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At least 1,027 records · Page 57

Structural Anomalies and Electronic Properties of an Ionic Liquid under Nanoscale Confinement

Ionic liquids (ILs) promise far greater electrochemical performance compared to aqueous systems, yet key physicochemical properties governing their assembly at interfaces within commonly used graphitic nanopores remain poorly understood. Here, we combine synchrotron X-ray scattering with first-principles molecular dynamics simulations to unravel key structural characteristics of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([TFSI] – ) ionic liquids confined in carbon slit pores. X-ray scattering reveals selective pore filling due to size exclusion, while filled pores exhibit disruption in the IL intermolecular structure, the extent of which increases for narrower slit pores. First-principles simulations corroborate this finding and quantitatively describe how perturbations in the local IL structure, particularly the hydrogen-bond network, depend strongly on the degree of confinement. Despite significant deviations in structure under confinement, electrochemical stability remains intact, which is important for energy storage based on nanoporous carbon electrodes (e.g., supercapacitors).

36 MATERIALS SCIENCE↗

Revealing the electronic structure of LiC 6 by soft X-ray spectroscopy

The electronic structure of LiC 6 has been investigated in this paper by soft X-ray absorption and emission spectroscopies. The results reveal that upon full lithiation of graphite, the Li 2s electrons are transferred into the carbon π* states in a near rigid-band behavior, resulting in the increased density of states near E F and the shift of σ* states to lower energies. Finally, in addition, the resonant inelastic X-ray scattering spectra of LiC 6 do not show strong dispersive features as that of graphite, indicating that the crystal momentum is not conserved during the scattering process due to the delocalization of electrons in the intermediate state.

36 MATERIALS SCIENCE↗

Structure, dynamics, and electrochemistry of choline chloride/ethylene glycol eutectic solvents at an electrode surface explored by molecular dynamics simulations

Choline chloride and ethylene glycol mixtures with 1:2, 1:4, and 1:6 molar ratios on the surfaces of graphite and gold electrodes were studied using classical molecular dynamics simulations. Both neutral and charged electrodes were considered. The liquid composition, solvation structure, molecular orientation, and dynamics at the electrode surface are significantly different from those of the bulk liquid. These properties strongly depend on the electrode material and charge density, whereas they are less sensitive to the overall solvent composition. The effect of the electrode on the composition, structure, and orientation of the liquid fades beyond ∼10 Å from the surface of the electrode. This distance corresponds to about two layers of the structured solvent, despite the fact that the layered structure extends to at least five layers or about 25 Å. However, the electrode influences solvent dynamics over a longer distance. The electrochemical properties of the eutectic solvent at both electrode surfaces were also studied. The simulations captured the experimental differential capacitance shapes for both electrode systems, although the magnitudes and exact shapes differ. The simulations further revealed that the solvent in the first solvation layer can both overscreen and underscreen the electrode charges depending on the electrode material and electrode potential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

SEP solar array Shuttle flight experiment

An experiment to verify the operational performance of a full-scale Solar Electric Propulsion (SEP) solar array is described. Scheduled to fly on the Shuttle in 1983, the array will be deployed from the bay for ten orbits, with dynamic excitation to test the structural integrity being furnished by the Orbiter verniers; thermal, electrical, and sun orientation characteristics will be monitored, in addition to safety, reliability, and cost effective performance. The blanket, with aluminum and glass as solar cell mass simulators, is 4 by 32 m, with panels (each 0.38 by 4 m) hinged together; two live Si cell panels will be included. The panels are bonded to stiffened graphite-epoxy ribs and are storable in a box in the bay. The wing support structure is detailed, noting the option of releasing the wing into space by use of the Remote Manipulator System if the wing cannot be refolded. Procedures and equipment for monitoring the array behavior are outlined, and comprise both analog data and TV recording for later playback and analysis. The array wing experiment will also aid in developing measurement techniques for large structure dynamics in space.

