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At least 1,081 records · Page 60

Ultra-low-density digitally architected carbon with a strutted tube-in-tube structure

Porous materials with engineered stretching-dominated lattice designs, which offer attractive mechanical properties with ultra-light weight and large surface area for wide-ranging applications, have recently achieved near-ideal linear scaling between stiffness and density. Here, rather than optimizing the microlattice topology, we explore a different approach to strengthen low-density structural materials by designing tube-in-tube beam structures. We develop a process to transform fully dense, three-dimensional printed polymeric beams into graphitic carbon hollow tube-in-tube sandwich morphologies, where, similar to grass stems, the inner and outer tubes are connected through a network of struts. Compression tests and computational modelling show that this change in beam morphology dramatically slows down the decrease in stiffness with decreasing density. In situ pillar compression experiments further demonstrate large deformation recovery after 30–50% compression and high specific damping merit index. Lastly, our strutted tube-in-tube design opens up the space and realizes highly desirable high modulus–low density and high modulus–high damping material structures.

36 MATERIALS SCIENCE↗

Surfactant-assisted synthesis of hybrid lithium iron phosphate nanoparticles for enhancing electrochemical performance

Hybrid nanoparticles of LiFePO{sub 4} with carbon and lithium phosphates were synthesized through organic-inorganic co-assembly procedure using a triblock copolymer (F108 or P123). We found that the triblock copolymers play a critical role in controlling size of hybrid particle and the degree of crystallinity of the inorganic nanostructures. The hybrid using P-123 had more graphitic carbon which resulted in fast electron mobility. Also, magic angle spinning nuclear magnetic resonance (MAS-NMR) revealed that the crystallinity of the hybrid using P123 is higher than that using F108 which is not measurable in X-ray diffraction. Electrochemical performance of the hybrid using P123 as a cathode material in Li-ion batteries showed superior rate capability at 20 C of charging rate and 2 C of discharging rate without capacity loss, in which discharge capacity was 102 mAh/g. - Graphical abstract: Hybrid nanoparticles were synthesized through organic-inorganic co-assembly based on synthetic procedure of mesoporous materials. P123-LFP showed superior high-rate capability at a 20 C charging rate and 2 C discharging rate without capacity loss in Li-ion battery. Highlights: Black-Right-Pointing-Pointer LiFePO{sub 4} nanohybrids are synthesized through the organic-inorganic co-assembly method. Black-Right-Pointing-Pointer Copolymers (F108 or P123) serve as structure directing agents and a carbon source. Black-Right-Pointing-Pointer P123 produces more graphitic carbon and higher crystalline nanohybrids. Black-Right-Pointing-Pointer Nanohybrids using P123 show superior rate capability in Li-ion battery.

36 MATERIALS SCIENCE↗

Ultrafast formation of a transient two-dimensional diamondlike structure in twisted bilayer graphene

Due to the absence of matching carbon atoms at honeycomb centers with carbon atoms in adjacent graphene sheets, theorists predicted that a sliding process is needed to form AA, AB', or ABC stacking when directly converting graphite into sp 3 bonded diamond. Here, using twisted bilayer graphene, which naturally provides AA and AB' stacking configurations, we report the ultrafast formation of a transient two-dimensional diamondlike structure (which is not observed in aligned graphene) under femtosecond laser irradiation. This photoinduced phase transition is evidenced by the appearance of bond lengths of 1.94 and 3.14 Å in the time-dependent differential pair distribution function using MeV ultrafast electron diffraction. Molecular dynamics and first-principles calculation indicate that sp 3 bonds nucleate at AA and AB' stacked areas in a moiré pattern. This work sheds light on the direct graphite-to-diamond transformation mechanism, which has not been fully understood for more than 60 years.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Functionalized Graphene via a One-Pot Reaction Enabling Exact Pore Sizes, Modifiable Pore Functionalization, and Precision Doping

