Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Graphite oxidation”

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 379 records · Page 21

Phosphorus-containing bisimide resins

The production of fire-resistant resins particularly useful for making laminates with inorganic fibers such as graphite fibers is discussed. The resins are by (1) condensation of an ethylenically unsaturated cyclic anhydride with a bis(diaminophenyl) phosphine oxide, and (2) by addition polymerization of the bisimide so obtained. Up to about 50%, on a molar basis, of benzophenonetetracarboxylic acid anhydride can be substituted for some of the cyclic anhydride to alter the properties of the products. Graphite cloth laminates made with these resins show 800 C char yields greater than 70% by weight in nitrogen. Limiting oxygen indexes of more than 100% are determined for these resins.

Varma, I. K.↗

Elucidating the role of earth alkaline doping in perovskite-based methane dry reforming catalysts

To elucidate the role of earth alkaline doping in perovskite-based dry reforming of methane (DRM) catalysts, we embarked on a comparative and exemplary study of a Ni-based Sm perovskite with and without Sr doping. While the Sr-doped material appears as a structure-pure Sm 1.5 Sr 0.5 NiO 4 Ruddlesden Popper structure, the undoped material is a NiO/monoclinic Sm 2 O 3 composite. Hydrogen pre-reduction or direct activation in the DRM mixture in all cases yields either active Ni/Sm 2 O 3 or Ni/Sm 2 O 3 /SrCO 3 materials, with albeit different short-term stability and deactivation behavior. The much smaller Ni particle size after hydrogen reduction of Sm 1.5 Sr 0.5 NiO 4 , and of generally all undoped materials stabilizes the short and long-term DRM activity. Carbon dioxide reactivity manifests itself in the direct formation of SrCO 3 in the case of Sm 1.5 Sr 0.5 NiO 4 , which is dominant at high temperatures. For Sm 1.5 Sr 0.5 NiO 4 , the CO : H 2 ratio exceeds 1 at these temperatures, which is attributed to faster direct carbon dioxide conversion to SrCO 3 without catalytic DRM reactivity. As no Sm 2 O 2 CO 3 surface or bulk phase as a result of carbon dioxide activation was observed for any material – in contrast to La 2 O 2 CO 3 – we suggest that oxy-carbonate formation plays only a minor role for DRM reactivity. Rather, we identify surface graphitic carbon as the potentially reactive intermediate. Graphitic carbon has already been shown as a crucial reaction intermediate in metal-oxide DRM catalysts and appears both for Sm 1.5 Sr 0.5 NiO 4 and NiO/monoclinic Sm 2 O 3 after reaction as crystalline structure. It is significantly more pronounced for the latter due to the higher amount of oxygen-deficient monoclinic Sm 2 O 3 facilitating carbon dioxide activation. Despite the often reported beneficial role of earth alkaline dopants in DRM catalysis, we show that the situation is more complex. In our studies, the detrimental role of earth alkaline doping manifests itself in the exclusive formation of the sole stable carbonated species and a general destabilization of the Ni/monoclinic Sm 2 O 3 interface by favoring Ni particle sintering.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Upcycling Polyethylene Waste Into Hybrid Graphitic Porous Carbon Materials Used in High-Performance Zinc-Ion Hybrid Capacitors

Polyethylene (PE) waste is a challenge to upcycle into useful materials because this plastic tends to decompose into volatile compounds when heated at relatively low temperatures. In this work, we report a chemical process that addresses this challenge by converting mixtures of linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), and high-density polyethylene (HDPE) waste into a hybrid graphitic porous carbon (HGPC) that can be used as a zinc-ion hybrid capacitor cathode. The process uses a low temperature thermal oxidation pre-treatment step, with assistance of an inert solid additive (KCl) to increase the effective surface area of the PE melt, to functionalize, cross-link, and stabilize the PE waste followed by carbonization and catalytic graphitization steps at higher temperatures with a potassium carbonate (K2CO3) catalyst. The PE waste derived HPGC (PW-HPGC) has a hybrid structure composed of graphene-like carbon nanosheets grown on the surface of carbon particles, high porosity with the Brunauer–Emmett–Teller (BET) specific surface area up to 1,763 m2g-1, and good graphitic degree with average Raman I2D/IG ratios of 0.53. When used as a cathode material for zinc-ion hybrid capacitors, this PW-HGPC exhibits an excellent specific capacity up to 126.7 mAhg-1 at high mass loading of 10 mgcm-2. Moreover, PW-HGPC exhibits remarkable cycling stability with capacity retention of >94% after 10,000 cycles at a current density of 2.0 A g-1.