Elms, R. V., Jr.↗

Interplay of Mechanochemistry and Material Processes in the Graphite to Diamond Phase Transformation

The manifestation of intramolecular strains in covalent systems is widely known to accelerate chemical reactions and open alternative reaction paths. This process is moderately well understood for isolated molecules and unimolecular processes. However, in condensed matter processes such as phase transformations, material properties and structure may influence typical mechanochemical effects. Therefore, we utilize steered molecular dynamics to induce out of plane strains in graphite and compress the system under a constant strain rate to induce phase transformation. We show that the out of plane strain allows phase transformations to initiate at small amounts of compressive strain. Yet, in contrast to typical mechanochemical results, the sum of compressive and out of plane work needed to form a diamond has a local minimum due to altered defect formation processes during phase transformation. Additionally, these altered processes slow the kinetics of the phase transformation, taking longer from initiation to total material transformation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of Molecular Simulation Model Accuracy on the Interfacial Properties of an Ionic Liquid: Overview of Recommended Practices

Increasing the energy storage capability of ionic liquid supercapacitors will require better understanding of ion-electrode interactions. We have probed the influence of these interactions on the structure and differential capacitance of of an ionic liquid ([EMIM][BF4]) at an ideal graphite interface as a function of model accuracy. Of note, differential capacitance is determined through newly derived and validated fluctuation formulas. In terms of model accuracy, we test electrostatic techniques, electrode charging techniques, and electrolyte interatomic potentials. For electrostatic summations, we employ high cost, high fidelity techniques as well as less expensive, approximate techniques for summation in slab geometry. For electrode charging, uniform, constant-charge and environmentally responsive, constant-potential conditions are employed. For the ionic liquid, constant charge and atomically polarizable models are employed. We comment on the role of model accuracy on the structure and energetics of the electric double layer as well as on the magnitude and shape of differential capacitance.

simulations↗

Advancing neutron diffraction for accurate structural measurement of light elements at megabar pressures

Over the last 60 years, the diamond anvil cell (DAC) has emerged as the tool of choice in high pressure science because materials can be studied at megabar pressures using X-ray and spectroscopic probes. In contrast, the pressure range for neutron diffraction has been limited due to low neutron flux even at the strongest sources and the resulting large sample sizes. Here, we introduce a neutron DAC that enables break-out of the previously limited pressure range. Key elements are ball-bearing guides for improved mechanical stability, gem-quality synthetic diamonds with novel anvil support and improved in-seat collimation. We demonstrate a pressure record of 1.15 Mbar and crystallographic analysis at 1 Mbar on the example of nickel. Additionally, insights into the phase behavior of graphite to 0.5 Mbar are described. These technical and analytical developments will further allow structural studies on low-Z materials that are difficult to characterize by X-rays.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Graphitization of Glassy Carbon after Compression at Room Temperature

Glassy carbon is a technologically important material with isotropic properties that is nongraphitizing up to ~3000 °C and displays complete or “superelastic” recovery from large compression. The pressure limit of these properties is not yet known. Here we use experiments and modeling to show permanent densification, and preferred orientation occurs in glassy carbon loaded to 45 GPa and above, where 45 GPa represents the limit to the superelastic and nongraphitizing properties of the material. Furthermore, the changes are explained by a transformation from its sp 2 rich starting structure to a sp 3 rich phase that reverts to fully sp 2 bonded oriented graphite during pressure release.

36 MATERIALS SCIENCE↗

Characterization of the dimensional stability of advanced metallic materials using an optical test bench structure

The dimensional stability of low-density high specific-strength metal-matrix composites (including 30 vol pct SiC(p)/SXA 24-T6 Al, 25 vol pct SiC(p)/6061-T6 Al, 40 vol pct graphite P100 fiber/6061 Al, 50 vol pct graphite P100 fiber/6061 Al, and 40 vol pct P100 graphite fiber/AZ91D Mg composites) and an Al-Li-Mg metal alloy was evaluated using a specially designed five-strut optical test bench structure. The structure had 30 thermocouple locations, one retroreflector, one linear interferometer multilayer insulation, and various strip heaters. It was placed in a 10 exp -7 torr capability vacuum chamber with a laser head positioned at a window port, and a laser interferometer system for collecting dimensional change data. It was found that composite materials have greater 40-C temporal dimensional stability than the AL-Li-Mg alloy. Aluminum-based composites demonstrated better 40-C temporal stability than Mg-based composites.