Functionalizing graphene with exact pore size, specific functional groups, and precision doping poses many significant challenges. Current methods lack precision and produce random pore sizes, sites of attachment, and amounts of dopant, leading to compromised structural integrity and affecting graphene’s applications. In this work, we report a strategy for the synthesis of functionalized graphitic materials with modifiable nanometer-sized pores via a Pictet–Spengler polymerization reaction. This one-pot, four-step synthesis uses concepts based on covalent organic frameworks (COFs) synthesis to produce crystalline two-dimensional materials that were confirmed by PXRD, TEM measurements, and DFT studies. These new materials are structurally analogous to doped graphene and graphene oxide (GO) but, unlike GO, maintain their semiconductive properties when fully functionalized.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Formation of Carbon Nanotube Based Gears: Quantum Chemistry and Molecular Mechanics Study of the Electrophilic Addition of o-Benzyne to Fullerenes, Graphene, and Nanotubes

Considerable progress has been made in recent years in chemical functionalization of fullerene molecules. In some cases, the predominant reaction products are different from those obtained (using the same reactants) from polycyclic aromatic hydrocarbons (PAHs). One such example is the cycloaddition of o-benzyne to C60. It is well established that benzyne adds across one of the rings in naphthalene, anthracene and other PAHs forming the [2+4] cycloaddition product (benzobicyclo[2.2.2.]-octatriene with naphthalene and triptycene with anthracene). However, Hoke et al demonstrated that the only reaction path for o-benzyne with C60 leads to the [2+2] cycloaddition product in which benzyne adds across one of the interpentagonal bonds (forming a cyclobutene ring in the process). Either reaction product results in a loss of aromaticity and distortion of the PAH or fullerene substrate, and in a loss of strain in the benzyne. It is not clear, however, why different products are preferred in these cases. In the current paper, we consider the stability of benzyne-nanotube adducts and the ability of Brenner's potential energy model to describe the structure and stability of these adducts. The Brenner potential has been widely used for describing diamondoid and graphitic carbon. Recently it has also been used for molecular mechanics and molecular dynamics simulations of fullerenes and nanotubes. However, it has not been tested for the case of functionalized fullerenes (especially with highly strained geometries). We use the Brenner potential for our companion nanogear simulations and believe that it should be calibrated to insure that those simulations are physically reasonable. In the present work, Density Functional theory (DFT) calculations are used to determine the preferred geometric structures and energetics for this calibration. The DFT method is a kind of ab initio quantum chemistry method for determining the electronic structure of molecules. For a given basis set expansion, it is comparable in accuracy to the MP2 method (better than Hartree Fock, but less accurate than more extensive electron correlation methods such as MP4 or CCSD). However, for systems with large numbers of basis functions it more efficient than any other methods that include electron correlation effects. In this presentation we show the results of DFT calculations for the reaction of benzyne with naphthalene, C60, and nanotube models. We compare energies for [2+2] and [2+4] cycloaddition products. The preferred products for the naphthalene and C60 reactions have been determined by experiment and, thus, these cases serve as a validation of our quantum chemical approach. We also compare the DFT and Brenner potential results. Finally we can predict the likelihood of reaction between benzyne and nanotubes.

Jaffe, Richard↗

Graphitic encapsulation of MgO and Fe{sub 3}C nanoparticles in the reaction of iron pentacarbonyl with magnesium

A simple method to produce highly ordered carbon nanostructures by combustion synthesis is presented. Graphite-encapsulated magnesium oxide, iron carbide nanoparticles and carbon nanobelts were synthesized by the one-step reduction of iron pentacarbonyl with magnesium. High-resolution transmission electron microscopy analysis of the products revealed nanocrystalline MgO and Fe{sub 3}C particles surrounded by a well-crystallized, tight graphite film. The possible formation mechanism is presented and discussed. - Highlights: • We present a simple method to produce highly ordered carbon nanostructures by combustion synthesis. • The cubic MgO particles are completely coated by tight graphitic shells. • The mechanism of formation a distant carbon film on MgO surface has been discussed. • The presented method can be applied to synthesis of other core-shell structures.

