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At least 199 records · Page 11

Fiber release characteristics of graphite hybrid composites

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.

Henshaw, J.↗

Upcycling Polyethylene Waste to Advanced Carbon Materials for Energy Storage Applications

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.

Gao, Yuan↗

Fretting of Secondary-Seal-Ring Candidate Materials in Air at Temperatures to 816 C

Superalloys containing chromium showed decreasing fretting damage with increasing temperature of 816 C. This trend was related to the ability of the alloys to generate self-protecting oxide films. The damage at 816 C was one-third to one-tenth of that at 23 C. Osmium, chromium, and chromium carbide platings were fretted at 23 and 450 C. Osmium was extremely protective at 23 C but oxidized excessively at 450 C. Chromium and chromium carbide gave about the same protection at 450 C as the oxide films that formed on the superalloys. High graphite and low graphite carbons were fretted at 23 and 327 C. High graphite carbon was superior at 327 C, but low graphite carbon was the best material examined at 23 C.

Bill, R. C.↗

Protective coatings for high-temperature polymer matrix composites

Plasma-enhanced chemical vapor deposition was used to deposit silicon nitride on graphite-fiber-reinforced polyimide composites to protect against oxidation at elevated temperatures. The adhesion and integrity of the coating were evaluated by isothermal aging (371 C for 500 hr) and thermal cycling. The amorphous silicon nitride (a-SiN:H) coating could withstand stresses ranging from approximately 0.18 GPa (tensile) to -1.6 GPa (compressive) and provided a 30 to 80 percent reduction in oxidation-induced weight loss. The major factor influencing the effectiveness of a-SiN:H as a barrier coating against oxidation is the surface finish of the polymer composite.

Harding, David R.↗

Complete Initial Studies in Microstructural Studies of Nuclear Graphite

Nuclear graphite is a critical material for the performance and safety of high-temperature reactors, making its study essential for the successful deployment of next-generation reactors in the United States. During the past year, Oak Ridge National Laboratory (ORNL) has contributed extensively to advancing the understanding of nuclear graphite’s properties, behavior, and applications; particular focus has been given to irradiation effects, oxidation mechanisms, thermal and mechanical performance, and long-term stability under reactor conditions. This report provides an update on the ongoing publications being prepared at ORNL. These studies are collectively intended to build a comprehensive knowledge base on nuclear graphite. The studies focus on key aspects such as microstructural characterization, oxidation behavior, advanced analytical techniques, molten salt infiltration, technique development, and billet-to-billet variability. By summarizing the progress of these publications, this report outlines ORNL’s contributions to the field, identifies knowledge gaps, and proposes future research directions. The findings presented in these studies will help enhance the understanding of nuclear graphite’s behavior, support the qualification of nuclear graphite materials, further the development of new techniques and guidelines for using microscopy techniques, and improve reactor safety and performance.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Cycling Performance and Structure Evolution of Co-Free Lithium- and Manganese-Rich Layered Oxides in Lithium-Ion Batteries

Lithium- and manganese-rich (LMR) layered oxides are high-capacity cathode materials that are being considered for electric vehicle (EV) lithium-ion batteries (LIBs). Here, we investigate the electrochemical cycling behavior of cells containing a cobalt-free LMR oxide, 0.3Li 2 MnO 3 ·0.7LiMn 0.5 Ni 0.5 O 2 , paired with either Li or graphite anodes. Two- and three-electrode cells are cycled under varying conditions to examine the effects of oxide activation, upper cutoff voltage, separator type, and electrolyte composition. Post-cycling characterization of harvested electrodes, with electrochemical, X-ray absorption spectroscopy, and solid-state 6 Li nuclear magnetic resonance spectroscopy techniques, are used to correlate cell performance changes with redox state evolution in the oxide and Li inventory shifts in the cell. Our results show that capacity fade and impedance rise primarily originate at the graphite anode and LMR cathode, respectively. Notably, while Ni undergoes reversible redox, Mn shows no evidence of bulk redox activity even in highly-aged electrodes: only relithiated LMR electrodes show some reduction of Mn. Graphite electrodes degrade due to particle isolation and SEI growth, exacerbated by Mn dissolution and deposition on graphite anodes. These findings highlight the coupled structural and electrochemical degradation mechanisms in LMR/graphite cells and underscore lithium inventory retention and electrode interfacial stability as critical factors for enhancing long-term performance.

