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At least 559 records · Page 31

Nitrogen Doping Enables Covalent-Like π–π Bonding between Graphenes

In neighboring layers of bilayer (and few-layer) graphenes, both AA and AB stacking motifs are known to be separated at a distance corresponding to van der Waals (vdW) interactions. In this Letter, we present for the first time a new aspect of graphene chemistry in terms of a special chemical bonding between the giant graphene "molecules". Through rigorous theoretical calculations, we demonstrate that the N-doped graphenes (NGPs) with various doping levels can form an unusual two-dimensional (2D) pi-pi bonding in bilayer NGPs bringing the neighboring NGPs to significantly reduced interlayer separations. The interlayer binding energies can be enhanced by up to 50% compared to the pristine graphene bilayers that are characterized by only vdW interactions. Such an unusual chemical bonding arises from the pi-pi overlap across the vdW gap while the individual layers maintain their in-plane pi-conjugation and are accordingly planar. Moreover, the existence of the resulting interlayer covalent-like bonding is corroborated by electronic structure calculations and crystal orbital overlap population (COOP) analyses. In NGP-based graphite with the optimal doping level, the NGP layers are uniformly stacked and the 3D bulk exhibits metallic characteristics both in the in-plane and along the stacking directions.

36 MATERIALS SCIENCE↗

Process of making carbon-carbon composites

A carbon composite structure, for example, an automotive engine piston, is made by preparing a matrix including of a mixture of non crystalline carbon particulate soluble in an organic solvent and a binder that has a liquid phase. The non crystalline particulate also contains residual carbon hydrogen bonding. An uncured structure is formed by combining the matrix mixture, for example, carbon fibers such as graphite dispersed in the mixture and/or graphite cloth imbedded in the mixture. The uncured structure is cured by pyrolyzing it in an inert atmosphere such as argon. Advantageously, the graphite reinforcement material is whiskered prior to combining it with the matrix mixture by a novel method involving passing a gaseous metal suboxide over the graphite surface.

Withers, James C.↗

Modeling Structured Electrodes and Graded Porosity for Improving Discharge Rate Capability in Ultra-Thick Graphite|LiNi 0.6 Mn 0.2 Co 0.2 O 2 Batteries

Long-range electric vehicles (EVs) require high-energy-density batteries that also meet the power demands of high current charge and discharge. Ultra-thick (>100 μm) Lithium-ion battery electrodes are critical to enable this need, but slow ion transport in conventional uniform electrodes (UEs) reduces battery capacity at increasing charge/discharge rates. We present a 3D computational analysis on the impact of structured electrode (SE) and graded electrode (GE) geometries on the discharge rate capability of ultra-thick graphite|LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC-622) battery cells based on the footprint of a commercial EV pouch cell. SE cathodes with either a “grid” or “line” geometry and GEs with two layers of porosity were modeled. Based on the results of 230 models, we found that the electrolyte volume fraction is a key parameter that impacts capacity improvements in UEs, GEs, and SEs at 2 C–6 C discharge rates. SEs have the greatest discharge rate capability, outperforming GEs and UEs due to reduced Lithium-ion concentration gradients across the electrode thickness, which mitigates electrolyte depletion at high rates. The best SE model has a “grid” geometry with gravimetric and volumetric energy density improvements of 0.9%–4% at C/2–2 C and 18%–24% at 4 C–6 C relative to UEs.