Hsieh, Cheng↗

Nanoscale MnO 2 cathodes for Li-ion batteries: effect of thermal and mechanical processing

This study investigates the effect of thermal and mechanical processing of MnO 2 nanoparticle cathodes on the electrochemical performance, ion intercalation mechanism and structural changes upon cycling. Specifically, thermal processing at different temperatures is utilized to tune the sub-nanoparticle polymorph composition, while mechanical processing (high energy ball-milling) is used to change the particle size and create a better contact between active material and conductive graphite additive. The combination of thermal and mechanical processing is also investigated for possible synergistic effects. The structural changes due to processing suggest that thermal treatment of the MnO 2 nanoparticles at 400 °C forms a high concentration of pyrolusite domains (1 $\times$ 1 channels) leading to improved reversibility of lithium intercalation/de-intercalation and capacity retention. It is also found that ball-milling for a short time (20 min) leads to some amorphization and decrease of the crystallite sizes resulting in improved capacity. The structural changes and ion intercalation mechanism of the pristine and processed electrode materials during cycling are investigated by ex situ synchrotron x-ray diffraction (XRD) and ex situ and in situ x-ray absorption near edge structure (XANES) studies.

25 ENERGY STORAGE↗

Synthesis, physical and chemical properties, and potential applications of graphite fluoride fibers

Graphite fluoride fibers can be produced by fluorinating pristine or intercalated graphite fibers. The higher the degree of graphitization of the fibers, the higher the temperature needed to reach the same degree of fluorination. Pitched based fibers were fluorinated to flourine-to-carbon atom rations between 0 and 1. The graphite fluoride fibers with a fluorine-to-carbon atom ration near 1 have extensive visible structural damage. On the other hand, fluorination of fibers pretreated with bromine or fluorine and bromine result in fibers with a fluorine-to-carbon atom ratio nearly equal to 0.5 with no visible structural damage. The electrical resistivity of the fibers is dependent upon the fluorine to carbon atom ratio and ranged from .01 to 10 to the 11th ohm/cm. The thermal conductivity of these fibers ranged from 5 to 73 W/m-k, which is much larger than the thermal conductivity of glass, which is the regular filler in epoxy composites. If graphite fluoride fibers are used as a filler in epoxy or PTFE, the resulting composite may be a high thermal conductivity material with an electrical resistivity in either the insulator or semiconductor range. The electrically insulating product may provide heat transfer with lower temperature gradients than many current electrical insulators. Potential applications are presented.

Hung, Ching-Cheh↗

Heat resistant composite structure for shuttle applications (Ryton-B)

A program was undertaken to characterize Ryton-B resin, develop graphite filament prepregs, undirectional laminates and determine the strength and heat resistance of the composite system. Through the use of a water soluble resin binder, high quality prepreg tape, three inches wide with 4 tows of HM-S were produced. The tape laminated to 0.00175 inch per ply. A wide range of properties in the cured resin and laminate were found using different curing conditions. The thermal stability and strength of molded laminates appears to be very dependent upon the cure cycle used for polymerization.

Source record↗

Sub-T/g/ annealing studies of advanced epoxy-matrix graphite-fiber-reinforced composites

Annealing at temperatures below the glass transition temperature (sub-T/g/ annealing) in structural epoxy network glasses is found to affect long-term mechanical properties of symmetrically (+ or - 45 deg) reinforced 16-lamina graphite/epoxy composites. Post-cured specimens of Thornel 300 graphite/Narmco 5208 epoxy are sub-T(g) annealed at 140 C for about 10, 100, 1000, 10,000, and 100,000 min with a prior quenching above T(g). The ultimate tensile strength, strain-to-break, and static toughness of the composite materials are found to decrease as a function of sub-T(g) annealing time, while no weight loss is observed. Time-dependent changes in properties are explained by a physical aging concept based on free-volume decreases in the nonequilibrium glassy state of network epoxies, and results imply that changes in composite properties may occur with the service time.