Badami, Pavan P. [Argonne National Laboratory (ANL↗

Leveling coatings for reducing the atomic oxygen defect density in protected graphite fiber epoxy composites

Pinholes or other defect sites in a protective oxide coating provide pathways for atomic oxygen in low Earth orbit to reach underlying material. One concept for enhancing the lifetime of materials in low Earth orbits is to apply a leveling coating to the material prior to applying any reflective and protective coatings. Using a surface tension leveling coating concept, a low viscosity epoxy was applied to the surface of several composite coupons. A protective layer of 1000 A of SiO2 was deposited on top of the leveling coating, and the coupons were exposed to an atomic oxygen environment in a plasma asher. Pinhole populations per unit area were estimated by counting the number of undercut sites observed by scanning electron microscopy. Defect density values of 180,000 defects/sq cm were reduced to about 1000 defects/sq cm as a result of the applied leveling coating. These improvements occur at a mass penalty of about 2.5 mg/sq cm.

Jaworske, D. A.↗

Leveling coatings for reducing the atomic oxygen defect density in protected graphite fiber epoxy composites

Pinholes or other defect sites in a protective oxide coating provide pathways for atomic oxygen in low Earth orbit to reach underlying material. One concept of enhancing the lifetime of materials in low Earth orbit is to apply a leveling coating to the material prior to applying any reflective and protective coatings. Using a surface tension leveling coating concept, a low viscosity epoxy was applied to the surface of several composite coupons. A protective layer of 1000 A of SiO2 was deposited on top of the leveling coating, and the coupons were exposed to an atomic oxygen environment in a plasma asher. Pinhole populations per unit area were estimated by counting the number of undercut sites observed by scanning electron microscopy. Defect density values of 180,000 defects/sq cm were reduced to about 1000 defects/sq cm as a result of the applied leveling coating. These improvements occur at a mass penalty of about 2.5 mg/sq cm.

Jaworske, D. A.↗

Preparation of a Bimetal Using Mechanical Alloying for Environmental or Industrial Use

Following the 1976 Toxic Substances Control Act ban on their manufacture, PCBs remain an environmental threat. PCBs are known to bio-accumulate and concentrate in fatty tissues. Further complications arise from the potential for contamination of commercial mixtures with other more toxic chlorinated compounds such as polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Until recently, only one option was available for the treatment of PCB-contaminated materials: incineration. This may prove to be more detrimental to the environment than the PCBs themselves due to the potential for formation of PCDDs. Metals have been used for the past ten years for the remediation of halogenated solvents and other contaminants in the environment; however, zero-valent metals alone do not possess the activity required to dehalogenate PCBs. Palladium has been shown to act as an excellent catalyst for the dechlorination of PCBs with active metals. This invention is a method for the production of a palladium/magnesium bimetal capable of dechlorinating PCBs using mechanical milling/mechanical alloying. Other base metals and catalysts may also be alloyed together (e.g., nickel or zinc) to create a similarly functioning catalyst system. Several bimetal catalyst systems currently can be used for processes such as hydrogen peroxide synthesis, oxidation of ethane, selective oxidation, hydrogenation, and production of syngas for further conversion to clean fuels. The processes for making these bimetal catalysts often involve vapor deposition. This technology provides an alternative to vapor deposition that may provide equally active catalysts. A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts. Preferably, the hydrogenation catalyst is a bimetallic particle formed from a zero-valent iron or zero-valent magnesium particle coated with palladium that is impregnated onto a high-surface-area graphite support. The zero-valent metal particles should be microscale or nanoscale zero-valent magnesium or zero-valent iron particles. Other zero-valent metal particles and combinations may be used. Additionally, the base material may be selected from a variety of minerals including, but not limited to, alumina and zeolites. The catalytic metal is preferably selected from the group consisting of noble metals and transition metals, preferably palladium. The mechanical milling process includes milling the base material with a catalytic metal impregnated into a high-surface-area support to form the hydrogenation catalyst. In a preferred mechanical milling process, a zero-valent metal particle is provided as the base material, preferably having a particle size of less than about 10 microns, preferably 0.1 to 10 microns or smaller, prior to milling. The catalytic metal is supported on a conductive carbon support structure prior to milling. For example, palladium may be impregnated on a graphite support. Other support structures such as semiconductive metal oxides may also be used.