36 MATERIALS SCIENCE↗

Thermally Driven Structure and Performance Evolution of Atomically Dispersed FeN 4 Sites for Oxygen Reduction

Abstract FeN 4 moieties embedded in partially graphitized carbon are the most efficient platinum group metal free active sites for the oxygen reduction reaction in acidic proton‐exchange membrane fuel cells. However, their formation mechanisms have remained elusive for decades because the Fe−N bond formation process always convolutes with uncontrolled carbonization and nitrogen doping during high‐temperature treatment. Here, we elucidate the FeN 4 site formation mechanisms through hosting Fe ions into a nitrogen‐doped carbon followed by a controlled thermal activation. Among the studied hosts, the ZIF‐8‐derived nitrogen‐doped carbon is an ideal model with well‐defined nitrogen doping and porosity. This approach is able to deconvolute Fe−N bond formation from complex carbonization and nitrogen doping, which correlates Fe−N bond properties with the activity and stability of FeN 4 sites as a function of the thermal activation temperature.

Li, Jiazhan↗

Synergistic Effects of Nano-zinc Oxide on Improving the Flame Retardancy of EVA Composites with an Efficient Triazine-Based Charring Agent

The synergistic effect of nano-zinc oxide (nano-ZnO) on the flame retardancy and thermal stability of intumescent flame retardant ethylene–vinyl acetate (EVA/IFR) consisting of novel hyperbranched triazine-based charring agent (HTCFA) and APP was evaluated by limiting oxygen index (LOI), UL-94 measurement, cone calorimeter test (CCT) and thermogravimetric analysis (TGA), and the residue analysis was also carried out through scanning electron microscopy (SEM), fourier transform infrared (FTIR), laser raman spectroscopy (LRS), and X-ray photoelectron spectroscopy (XPS). The results showed that introducing a certain amount of nano-ZnO could obviously enhance LOI value and UL-94 rating, and effectively restrain the combustion performance of EVA/IFR composites, leading to the decrease of heat and smoke release. The addition of 0.5 wt% nano-ZnO into EVA/IFR composite obtained the highest catalytic effectivity (CAT-EFF). TGA results uncovered a distinct synergistic carbonization effect existed between nano-ZnO and IFR, and nano-ZnO could obviously improve the high-temperature thermal stability and promote the char formation of IFR and EVA/IFR. Analysis of final char residues proved that the incorporation of appropriate amount of nano-ZnO contributed to remaining more P and forming more high-quality graphitization char layers with richer P–O–C and P–N cross-linking structures in condensed phase owing to the catalytic carbonization effect of nano-ZnO on IFR system, which played a critical role in remarkable improvement of flame retardancy and smoke suppression properties of composites.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

CO 2 Activation on Ni(111) and Ni(100) Surfaces in the Presence of H 2 O: An Ambient-Pressure X-ray Photoelectron Spectroscopy Study

Nickel-based catalysts play an important role in the chemical transformation of CO 2 . A fundamental understanding of the interaction between CO 2 and Ni surfaces at atomic level is necessary. In this study, the interfacial reactions of CO 2 and CO 2 + H 2 O mixture on Ni(111) as well Ni(100) surfaces were investigated using ambient pressure X-ray photoelectron spectroscopy as well as theoretical calculations. The results indicate that the distributions of dissociation products are very different on the Ni(111) and Ni(100) surfaces. Carbonate, CO, and graphitic carbon formed on both Ni(111) and Ni(100) surfaces in the presence of 0.2 Torr CO 2 . However, more than 90% adsorption species on the Ni(111) surface is the carbonate, whereas the Ni(100) surface is mainly covered by adsorbed CO* and graphitic carbon. The co-adsorption of H 2 O weakens the influence of structure effect on the interfacial interaction between CO 2 and Ni surfaces. Furthermore, the density functional theory calculations suggest that the activation of CO 2 on Ni(111) and Ni(100) tends to follow different reaction paths, which are consistent with the experimental results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Viability of Additively Manufactured Electrodes for Lithium-Ion Batteries