Kong, E. S. W.↗

Fabrication and Testing of a Large Primary Reflector Structure

This paper discusses the fabrication considerations and proposed testing concepts related to a large twelve meter, graphite-epoxy space truss that is being developed to provide support of the primary mirror system for the Beam Transmission Optical System (BTOS).

space truss primary reflector free electron laser ↗

Effect of temperature on composite sandwich structures subjected to low velocity impact

The effect of low velocity projectile impact on sandwich-type structural components was investigated. The materials used in the fabrication of the impact surface were graphite-, Kevlar-, and boron-fibers with appropriate epoxy matrices. The testing of the specimens was performed at moderately low- and high-temperatures as well as at room temperature to assess the impact-initiated strength degradation of the laminates. Eleven laminates with different stacking sequences, orientations, and thicknesses were tested. The low energy projectile impact is considered to simulate the damage caused by runway debris, the dropping of the hand tools during servicing, etc., on the secondary aircraft structures fabricated with the composite materials. The results show the preload and the impact energy combinations necessary to cause catastrophic failure in the laminates tested. A set of faired curves indicating the failure thresholds is shown separately for the tension-and compression-loaded laminates. The specific-strengths and -modulii for the various laminates tested are also given.

Sharma, A. V.↗

Electrochemical Ultracapacitors Using Graphitic Nanostacks

Electrochemical ultracapacitors (ECs) have been developed using graphitic nanostacks as the electrode material. The advantages of this technology will be the reduction of device size due to superior power densities and relative powers compared to traditional activated carbon electrodes. External testing showed that these materials display reduced discharge response times compared to state-of-the-art materials. Such applications are advantageous for pulsed power applications such as burst communications (satellites, cell phones), electromechanical actuators, and battery load leveling in electric vehicles. These carbon nanostructures are highly conductive and offer an ordered mesopore network. These attributes will provide more complete electrolyte wetting, and faster release of stored charge compared to activated carbon. Electrochemical capacitor (EC) electrode materials were developed using commercially available nanomaterials and modifying them to exploit their energy storage properties. These materials would be an improvement over current ECs that employ activated carbon as the electrode material. Commercially available graphite nanofibers (GNFs) are used as precursor materials for the synthesis of graphitic nanostacks (GNSs). These materials offer much greater surface area than graphite flakes. Additionally, these materials offer a superior electrical conductivity and a greater average pore size compared to activated carbon electrodes. The state of the art in EC development uses activated carbon (AC) as the electrode material. AC has a high surface area, but its small average pore size inhibits electrolyte ingress/egress. Additionally, AC has a higher resistivity, which generates parasitic heating in high-power applications. This work focuses on fabricating EC from carbon that has a very different structure by increasing the surface area of the GNF by intercalation or exfoliation of the graphitic basal planes. Additionally, various functionalities to the GNS surface will be added that can exhibit pseudocapacitance. This pseudocapacitance exhibits faradaic (charge transfer) properties that can further increase the overall relative and volumetric capacitance of the material. A process is also proposed to use GNF as a precursor material to fabricate GNS that will be used as EC electrodes. This results in much better electrical conductivity than activated carbon. This is advantageous for high-pulsed-power applications to reduce parasitic heating. Larger average pore size allows more complete electrolyte wetting (faster charge transfer kinetics). These properties contribute to a lowered equivalent series resistance (ESR), increased specific power, shorter charging times, and decreased parasitic heating. The high density of basal plane edges provides nucleation sites for activation (addition of hydrophilic functional groups) that facilitate electrolyte wetting, and will contribute to pseudocapacitance.

Marotta, Christopher↗

Using High-Fidelity Analysis Methods and Experimental Results to Account for the Effects of Imperfections on the Buckling Response of Composite Shell Structures

The results of an experimental and analytical study of the effects of initial imperfections on the buckling response of unstiffened thin-walled compression-loaded graphite-epoxy cylindrical shells are presented. The analytical results include the effects of traditional and nontraditional initial imperfections and uncertainties in the values of selected shell parameters on the buckling loads of the shells. The nonlinear structural analysis results correlate very well with the experimental results. The high-fidelity nonlinear analysis procedure used to generate the analytical results can also be used to form the basis of a new shell design procedure that could reduce the traditional dependence on empirical results in the shell design process. KEYWORDS: high-fidelity nonlinear structural analysis, composite shells, shell stability, initial imperfections

Starnes, James H., Jr.↗