hybrid graphitic porous carbon↗

DOE ART Graphite Program Intro Status 2023

General description of the ART Graphite Program with Status for 2023. This includes list of staff members, and brief description of behavior models, licensing & code, graphite R&D, As-Fab'd Properties, Machanism and Analysis, Irradiation. Also detail FY23 Activites, with AGC Update, Oxidation Activiteis, Baseline STatus, ASME Code Development, VIC Project Update, Molten salt studies. Slide included to highlight each employee contributions for work and papers and NEUPs.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Transformation of Graphitic and Amorphous Carbon Dust to Complex Organic Molecules in a Massive Carbon Cycle in Protostellar Nebulae

More than 95% of silicate minerals and other oxides found in meteorites were melted, or vaporized and recondensed in the Solar Nebula prior to their incorporation into meteorite parent bodies. Gravitational accretion energy and heating via radioactive decay further transformed oxide minerals accreted into planetesimals. In such an oxygen-rich environment the carbonaceous dust that fell into the nebula as an intimate mixture with oxide grains should have been almost completely converted to CO. While some pre-collapse, molecular-cloud carbonaceous dust does survive, much in the same manner as do pre-solar oxide grains, such materials constitute only a few percent of meteoritic carbon and are clearly distinguished by elevated D/H, N-15/N-16, C-13/C-12 ratios or noble gas patterns. Carbonaceous Dust in Meteorites: We argue that nearly all of the carbon in meteorites was synthesized in the Solar Nebula from CO and that this CO was generated by the reaction of carbonaceous dust with solid oxides, water or OH. It is probable that some fraction of carbonaceous dust that is newly synthesized in the Solar Nebula is also converted back into CO by additional thermal processing. CO processing might occur on grains in the outer nebula through irradiation of CO-containing ice coatings or in the inner nebula via Fischer-Tropsch type (FTT) reactions on grain surfaces. Large-scale transport of both gaseous reaction products and dust from the inner nebula out to regions where comets formed would spread newly formed carbonaceous materials throughout the solar nebula. Formation of Organic Carbon: Carbon dust in the ISM might easily be described as inorganic graphite or amorphous carbon, with relatively low structural abundances of H, N, O and S . Products of FTT reactions or organics produced via irradiation of icy grains contain abundant aromatic and aliphatic hydrocarbons. aldehydes, keytones, acids, amines and amides.. The net result of the massive nebular carbon cycle is to convert relatively inert carbonaceous dust from the ISM into the vital organic precursors to life such as amino acids and sugars intimately mixed with dust and ice in primitive planetesimals. Since the number of carbon atoms entering the Solar Nebula as dust exceeds the number of atoms entering the nebula as oxide grains. the formation of large quantities of complex organic molecules may represent the largest single chemical cycle in the nebula.

Nuth, Joseph A., III↗

Graphite-Embedded High-Performance Insulated Metal Substrate for Wide-Bandgap Power Modules

Emerging wide-bandgap (WBG) semiconductor devices such as silicon carbide (SiC) metal–oxide semiconductor field-effect transistors (MOSFETs) and gallium nitride high-electron-mobility transistors can handle high power in reduced semiconductor areas better than conventional Si-based devices owing to superior material properties. With increased power loss density in a WBG-based converter and reduced die size in power modules, thermal management of power devices must be optimized for high performance. Here, we present a graphite-embedded insulated metal substrate (thermally-annealed-pyrolytic-graphite-embedded insulated metal substrate—IMSwTPG) designed for WBG power modules. Theoretical thermal performance analysis of graphite-embedded metal cores is presented, with design details for IMSwTPG with embedded graphite to replace a direct-bonded copper (DBC) substrate. The proposed IMSwTPG is compared with an aluminum nitride-based DBC substrate using finite-element thermal analysis for steady-state and transient thermal performance. The solutions’ thermal performances are compared under different coolant temperature and thermal loading conditions, and the proposed substrate's electrical performance is validated with static and dynamic characterization. Using graphite-embedded substrates, junction-to-case thermal resistance of SiC MOSFETs can be reduced up to 17%, and device current density can be increased by 10%, regardless of the thermal management strategy used to cool the substrate. Reduced transient thermal impedance of up to 40% of dies owing to increased heat capacity is validated in transient thermal simulations and experiments. The half-bridge power module's electrical performance is evaluated for on -state resistance, switching performance, and switching loss at three junction temperature conditions. The proposed substrate solution has minimal impact on conduction and switching performance of SiC MOSFETs.