25 ENERGY STORAGE↗

Oxidation Behavior and Property Degradation of Nuclear Graphites

During its multidecade operation in the core of nuclear reactors, graphite components are subjected to aggressive and continuous exposure to a high field of ionizing and neutron irradiation, high temperature, and various types of present and postulated chemical attacks. High density, high crystallinity polygranular synthetic graphite is unique among other materials for its extraordinary capacity of resisting and adapting to the aggression inflicted by high temperature, high energy neutron bombardment and ionizing gamma radiation. But, as a carbonaceous material, even though of very high purity, graphite is reactive towards common oxidizing agents: oxygen, carbon dioxide, water. Safe operation of HTGRs relies, among other aspects, on engineered safeguard systems for efficient and continuous protection of graphite components against oxidation. Graphite oxidation behavior was, and continues to be, an important direction of theoretical and experimental research, engineering analyses, models and simulations, and design and safety regulations. The avalanche of publications, reports, experimental data, computer codes, and regulatory documents related to oxidation behavior of nuclear graphite is now accelerating to new levels, prompted by the increased interest for nuclear energy as a clean, carbon-free energy source. Even though public’s perception of nuclear energy advantages may still be influenced by the memories of past accidents of nuclear reactors from generations II and III, the community of informed scientists and engineers, regulators and statemen knows that generation IV of nuclear reactors is designed at very high safety standards, doubled by great advances of scientific knowledge and technological progress. One of routes of these recent advances is directed at better understanding of graphite oxidation behavior, its relationship with graphite manufacturing and microstructural properties, along with the effects of various environmental factors and process variables. Together, the recent progress in manufacturing, properties characterization, and modeling of intricated physical and chemical processes that concur to the oxidation behavior led to development of powerful simulation codes able to analyze various scenarios of normal operation and hypothetical off-normal events, and thus to clearly specify the allowable parameters envelopes for the designers, constructors, and operators of current and future modular HTGRs. This review begins with an introduction on manufacturing methods, structure, and properties of nuclear graphite, including basic requirements that this specialty graphite type must satisfy for nuclear use. It continues with a chapter on environmental effects on nuclear graphite, where emphasis is placed less on irradiation and much more on oxidation phenomena, their safety implications, and the basic traits of chronic and acute oxidation by air (oxygen) and water (humidity, steam). Particular attention is placed on the three graphite grades of interest for this document (IG-110, NBG-18, PCEA). A chapter on properties degradation induced by oxidation follows, with focus on density, dimensional, and mechanical properties changes. The next chapter is intended as a brief review of various approaches used for modeling of graphite oxidation behavior. It summarizes the progress of oxidation models, from the early attempts to complex computational approaches interfaced with specialized computer codes designed for nuclear reactor simulations. Last, a list is presented of knowledge gaps where more research is needed. A short summary concludes the review.

36 MATERIALS SCIENCE↗

Understanding the nature of “superhard graphite”

Numerous experiments showed that on cold compression graphite transforms into a new superhard and transparent allotrope. Several structures with different topologies have been proposed for this phase. While experimental data are compatible with most of these models, the only way to solve this puzzle is to find which structure is kinetically easiest to form. Using state-of-the-art molecular-dynamics transition path sampling simulations, we investigate kinetic pathways of the pressure-induced transformation of graphite to various superhard candidate structures. Unlike hitherto applied methods for elucidating nature of superhard graphite, transition path sampling realistically models nucleation events necessary for physically meaningful transformation kinetics. We demonstrate that nucleation mechanism and kinetics lead to M-carbon as the final product. W-carbon, initially competitor to M-carbon, is ruled out by phase growth. Bct-C 4 structure is not expected to be produced by cold compression due to less probable nucleation and higher barrier of formation.

58 GEOSCIENCES↗

Detection and Characterization of Imperfections in Composite Pressure Vessels

The thermographic evaluation of composite structures for delaminations, disbonds, inclusions, porosity and microcracking has proven to be a valuable asset in the field of nondestructive testing. Coupling large area coverage, variable sensitivity and minimal surface contact with a photographic type image representation of structural anomalies; thermography has become a primary inspection method for composite structures. Thermography works well for locating both surface and subsurface defects in most composite systems ranging in thickness of up to 0.25 inch (0.64 cm) or more. The thermographic method for inspection of composite structures typically involves applying an external source of heat to the structure and then recording the changes in the surface heat profile manifested by embedded defects or by material property variations. If these temperature variations are large enough and an infrared camera with sufficient sensitivity is used, then the material or structural abnormality can be detected and referred back to its source. Interpreting the information given in a thermogram, can be a difficult task under ideal circumstances and extremely challenging in a real world setting. Variables including depth, thermal conductivity, orientation and size of the abnormality can all have a great influence on how its heat pattern will be seen by the imager. The work discussed in this paper illustrates how the microstructure of several commonly found defects in composite structures relate to their thermographic image counterpart. Two test cases are studied herein, including a large graphite/epoxy RP-1 fuel tank and a graphite composite cryogenic fuel feedline. The structures used in this study were designed to serve as manufacturing proof of concept specimens and to undergo hydroburst testing to verify manufacturing practices and structural design. Prior to hydrostatic testing the structures underwent 100% thermographic evaluation to ensure that no manufacturing or handling damage was present. Due to a large inclusion found in the feedline, it was pulled from service and dissected without performing the hydroproof The thermographic indications found in the RP-1 tank were below critical limits so it underwent a complete hydroproof loading series and finally a hydroburst. Following the hydroburst samples were cut from the tank in regions where thermography had located damage before the test. These regions were thermographically and then were cross-sectioned and photomicrographed.