As the global economy becomes increasingly electrified, the demand for batteries and energy storage is expected to rise significantly, particularly in the transportation and electricity sectors. Lithium-ion batteries (LIBs) are currently the most advanced and widely used technology in this field. Traditionally, LIBs are manufactured using simple 2D planar geometries to maximize production efficiency and minimize costs. However, this approach limits energy density due to the restricted design flexibility of the electrodes. Additive manufacturing (AM) offers a promising solution to enhance the energy density and efficiency of LIBs by enabling the design of architectures that reduce diffusive losses and allow for a greater amount of active material to be incorporated within the same device footprint, thereby minimizing the use of inactive materials. Different AM techniques come with their own set of limitations, including printing speed, material compatibility, and scale, which must be considered when designing electrodes. Scalable and cost-effective methods are particularly important for electric vehicle batteries, while achieving higher energy densities in microbatteries is crucial for the miniaturization of wearable electronics and medical devices. Here, in this study, we simulate various 3D porous electrode designs for LIBs using graphite and nickel manganese cobalt oxide (NMC) electrodes. These designs are selected to represent structures that could be produced using different AM techniques, such as direct ink writing, fused deposition modeling, and stereolithography. Our results indicate that at higher charging rates and increased areal mass loading, 3D structures can outperform traditional 2D electrodes, although the benefits may diminish with more complex designs that are harder to manufacture. The observed gains in energy density are attributed to improved electrode utilization and reduced diffusive energy losses. This comprehensive analysis of structure–performance relationships will provide valuable insights to guide future research on 3D designs, material selection, and AM techniques for additively manufactured battery electrodes.

25 ENERGY STORAGE↗

Controllable conversion of quasi-freestanding polymer chains to graphene nanoribbons

In the bottom-up synthesis of graphene nanoribbons (GNRs) from self-assembled linear polymer intermediates, surface-assisted cyclodehydrogenations usually take place on catalytic metal surfaces. Here we demonstrate the formation of GNRs from quasi-freestanding polymers assisted by hole injections from a scanning tunnelling microscope (STM) tip. While catalytic cyclodehydrogenations typically occur in a domino-like conversion process during the thermal annealing, the hole-injection-assisted reactions happen at selective molecular sites controlled by the STM tip. The charge injections lower the cyclodehydrogenation barrier in the catalyst-free formation of graphitic lattices, and the orbital symmetry conservation rules favour hole rather than electron injections for the GNR formation. The created polymer–GNR intraribbon heterostructures have a type-I energy level alignment and strongly localized interfacial states. Lastly, this finding points to a new route towards controllable synthesis of freestanding graphitic layers, facilitating the design of on-surface reactions for GNR-based structures.

36 MATERIALS SCIENCE↗

Interface synergism and engineering of Pd/Co@N-C for direct ethanol fuel cells

Direct ethanol fuel cells have been widely investigated as nontoxic and low-corrosive energy conversion devices with high energy and power densities. It is still challenging to develop high-activity and durable catalysts for a complete ethanol oxidation reaction on the anode and accelerated oxygen reduction reaction on the cathode. The materials’ physics and chemistry at the catalytic interface play a vital role in determining the overall performance of the catalysts. Herein, we propose a Pd/Co@N-C catalyst that can be used as a model system to study the synergism and engineering at the solid-solid interface. Particularly, the transformation of amorphous carbon to highly graphitic carbon promoted by cobalt nanoparticles helps achieve the spatial confinement effect, which prevents structural degradation of the catalysts. The strong catalyst-support and electronic effects at the interface between palladium and Co@N-C endow the electron-deficient state of palladium, which enhances the electron transfer and improved activity/durability. The Pd/Co@N-C delivers a maximum power density of 438 mW cm -2 in direct ethanol fuel cells and can be operated stably for more than 1000 hours. This work presents a strategy for the ingenious catalyst structural design that will promote the development of fuel cells and other sustainable energy-related technologies.