42 ENGINEERING↗

Ceramic Composite Inert Matrix Fuel Forms in High-Temperature Gas-Cooled Microreactors

Here, this work optimizes micro-prismatic high-temperature gas reactor (HTGR) designs to reduce the energy-normalized mass of spent nuclear fuel (SNF) and high-level waste (HLW) produced. The optimization was performed for the current graphite moderator and an inert matrix fuel (IMF) concept employing different composite moderators in a prismatic design architecture. The fuel matrix is magnesium oxide (MgO) with entrained tristructural-isotropic (TRISO) fuel. The moderator materials, including beryllium oxide (MgO-BeO) and beryllium (MgO-Be) at 40 vol % loading and yttrium hydride (MgO-YH x=1.9 ) and zirconium hydride (MgO-ZrH x=1.9 ) at 15 vol % loading, were entrained within the MgO host matrix. A generic graphite micro-prismatic HTGR is used as the baseline point design where the external dimensions are held constant. The composite moderator designs use 19.9% enriched uranium nitride TRISO fuel and hexagonal assemblies. For each IMF concept, an optimization study was performed to maximize the discharge burnup of the fuel by varying the TRISO packing fraction and the lattice pitch of the assemblies. The mass of SNF and HLW, other waste metrics, fuel cost, environmental impact metrics, and the activity of the SNF and HLW at 100 years and 100 000 years were calculated for the optimized IMF and graphite reference designs. The IMF results were subsequently compared to those of the graphite reference and the values for a light water reactor (LWR) and a small modular LWR. For the SNF and HLW, all the IMF concepts and the graphite reference produced less waste compared to the traditional LWR designs. However, the IMF concepts outperformed the graphite reference regarding the mass of SNF and HLW. For the other waste metrics, the IMF concepts showed reductions in fuel cost with improved environmental metrics relative to the graphite reference. Overall, the IMF concepts significantly reduced the SNF and HLW produced per unit of energy generated compared to traditional LWR designs.

TRISO↗

Operando study of mechanical integrity of high-volume expansion Li-ion battery anode materials coated by Al 2 O 3

Group IV elements and their oxides, such as Si, Ge, Sn and SiO have much higher theoretical capacity than commercial graphite anode. However, these materials undergo large volume change during cycling, resulting in severe structural degradation and capacity fading. Al 2 O 3 coating is considered an approach to improve the mechanical stability of high-capacity anode materials. To understand the effect of Al 2 O 3 coating directly, we monitored the morphology change of coated/uncoated Sn particles during cycling using operando focused ion beam–scanning electron microscopy. Here, the results indicate that the Al 2 O 3 coating provides local protection and reduces crack formation at the early stage of volume expansion. The 3 nm Al 2 O 3 coating layer provides better protection than the 10 and 30 nm coating layer. Nevertheless, the Al 2 O 3 coating is unable to prevent the pulverization at the later stage of cycling because of large volume expansion.

25 ENERGY STORAGE↗

Selected fretting-wear-resistant coatings for titanium - 6-percent-aluminum - 4-percent-vanadium alloy

A titanium - 6-percent-aluminum - 4-percent-vanadium alloy (Ti-6Al-4V) was subjected to fretting-wear exposures against uncoated Ti-6Al-4V as a baseline and against various coatings and surface treatments applied to Ti-6Al-4V. The coatings evaluated included plasma-sprayed tungsten carbide with 12 percent cobalt, aluminum oxide with 13 percent titanium oxide, chromium oxide, and aluminum bronze with 10 percent aromatic polyester; polymer-bonded polyimide, polyimide with graphite fluoride, polyimide with molybdenum disulfide (MoS2), and methyl phenyl silicone bonded MoS2, preoxidation surface treatment, a nitride surface treatment, and a sputtered MoS2 coating. Results of wear measurements on both the coated and uncoated surfaces after 300,000 fretting cycles indicated that the polyimide coating was the most wear resistant and caused the least wear to the uncoated mating surface.

Bill, R. C.↗

All-aromatic biphenylene end-capped polyquinoline and polyimide matrix resins

Biphenylene end-capped polyquinoline and polyimide resins afford low void content graphite-reinforced composites with good initial properties. However, with both resins, rapid degradation occurs during oxidative isothermal aging at elevated temperatures. The degradation is not observed during isothermal aging under a nitrogen atmosphere which suggests that the biphenylene end-cap (or the resulting crosslink/chain extension structures) is not particularly thermooxidatively stable. The nature of the thermooxidative instability is currently under investigation.