Walker, James L.↗

Single Atomic Iron Site Catalysts via Benign Aqueous Synthesis for Durability Improvement in Proton Exchange Membrane Fuel Cells

Atomically-dispersed iron-nitrogen-carbon (Fe–N–C) catalysts have arisen as promising candidates for replacing the costly precious metal catalysts in fuel cells but still face some grand challenges, such as insufficient site density and durability. Herein, we report a self-assembly method in an aqueous solution to develop an atomically-dispersed iron catalyst with high oxygen reduction reaction (ORR) activity and stability in acidic electrolytes. As determined by high-resolution transmission electron microscopy (HR-TEM), X-ray absorption spectroscopy (XAS), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), this benign aqueous synthesis strategy facilitates the formation of homogeneous atomic nitrogen-coordinated iron sites embedded in a popcorn-like porous graphitic carbon matrix. These catalyst properties contribute to the improved ORR kinetic current density and mass transport. By controlling synthesis chemistry, the correlation between structure and property is systematically investigated. In this work, the iron content is the most critical material property and can regulate site density and graphitic carbon structures in the catalyst, impacting catalytic activity and stability. The enhanced performance and durability were examined in both acidic aqueous electrolytes and membrane electrode assemblies.

25 ENERGY STORAGE↗

Combustion synthesis of CdS/reduced graphene oxide composites and their photocatalytic properties

Highlights: • CdS/reduced graphene oxide composites were prepared by a combustion method. • The phase changed from hexagonal to cubic phase by increasing the added amount of GO. • The composites showed excellent visible-light photocatalytic properties. • The plausible mechanism of photodegradation was discussed. - Abstract: CdS/reduced graphene oxide composites were synthesized by a simple one-pot combustion method using cadmium nitrate, thiourea and graphite as raw materials. The structure, morphologies, and photocatalytic properties of the as-prepared samples were studied by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, photoluminescence and ultraviolet–visible spectrophotometry. The results show that the structure of CdS in as-prepared samples changes from hexagonal to cubic phase by increasing the added amount of graphene oxide. During combustion reaction, graphene oxide was reduced to reduced graphene oxide. As-obtained CdS/reduced graphene oxide composites show high visible-light photoactivities, attributed to the minimized recombination of photoinduced electrons and holes and the high surface area of reduced graphene oxide sheets.

36 MATERIALS SCIENCE↗

Electronic and total energy properties of ternary and quaternary semiconductor compounds, alloys, and superlattices: Theoretical study of Cu/graphite bonding

The goals of the research were to provide a fundamental science basis for why the bonding of Cu to graphite is weak, to critically evaluate the previous analysis of the wetting studies with particular regard to the values used for the surface energies of Cu and graphite, and to make recommendations for future experiments or other studies which could advance the understanding and solution of this technological problem. First principles electronic structure calculations were used to study the problem. These are based on density functional theory in the local density approximation and the use of the linear muffin-tin orbital band structure method. Calculations were performed for graphite monolayers, single crystal graphite with the hexagonal AB stacking, bulk Cu, Cu(111) surface, and Cu/graphite superlattices. The study is limited to the basal plane of graphite because this is the graphite plane exposed to Cu and graphite surface energies and combined with the measured contact angles to evaluate the experimental adhesion energy.