25 ENERGY STORAGE↗

Detecting divertor damage during steady state operation of Wendelstein 7-X from thermographic measurements

Wendelstein 7-X (W7-X) aims to demonstrate the reactor capability of the stellarator concept, by creating plasmas with pulse lengths of up to 30 min at a heating power of up to 10 MW. The divertor plasma facing components will see convective steady state heat flux densities of up to 10 MW/m 2 . These high heat flux target elements are actively cooled and are covered with carbon fibre reinforced carbon (CFC) as plasma facing material. The CFC is bonded to the CuCrZr cooling structure. Over the life time of the experiment this interface may weaken and cracks can occur, greatly reducing the heat conduction between the CFC tile and the cooling structure. Furthermore, there is not only the need to monitor the divertor to prevent damage by overheating but also the need to detect these fatigue failures of the interface. A method is presented for an early detection of fatigue failures of the interface layer, solely by using the information delivered by the IR-cameras monitoring the divertor. This was developed and validated through experiments made with high heat flux target elements prior to installation in W7-X.

47 OTHER INSTRUMENTATION↗

Precise measurement of single carbon nanocoils using focused ion beam technique

We have developed a precise resistivity measurement system for quasi-one-dimensional nanomaterials using a focused ion beam. The system enables the resistivity of carbon nanocoils (CNCs) to be measured and its dependence on coil geometry to be elucidated. At room temperature, the resistivity of CNCs tended to increase with coil diameter, while that of artificially graphitized CNCs remained constant. These contrasting behaviors indicate coil-diameter-induced enhancement in structural disorder internal to CNCs. Low-temperature resistivity measurements performed on the CNCs revealed that electron transport through the helical axis is governed by the variable range hopping mechanism. The characteristic temperature in variable range hopping theory was found to systematically increase with coil diameter, which supports our theory that the population of sp{sup 2}-domains in CNCs decreases considerably with coil diameter.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

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↗

Graphene-based modulation-doped superlattice structures

The electronic transport properties of graphene-based superlattice structures are investigated. A graphene-based modulation-doped superlattice structure geometry is proposed consisting of periodically arranged alternate layers: InAs/graphene/GaAs/graphene/GaSb. The undoped graphene/GaAs/graphene structure displays a relatively high conductance and enhanced mobilities at increased temperatures unlike the modulation-doped superlattice structure, which is more steady and less sensitive to temperature and the robust electrical tunable control on the screening length scale. The thermionic current density exhibits enhanced behavior due to the presence of metallic (graphene) monolayers in the superlattice structure. The proposed superlattice structure might be of great use for new types of wide-band energy gap quantum devices.

36 MATERIALS SCIENCE↗

Preparation of Mesophase Pitch Feedstock for Carbon Fiber

A filtration process of the low cost mesophase pitch developed by Advanced Carbon Products, LLC (ACP) was developed. The mesophase pitch was melt spun into fiber at the University of Kentucky Center for Applied Energy Research (UKY), and converted to carbon fiber. The melt spinning process was moderately stable, but resulted in some void structure in the green fibers. The tensile properties of the resulting carbon fibers, after graphitization heat treatment, were tested yielding a modulus value of approximately 560 GPa or 81 MSI. This demonstrated that a high modulus graphitic carbon fiber is certainly possible from the ACP 20 mesophase pitch. For future work, a better balance between the softening point temperature, the spinning temperature, and filtering must be met to reduce the volatiles generated in the pitch during spinning. This would reduce voids in the fiber, facilitate spinning, and generate finer, higher performance graphitic fiber.

36 MATERIALS SCIENCE↗

INL Report: Multiphysics Modeling and Simulation of Deimos, an Advanced Reactor Experiment

When designing a novel reactor, nuclear experiments are essential to validate the predictive capability of modeling/simulation tools and to justify the investment of a full-scale prototype. Being able to accurately predict temperature reactivity coefficients is of high importance to reactor designers as it impacts the safety and performance of the system. Deimos is a proposed graphite-moderated, beryllium-reflected, high assay low-enriched uranium (HALEU) tri-structural isotropic (TRISO) fueled experiment for NCERC. Deimos is a valuable experiment for validating the predictive performance of modeling and simulation tools since it comprises a relatively thermal energy spectrum with 84% thermal neutrons causing fission, 15% epithermal neutrons causing fission, and 1% fast neutrons causing fission. Additionally, by electrically heating the experiment, reactivity can be validated at various temperatures. Deimos will serve as a testbed for future advanced reactor concepts.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