Quinn, Jacqueline↗

Improved PMR Polyimides For Heat-Stable Laminates

Second-generation PMR-type polyimides (PMR-II polyimides) of enhanced thermo-oxidative stability prepared by substitution of para-aminostyrene (PAS) end caps for nadic-ester (NE) end caps used in prior PMR-II polyimides. Laminates unidirectionally reinforced with graphite fibers and made with PAS-capped resins exhibited thermo-oxidative stabilities significantly greater than those of similar laminates made with NE-capped PMR-II resins. One new laminate exhibited high retention of weight and strength after 1,000 h of exposure to air at 371 degrees C.

Vannucci, R. D.↗

Proceedings of the 7th Semiannual Meeting of the Nozzle Initiative Industry Advisory Committee on Standardization of Carbon-Phenolic Test Methods and Specifications

The application of carbon fibers and fabrics (CF) for producing rocket nozzles is discussed. These materials which are essential for fabricating the carbon composites used in aerospace systems gasify when exposed to high temperatures and the mechanical properties of the composites degrade. The oxidation kinetics under isothermal (IC) and non-isothermal (NIC) conditions are examined and a comparison is made between the characteristics of IC and NIC oxidation. Several CF, chars, and carbon blacks were examined, including a microporous char, a graphitized rayon fabric, and several carbonized rayon fabrics. A summary is given of the advantages and drawbacks of isothermal and non-isothermal oxidation of carbons. The proceedings are assembled in the form of a roundtable discussion.

Hall, William B.↗

Thermal stability relationships between PMR-15 resin and its composites

A study was conducted to investigate the relationship between the thermo-oxidative stability of PMR-15 matrix resin and the stability of graphite-fiber-reinforced composites that contain this resin as the matrix material. Three areas were investigated. The first was the effect of fiber/matrix interfacial bond strength on the isothermal aging weight loss of composites. By using type-A graphite fibers produced by Hercules, it was possible to study composites reinforced with fibers that were processed to receive different surface treatments. One of the fibers was untreated, a second fiber was treated by oxidation to enhance fiber/matrix bonding, and the third type of fiber was coated with an epoxy sizing. These treatments produced three significantly different interfacial bond strengths. The epoxy sizing on the third fiber was quickly oxidized from the bare fiber surfaces at 288, 316, and 343 C. The weight loss due to the removal of the sizing was constant at 1.5 percent. This initial weight loss was not observed in thermo-oxidative stability studies of composites. The PMR-15 matrix satisfactorily protected the reinforcemnt at all three temperatures.

Bowles, Kenneth J.↗

A study of graphite ablation in combined convective and radiative heating.

Comparison of graphite ablation experiment results in the diffusion-controlled oxidation and sublimation regimes with results of an equilibrium chemistry, film coefficient ablation analysis. Mass transfer and energy transfer effects are considered. Tests were conducted in an arcjet facility at convective heating rates of 600 to 800 W/sq cm, radiative heating rates up to 2900 W/sq cm, with test specimen surface pressures of 0.06, 0.1, and 0.3 atm in an air stream. The experimental and analytical mass loss and surface temperature results agreed well when the carbon vapor thermodynamic properties from the JANAF tables are used in the analysis.

Wakefield, R. M.↗

Investigation of nonlinear mechanical behavior of two superfine-grained graphites with DIC assisted disc splitting test