Lambrecht, Walter R. L.↗

Chemical Distribution and Bonding of Lithium in Intercalated Graphite: Identification with Optimized Electron Energy Loss Spectroscopy

Direct mapping of the lithium spatial distribution and the chemical state provides critical information on structure-correlated lithium transport in electrode materials for lithium batteries. Nevertheless, probing lithium, the lightest solid element in the periodic table, poses an extreme challenge with traditional X-ray or electron scattering techniques due to its weak scattering power and vulnerability to radiation damage. Here, we report nanoscale maps of the lithium spatial distribution in electrochemically lithiated graphite using electron energy loss spectroscopy in the transmission electron microscope under optimized experimental conditions. The electronic structure of the discharged graphite was obtained from the near-edge fine structure of the Li and C K-edges and ab initio calculations. A 2.7 eV chemical shift of the Li K-edge, along with changes in the density of states, reveals the ionic nature of the intercalated lithium with significant charge transfer to the graphene sheets. Direct mapping of lithium in graphite revealed nanoscale inhomogeneities (nonstoichiometric regions), which are correlated with local phase separation and structural disorder (i.e., lattice distortion and dislocations) as observed by high-resolution transmission electron microscopy. The surface solid-electrolyte interphase (SEI) layer was also imaged and determined to have a thickness of 10-50 nm, covering both edge and basal planes with LiF as its primary inorganic component. The Li K-edge spectroscopy and mapping, combined with electron microscopy-based structural analysis provide a comprehensive view of the structure-correlated lithium intercalation in graphite and of the formation of the SEI layer.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

AGC 2 Irradiated Material Properties Analysis

The Advanced Reactor Technologies Graphite Research and Development Program is conducting an extensive graphite irradiation experiment to provide data for licensing of a high temperature reactor (HTR) design. In past applications, graphite has been used effectively as a structural and moderator material in both research and commercial high temperature gas cooled reactor designs. , Nuclear graphite H 451, used previously in the United States for nuclear reactor graphite components, is no longer available. New nuclear graphite grades have been developed and are considered suitable candidates for new HTR reactor designs. To support the design and licensing of HTR core components within a commercial reactor, a complete properties database must be developed for these current grades of graphite. Quantitative data on in service material performance are required for the physical, mechanical, and thermal properties of each graphite grade, with a specific emphasis on data accounting for the life limiting effects of irradiation creep on key physical properties of the HTR candidate graphite grades. Further details on the research and development activities and associated rationale required to qualify nuclear grade graphite for use within the HTR are documented in the graphite technology research and development plan.

36 MATERIALS SCIENCE↗

AGC 2 Irradiation Creep Strain Data Analysis

The Advanced Reactor Technologies Graphite Research and Development Program is conducting an extensive graphite irradiation experiment to provide data for licensing of a high temperature reactor (HTR) design. In past applications, graphite has been used effectively as a structural and moderator material in both research and commercial high temperature gas cooled reactor designs. Nuclear graphite H-451, used previously in the United States for nuclear reactor graphite components, is no longer available. New nuclear graphite grades have been developed and are considered suitable candidates for new HTR reactor designs. To support the design and licensing of HTR core components within a commercial reactor, a complete properties database must be developed for these current grades of graphite. Quantitative data on in service material performance are required for the physical, mechanical, and thermal properties of each graphite grade, with a specific emphasis on data accounting for the life limiting effects of irradiation creep on key physical properties of the HTR candidate graphite grades. Further details on the research and development activities and associated rationale required to qualify nuclear grade graphite for use within the HTR are documented in the graphite technology research and development plan.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

AGC-3 Irradiation Creep Strain Data Analysis

The Advanced Reactor Technologies Graphite Research and Development Program is conducting an extensive graphite irradiation experiment to provide data for licensing of a high temperature reactor (HTR) design. In past applications, graphite has been used effectively as a structural and moderator material in both research and commercial high temperature gas cooled reactor designs. , Nuclear graphite H 451, used previously in the United States for nuclear reactor graphite components, is no longer available. New nuclear graphite grades have been developed and are considered suitable candidates for new HTR reactor designs. To support the design and licensing of HTR core components within a commercial reactor, a complete irradiated properties database must be developed for these current grades of graphite. Quantitative data on in service material performance are required for the physical, mechanical, and thermal properties of each graphite grade, with a specific emphasis on data accounting for the life limiting effects of irradiation creep on key physical properties of the HTR candidate graphite grades. Further details on the research and development activities and associated rationale required to qualify nuclear grade graphite for use within the HTR are documented in the graphite technology research and development plan.