Droske, J. P.↗

High molecular weight first generation PMR polyimides for 343 C applications

The effect of molecular weight on 343 C thermo-oxidative stability (TOS), mechanical properties, and processability, of the first generation PMR polyimides was studied. Graphite fiber reinforced PMR-15, PMR-30, PMR-50, and PMR-75 composites (corresponding to formulated molecular weights of 1500, 3000, 5000, and 7500, respectively) were fabricated using a simulated autoclave process. The data reveals that while alternate autoclave cure schedules are required for the high molecular weight resins, low void laminates can be fabricated which have significantly improved TOS over PMR-15, with only a small sacrifice in mechanical properties.

Malarik, Diane C.↗

High molecular weight first generation PMR polyimides for 343 C applications

The effect of molecular weight on 343 C thermo-oxidative stability (TOS), mechanical properties, and processability, of the first generation PMR polyimides was studied. Graphite fiber reinforced PMR-15, PMR-30, PMR-50, and PMR-75 composites (corresponding to formulated molecular weights of 1500, 3000, 5000, and 7500, respectively) were fabricated using a simulated autoclave process. The data reveal that while alternate autoclave cure schedules are required for the high molecular weight resins, low void laminates can be fabricated which have significantly improved TDS over PMR-15, with only a small sacrifice in mechanical properties.

Malarik, D. C.↗

Thermal Energy Grid Storage (TEGS) Using Multi-Junction Photovoltaics (MPV) (Final Technical Report)

The project aimed to develop a thermal energy storage battery that converts electricity to heat and stores heat at ultra-high temperatures (>2000°C) in graphite blocks. The thermal battery discharge uses TPV cells that directly convert thermal energy to electrical energy without any moving parts. All components of this technology were successfully demonstrated at the laboratory scale in this project. Development of extremely low cost (< $20/kWh) grid level energy storage is a crucial necessity to reach high penetrations of renewables. The thermal battery technology developed in this project is expected to meet the cost targets that would enable full renewable penetration. The project focused on four key aspects of this technology: Converting electricity to ultra-high temperature heat: This was done through development of graphite Joule heaters. Major issues related to arcing, heater evaporation and deterioration due to long term oxidation were addressed to ensure lifetime exceeding the service lifetime of the battery. Converting ultra-high temperature heat back to electricity: This was done through development of beyond state-of-the-art TPV cells. We demonstrated energy conversion efficiency of >40% that is a world record and exceeds the average energy conversion efficiency of turbines in the USA. The findings are peer-reviewed and published in Nature, and received a wide media attention globally. Protecting the TPV cells to ensure lifetime: Deposition of volatilized material, such as sublimated material or particles, on the TPV cell could greatly reduce the efficiency and lifetime of the TPV cells by blocking their view to the heat source and causing cell overheating. In this project we developed and demonstrated an approach that reduces the deposition rate, ensuring long > 30 year life. Technoeconomic feasibility and commercialization: In collaboration with the project’s technical advisory board, we developed a technoeconomic model. The model shows that, at large scales (> 1GWh) the thermal battery technology is projected to reach a cost of energy stored below $10/kWh-e, with a cost per unit power < $0.5/W-e and a roundtrip efficiency of 50%. These results, along with the technical achievements in the project led to the creation of a startup company (i.e., Fourth Power) that is pursuing commercialization of the technology.

25 ENERGY STORAGE↗

High-pressure high-temperature synthesis and thermal equation of state of high-entropy transition metal boride

High-entropy transition metal boride (Hf 0.2 Ti 0.2 Zr 0.2 Ta 0.2 Mo 0.2 )B 2 sample was synthesized under high-pressure and high-temperature starting from ball-milled oxide precursors (HfO 2 , TiO 2 , ZrO 2 , Ta 2 O 5 , MoO 3 ) mixed with graphite and boron-carbide. Experiments were conducted in a large-volume Paris Edinburgh press combined with an in-situ Energy Dispersive X-ray Diffraction. The hexagonal AlB 2 phase with an ambient pressure volume V 0 = 27.93 ± 0.03 Å 3 was synthesized at a pressure of 0.9 GPa and temperatures above 1373K. High-pressure high-temperature studies on the synthesized high-entropy transition metal boride sample were performed to 7.6 GPa and 1873 K. The thermal equation of state fitted to the experimental data resulted in an ambient pressure bulk-modulus K 0 = 344 ± 39 GPa, dK/dT = –0.108 ± 0.027 GPa/K, and a temperature dependent volumetric thermal expansion coefficient α = α 0 + α 1 T + α 2 T –2 . The thermal stability combined with a high bulk-modulus establishes this high-entropy transition metal boride as an ultrahard high-temperature ceramic material.