Using standardized uniaxial tensile test specimens is not practical due to the limited volumes in irradiation capsules, molten salt degradation facilities, or oxidation apparatus. The ASTM International Standard Test Method for Tensile Strength Estimate by Disc Compression of Manufactured Graphite (ASTM D8289) was developed to provide a convenient way for estimating tensile strength. Unlike the traditional uniaxial tensile test in ASTM C749 (International Standard Test Method for Tensile Stress–Strain of Carbon and Graphite), which uses dog-bone shaped specimens larger than 12.95 mm × 120.65 mm, the ASTM D8289 standard uses smaller discs with diameters of 6–12.7 mm. A digital image correlation (DIC) system, which uses a full-field noncontact surface displacement measurement technique, was applied along with the ASTM D8289 disc splitting test on IG-110 samples and compared with previous measurements from Mersen 2114 samples. Results confirmed that the DIC technique can measure the surface displacement/strain on these small (Ø6 mm × 3 mm) graphite specimens with good repeatability. However, Mersen 2114 and IG-110 samples exhibited strain discrepancies when DIC measurements were compared with analytical and finite element simulation values. The loading history and strain results also indicated different mechanical behaviors between Mersen 2114 and IG-110, particularly the nonlinear behavior of the IG-110 samples. Good agreement was observed by comparing the splitting tensile strengths of two superfine-grained grades with results from other work. The specimen size effect is discussed when comparing the splitting tensile strength with corresponding uniaxial tensile strength of these two graphite grades.

Lin, Lianshan [ORNL] (ORCID:0000000203399219)↗

Thermo-Oxidative Stability of Graphite/PMR-15 Composites: Effect of Fiber Surface Modification on Composite Shear Properties

Experiments were conducted to establish a correlation between the weight loss of a polyimide (PMR- 15) matrix and graphite fibers and the in-plane shear properties of their unidirectional composites subjected to different isothermal aging times up to 1000 hr at 316 C. The role of fiber surface treatment on the composite degradation during the thermo-oxidative aging was investigated by using A4 graphite fibers with three surface modifications: untreated (AU-4), surface treated (AS-4), and surface treated and sized with an epoxy-compatible sizing (AS-4G). The weight loss of the matrix fibers, and composites was determined during the aging. The effect of thermal aging was seen in all the fiber samples in terms of weight loss and reduction in fiber diameter. Calculated values of weight loss fluxes for different surfaces of rectangular unidirectional composite plates showed that the largest weight loss occurred at those cut surfaces where fibers were perpendicular to the surface. Consequently, the largest amount of damage was also noted on these cut surfaces. Optical observation of the neat matrix and composite plates subjected to different aging times revealed that the degradation (such as matrix microcracking and void growth) occurred in a thin surface layer near the specimen edges. The in-plane shear modulus of the composites was unaffected by the fiber surface treatment and the thermal aging. The shear strength of the composites with the untreated fibers was the lowest and it decreased with aging. A fracture surface examination of the composites with untreated fibers suggested that the weak interface allowed the oxidation reaction to proceed along the interface and thus expose the inner material to further oxidation. The results indicated that the fiber-matrix interface affected the composite degradation process during its thermal aging and that the the weak interface accelerated the composite degradation.

Madhukar, Madhu S.↗

Effect of fiber reinforcements on thermo-oxidative stability and mechanical properties of polymer matrix composites

A number of studies have investigated the thermo-oxidative behavior of polymer matrix composites. Two significant observations have been made from these research efforts: (1) fiber reinforcement has a significant effect on composite thermal stability; and (2) geometric effects must be considered when evaluating thermal aging data. A compilation of some results from these studies is presented, and this information shows the influence of the reinforcement fibers on the oxidative degradation of various polymer matrix composites. The polyimide PMR-15 was the matrix material that was used in these studies. The control composite material was reinforced with Celion 6000 graphite fiber. T-40R graphite fibers, along with some very stable ceramic fibers were selected as reinforcing fibers because of their high thermal stability. The ceramic fibers were Nicalon (silicon carbide) and Nextel 312 (alumina-silica-boron oxide). The mechanical properties of the two graphite fiber composites were significantly different, probably owing to variations in interfacial bonding between the fibers and the polyimide matrix. The Celion 6000/PMR-15 bond is very tight but the T-40/PMR-15 bond is less tight. Three oxidation mechanisms were observed: (1) the preferential oxidation of the Celion 6000 fiber ends at cut surfaces, leaving a surface of matrix material with holes where the fiber ends were originally situated; (2) preferential oxidation of the composite matrix; and (3) interfacial degradation by oxidation. The latter two mechanisms were also observed on fiber end cut surfaces. The fiber and interface attacks appeared to initiate interfiber cracking along these surfaces.