42 ENGINEERING↗

Electrical machine cooling structure

A stator assembly that includes a graphite sheet-like element that has fold(s) so as to define at least two planar sections. The face of one of the planar section abuts a surface of a heat generating location(s) of the stator assembly and a face of another planar section abuts one the tooth or the slot bottom of the stator assembly. Also, a subassembly that includes an electrical machine stator assembly that includes a sheet-like element of a material having high thermal conductivity, wherein a portion of the element abuts the end winding(s) such that the sheet-like element conducts heat to the magnetic core, the stator housing, and/or a winding heat conduction element.

42 ENGINEERING↗

Study on Water-ingress Accident during the Initial Core and the Running-in Phase of HTR-PM - 18429

Water ingress accident is one of the typical accidents with potential hazard to the high temperature gas-cooled reactor (HTGR), which will cause reactivity introduction, as well as the chemical corrosion of the graphite fuel elements and reflector structure material. Besides, increase of the primary pressure may result in the opening of the safety valves, consequently leading the release of radioactive isotopes. Therefore high attention has been paid to water ingress phenomenon during the design of the HTGR to verify its inherent safety characteristics. The online continuous discharge and multi-pass of the fuel elements is another important characteristics for the pebble-bed HTGR which can effectively increase the reactor operation availability. From the initial core, a long period of time, namely the running-in phase, is needed to reach the final long-term stable equilibrium core. During this period of time, the core states are totally different, including the number of the fuel elements, the fuel enrichment, the accumulation of the fission product, the temperature feedback coefficient of the reactivity, and so on. In this paper, based on the design of 250 MW Pebble-bed Module High Temperature gas-cooled Reactor (HTR-PM) and a candidate proposal for its initial core and running-in phase, considering three typical states during the running-in phase, the design basis accident of a double-ended guillotine break of one heating tube has been analyzed with the TINTE code, and the results are compared with that of the equilibrium core. Some important parameters during the transient process, including the power, the temperature of the fuel element, the pressure of the primary coolant, as well as the graphite corrosion rate, are studied. To a certain extent, the results can verity the design of the initial core and the running-in phase, and also further prove the safety feature of the HTR. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Hygrothermal effects on the mechanical behaviour of graphite fibre-reinforced epoxy laminates beyond initial failure

The critical load levels and associated cracking beyond which a multidirectional laminate can be considered as structurally failed has been determined by loading graphite fiber-reinforced epoxy laminates to different strain levels up to ultimate failure. Transverse matrix cracking was monitored by acoustic and optical methods. The residual stiffness and strength parallel and perpendicular to the cracks were determined and related to the environmental/loading history. Within the range of experimental conditions studied, it is concluded that the transverse cracking process does not have a crucial effect on the structural performance of multidirectional composite laminates.

Ishai, O.↗

Transition from half metal to semiconductor in Li doped g-C{sub 4}N{sub 3}

We have investigated the structural and magnetic properties of Li doped graphitic carbon nitride (g-C{sub 4}N{sub 3}) using the van der Waals density functional theory. A free standing g-C{sub 4}N{sub 3} was known to show a half metallic state with buckling geometry, but this feature completely disappears in the presence of Li doping. Besides this structural modification, very interestingly, we have obtained that the Li doped g-C{sub 4}N{sub 3} shows dramatic change in its electronic structure. Both ferromagnetic and nonmagnetic states are almost degenerated in one Li atom doped system. However, the transition from half metallic state to semiconductor is observed with further increase of Li concentration and the calculated energy gap is 1.97 eV. We found that Li impurity plays as a donor element and charge transfer from the Li atom to neighboring N atoms induces a band gap. Overall, we have observed that the electronic and magnetic properties of g-C{sub 4}N{sub 3} are substantially modified by Li doping.

36 MATERIALS SCIENCE↗