36 MATERIALS SCIENCE↗

Chemical interactions in the aluminum-carbon and aluminum-silicon carbide systems

XPS was used to investigate the influence of O2 and H2O on the formation of aluminum carbide at Al-C and Al-SiC interfaces. It was determined that dosing the interfaces with H2O catalyzed the formation of aluminum carbide in both systems. This result is consistent with the oxidation model of carbide formation (developed to understand the kinetics of aluminum carbide formation at graphite-aluminum interfaces). These results imply that the formation of aluminum carbide in graphite- and SiC-reinforced metal-matrix composites, which severely degrades the composite mechanical properties by degrading the fiber and interface strength is catalyzed.

Maruyama, Benji↗

Low-Toxicity PMR Polyimide

New low-toxicity PMR system developed and designated LaRC-RP46. Exhibits better processability, toughness, and thermo-oxidative stability than does PMR-15. Polyimide inexpensive and readily processed into high-quality graphite-fiber-reinforced composite. Used as high-performance, high-temperature-resistant adhesive, molding, composite, film, and coating material where low toxicity desired characteristic. Significantly extends applications of PMR-type polyimides.

Pater, Ruth H.↗

Comparison of Graphite Fabric Reinforced PMR-15 and Avimid N Composites After Long Term Isothermal Aging at Various Temperatures

Extensive effort is currently being expended to demonstrate the feasibility of using high-performance, polymer-matrix composites as engine structural materials over the expected operating lifetime of the aircraft, which can extend from 18,000 to 30,000 hr. The goal is to develop light-weight, high-strength, and high-modulus materials for use in higher temperature sections of advanced 21 st century aircraft propulsion systems. To accomplish this goal, it is necessary to pursue the development of thermal and mechanical durability models for graphite-fiber-reinforced, polymer-matrix composites. Numerous investigations have been reported regarding the thermo-oxidative stability (TOS) of the polyimide PMR-15 (1-5). A significant amount of this work has been directed at edge and geometry effects, reinforcement fiber influences, and empirical modeling of high-temperature weight loss behavior. It is yet to be determined if the information obtained from the PMR-15 composite tests is applicable to other polyimide-matrix composites. The condensation-curing polymer Avimid N is another advanced composite material often considered for structural applications at high temperatures. Avimid N has better thermo-oxidative stability than PMR-15 (6), but the latter is more easily processed. The most comprehensive study of the thermo-oxidative stability of Avimid N neat resin and composites at 371 (infinity)C is found in Salin and Seferis (7). The purposes of the work described herein were to compare the thermal aging behavior of these two matrix polymers and to determine the reasons for and the consequences of the difference in thermal durability. These results might be of some use in improving future polymer development through the incorporation of the desirable characteristics of both polyimides.

Bowles, Kenneth J.↗

A Study of Space Environment Effect on Highly Thermally Conductive Hybrid Carbon Fiber Polymer Composites

A set of novel highly thermally conductive hybrid carbon fiber (CF) polymer composites has been developed for lightweight thermal radiator applications in space missions. This study investigates the effects of the space environment on these materials following exposure in low-Earth orbit (LEO) during the Materials International Space Station Experiment (MISSE)-17 flight mission, where samples experienced 159 days of combined atomic oxygen (AO), ultraviolet (UV) radiation, high vacuum, space radiation and thermal cycling. Post-flight characterization included weight loss, surface morphology, thermo-optical properties, molecular structures, glass transition temperature, thermal degradation and thermal conductivity analyses. The pyrolytic graphite sheet (PGS) samples exhibited negligible weight loss, stable thermo-optical property, and only minor oxidation signature on the exposed surface. Although AO erosion of the epoxy polymer matrix was evident, carbon nanotube (CNT)-infused PGS/CF epoxy composites retained high thermal emissivity and preserved their high thermal conductivities. These results demonstrate that the novel highly thermally conductive hybrid CF composites possess strong environmental resilience and are promising candidates for lightweight thermal radiators and thermal management components in future space exploration missions.

Space Environment↗