherically tipped carbon-graphite rider specimens were tested in sliding contact with rotating Inconel X-750 disks in air. A surface speed of 1.33 m/sec, a load of 500 g, and a specimen temperature of 650 C were used. Results indicate: (1) hardness is not a major factor in determining friction and wear under the conditions of these studies. (2) Friction and wear as low as or lower than those observed for a good commercial seal material were attained with some of the experimental materials studied. (3) The inclusion of boron carbide (as an oxidation inhibitor) has a strong influence on wear rate. (4) Phosphate treatment reduces the friction coefficient when boron carbide is not present in the base material.
High temperature oxidation resistant coatings for superalloys, refractory metals, and graphite
Nanoparticles have been developed over the past 10 years and have found several applications. This work presents the use of carbon nano-onions as a potential oil additive for aerospace applications. Researchers at the NASA Glenn Research Center tested lubricant lifetimes in ambient air and ultrahigh vacuum and characterized the breakdown products of the friction and wear. These carbon nanoparticles can provide adequate lubrication very similar to that of graphitic material when run in air. Soot represents one of the very first nanostructured materials, although it has rarely been considered as such. Changes in the carbon nanostructure, resulting in increased graphitic layer plane length, correlate with reactivity loss. Upon heating spherically shaped nanometer-sized carbon black in the absence of oxidant, graphene sheets form, and the initial soot particle templates the growth of a graphitic particle into what is best described as a sphere with many flat sides having a hollow interior. Because there are no edge sites, these polygonal graphitic particles, or nano-onions, are relatively resistant to oxidation. Graphite is used as a solid lubricant because of its stability at moderately high temperatures. However, the temperature at which graphite oxidizes rapidly is strongly influenced by surface area. With the size of particles typically employed in lubrication, a great amount of thermal stability is lost because of size reduction either during preparation or during lubrication of contacting parts. Therefore, we have undertaken a study of the lubricating ability of graphitic nano-onions (ref. 1).
Oxidation experiments were conducted with several experimental mechanical carbons at 650 C in air flowing at 28 cu cm/sec (STP). Experiments indicate that boron carbide addition and zinc phosphate treatment definitely improved oxidation resistance. Impregnation with coal tar pitch before final graphitization had some beneficial effect on oxidation resistance and it markedly improved flexure strength and hardness. Graphitization temperature alone did not affect oxidation resistance, but with enough added boron carbide the oxidation resistance was increased although the hardness greatly decreased.
This work presents the oxidation behavior of matrix graphite in air. Matrix graphite, graphite powder/flakes bonded by a small amount of non-graphitic carbon, surrounds coated fuel particles in order to form cylindrical fuel compacts (in prismatic core designs) or spheres (in pebble-bed reactor designs). This work focuses on oxidation tests conducted on two matrix graphite materials, one provided by Kairos Power and the other A3 matrix graphite. Some of the tests followed American Society for Testing and Materials (ASTM) oxidation testing standards using a vertical furnace system and others were performed in a thermogravimetric analyzer (TGA). It was determined that, at temperatures of 450 °C–700 °C, the oxidation rate of the Kairos matrix graphite follows the Arrhenius equation. In comparison with A3 matrix graphite, the Kairos matrix graphite shows better oxidation resistance at high temperatures (≥550 °C), but also a higher oxidation rate at low temperatures. Both the A3 matrix graphite and the Kairos matrix graphite materials may experience preferential oxidation of the partially graphitized binder. An oxygen penetration gradient was also observed when using the three characterization methods (i.e., optical microscope, x-ray tomography [XCT], and density profile by the lathe) enlisted in this research. In conclusion, the oxygen penetration depth increases with decreasing isothermal oxidation temperature, while the center of the oxidized samples (10% weight loss) remains almost untouched even at 500 °C.
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.
Graphite is proposed for use in High-temperature Gas-cooled Reactors (HTGRs) as the fuel matrix, neutron moderator/reflector, and core structural material. One important property of nuclear grade graphite is their resistance to oxidation in high-temperature environment. Extensive investigation has been performed in the literature for graphite oxidation by air. However, available experimental data are still limited for graphite oxidation by steam under conditions comparable to a postulated steam ingress accident in HTGRs. In this study, the oxidation rate of graphite IG-110 by steam was measured at temperatures from 850 to 1100 °C with the steam partial pressure varying from 0.5 to 20.0 kPa and the hydrogen partial pressure varying from 0 to 2.0 kPa. Further analysis confirms the oxidation process in this present study is dominated by the chemical kinetics, which lends credit to the data for being used to develop numerical models. It was observed that the increase of the kinetic oxidation rate with the steam partial pressure tends to become less apparent if the steam partial pressure keeps increasing. In addition, it was found that the partitioning of hydrogen inhibits the graphite-steam reaction process even with the steam partial pressure up to 20.0 kPa. However, this inhibiting effect starts to become saturated when the hydrogen partial pressure exceeds 1.0 kPa. The oxidation rates were fitted to the conventional Langmuir-Hinshelwood (LH) and Boltzmann-enhanced Langmuir-Hinshelwood (BLH) models by a multivariable optimization algorithm. The BLH model exhibits a better accuracy than the LH model within the specified experimental conditions. The predicted oxidation rate using the BLH model shows a mean relative difference of about 24% with the maximum difference of about 55% when compared with our experimental data.
A broad group of fibers and matrices were combined to create a wide range of composite properties. Primary material fabrication procedures were developed which readily permit the fabrication of flat plate and shaped composites. Composite mechanical properties were measured under a wide range of test conditions. Tensile, flexure mechanical fatigue, thermal fatigue, fracture toughness, and fatigue crack growth resistance were evaluated. Selected fiber-matrix combinations were shown to maintain their strength at up to 1300 K when tested in an inert atmosphere. Composite high temperature mechanical properties were shown to be limited primarily by the oxidation resistance of the graphite fibers. Composite thermal dimensional stability was measured and found to be excellent.
Recent graphite fiber developments have resulted in high strength, intermediate modulus graphite fibers having improved thermo-oxidative resistance. These improved fibers, obtained from various commercial suppliers, were used to fabricate PMR-15 and PMR-11 polyimide composites. Studies were performed to investigate the effects of the improved high strength graphite fibers on composite properties after exposure in air at 600 F. The use of the more oxidatively resistant fibers did not result in improved performance at 600 F. Two of the improved fibers were found to have an adverse effect on the long-term performance of PMR composites. The influence of various factors such as fiber physical properties, surface morphology and chemical composition are also discussed.
A new tip for scanning tunneling microscopy and a tip repair procedure that allows one to reproducibly obtain atomic images of highly oriented pyrolytic graphite with previously inoperable tips are reported. The tips are shown to be relatively oxide-free and highly resistant to oxidation. The tips are fabricated with graphite by two distinct methods.
Oxidation experiments were conducted with some experimental and commercial mechanical carbons at 650 C in dry air flowing at 28 cc/sec (STP). In general, purification of these carbon-graphites with chlorine at 2800 C improved oxidation resistance. Additional improvements in oxidation resistance were obtained from purification followed by an antioxidant (zinc phosphate) treatment. For the commercial materials, purification alone gave greater oxidation resistance than the antioxidant treatment alone. The reverse, however, was the case for the experimental materials.