Bowles, Kenneth J.↗

New Potential Sources for Black Onaping Carbon

One intriguing and important issue of the Sudbury Structure concerns the source of the relatively large amount of C in the Onaping Formation Black member. This dilemma was recently addressed, and the conclusion was reached that an impactor could not have delivered all of the requisite C. Becker et al. have suggested that much of the C came from the impactor and reported the presence of interstellar He "caged" inside some fullerenes that may have survived the impact. So, conceivably, the C inventory in the Sudbury Structure comes from both target and impactor materials, although the known target rocks have little C. We discuss here the possibility of two terrestrial sources for at least some of the C: (1) impact evaporation/dissociation of C from carbonate target rocks and (2) the presence of heretofore-unrecognized C-rich (up to 26 wt%) siliceous "shale," fragments, which are found in the upper, reworked Black member. Experimental: Hypervelocity impact of a 0.635-diameter Al projectile into dolomite at 5.03 km/s (performed at the Ames Research Center vertical gun range) produced a thin, black layer (= 0.05 mm thick) that partially lined the crater and coated impactor remnants. Scanning electronic microscope (SEM) imagery shows this layer to be spongelike on a submicron scale and Auger spectroscopic analyses yield: 33% C, 22% Mg, 19% 0, and 9% Al (from the projectile). Elemental mapping shows that all of the available 0 is combined with Ca and Mg, Al is not oxidized, and C is in elemental form. Dissociation efficiency of C from CO2 is estimated to be <10% of crater volume. Raman spectroscopy indicates that the C is highly disorganized graphite. Another impact experiment [4] also produced highly disordered graphite from a limestone target (reducing collector), in addition to small amounts of diamond/lonsdaleite/chaoite (oxidizing collector). These experiments confirm the reduction of C from carbonates in impact vapor plumes. Observational: SEM observations and microprobe analyses of small, black shalelike inclusions in the upper Black Onaping indicate high C contents (7-26 wt% avg. = 16%). They contain mostly quartz and carbonaceous matter with small amounts of altered K-feldspar, clays, Fe oxide, and a sulfide. No evidence of shock is seen in quartz, and overall characteristics indicate a natural, lightly metamorphosed carbonaceous shale or mudstone that probably existed as a preimpact rock in the target region and distal fragments washed in during early crater filling. Fragments range in size from tens of microns to cm and increase in abundance in the upper Black toward the Onwatin contact, although their distribution is highly irregular. This increase corresponds to an increase in "organic" C with increasingly negative delta-13 C values and S, together with a decrease in fullerene abundance. In addition, we have found soot in acid-demineralized residues of the Onwatin but not in the Onaping samples. These data could be consistent with impact plume and atmospheric chemical processes, with possible diageneric ovedays. We are analyzing carbonaceous fractions of the Onaping and Onwatin to determine diagnostic C isotopic signatures Analyses by Whitehead et al. on bulk samples revealed no definitive source or processes, although delta-13 C values for "organic" C overlapped those for some meteorites. Discussion: If impact evaporation of Sudbury target carbonates did occur, then where are the carbonates? Distal carbonate (limestone/dolostone) exposures of the Espanola Formation (Huronian Supergroup) are generally thin-bedded, although remnants that partially encompass the Sudbury Crater are variable in thickness and may locally reach 250 m . If a carbonate thickness of 100-200 in existed at the target site, then copious amounts of C could have been reduced by impact processing of carbonates and also C-shale, depending on the efficiency of the processing and the amount of postimpact oxidation. Conclusion: The Sudbury crater offers a unique opportunity to study preserved characteristics of immediate carbonaceous fallback matter and particles of short-term residency in the impact plume as well as dust/aerosols from postimpact atmospheric processing.

Bunch, T. E.↗

A Study of the Oxidation of Materials in an ARC-Image Furnace

A series of tests on silicon carbide, graphite, nylon, Bakelite, Fiberglas phenolic, and ammonium chloride has been conducted in an arc-image furnace, with radiant heat fluxes at the specimen surfaces ranging from 100 to 1,000 Btu per square foot-sec. The effects of radiant heat flux and concentration of oxygen in the specimen environment on the rate of material loss were determined. It was found that for the upper half of the heat-flux range the rate-controlling process for materials that oxidize was the diffusion rate of oxygen to the specimen surface.

Wilson, R. Gale↗