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At least 505 records · Page 28

Cobalt nanoparticles confined in carbon matrix for probing the size dependence in Fischer-Tropsch synthesis

The size effect of the metallic Co (Co 0 ) over supported catalysts for Fischer-Tropsch synthesis (FTS) has imposed great importance for developing a high-performance catalyst. However, the lack of well-structured catalysts makes the clarification of the intrinsic size-dependence of Co 0 still a challenge. In this work, the Co/C catalysts with Co 0 particles from 8.4 ± 1.9 to 74.8 ± 11.6 nm were synthesized by well-controlled pyrolysis of ZIF-67. Based on different characterizations, Co/C catalysts via pyrolyzing ZIF-67 above 450 °C were confirmed as Co0 entrapped in partially graphitized carbon matrix polished by a certain amount of pyridinic and graphitic N and a small portion of adsorbed oxygen. Without the limitation of high-temperature reduction and the dispersion-reducibility dependence, the intrinsic size effect of Co 0 on the activity and product selectivity of FTS was rigorously revealed, and the critical size was determined to be 10.5 ± 1.9 nm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Graphene growth by molecular beam epitaxy on the carbon-face of SiC

Graphene layers have been grown by molecular beam epitaxy (MBE) on the (0001) C-face of SiC and have been characterized by atomic force microscopy, low energy electron diffraction (LEED), and UV photoelectron spectroscopy. Contrary to the graphitization process, the step-terrace structure of SiC is fully preserved during the MBE growth. LEED patterns show multiple orientation domains which are characteristic of graphene on SiC (0001), indicating non-Bernal rotated graphene planes. Well-defined Dirac cones, typical of single-layer graphene, have been observed in the valence band for few graphene layers by synchrotron spectroscopy, confirming the electronic decoupling of graphene layers.

36 MATERIALS SCIENCE↗

Transient RF and Optical Plasma Signatures, STL-024-17, Year 1 of 2

Presentation addresses effort to improve understanding of correlations between physical processes and RF signatures by characterizing spectroscopically distinct species (ionic, atomic, molecular) and spectroscopically indistinct charged clusters associated with laser ablation of graphite, and other relevant substrates, under controlled conditions.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Low-Temperature Annealing of Nanoscale Defects in Polycrystalline Graphite

Polycrystalline graphite contains multi-scale defects, which are difficult to anneal thermally because of the extremely high temperatures involved in the manufacturing process. In this study, we demonstrate annealing of nuclear graphite NBG-18 at temperatures below 28 °C, exploiting the electron wind force, a non-thermal stimulus. High current density pulses were passed through the specimens with a very low-duty cycle so that the electron momentum could mobilize the defects without heating the specimen. The effectiveness of this technique is presented with a significant decrease in electrical resistivity, defect counts from X-ray computed tomography, Raman spectroscopy, and nanoindentation-based mechanical characterization. Such multi-modal evidence highlights the feasibility of nanoscale defect control at temperatures about two orders of magnitude below the graphitization temperature.

Liu, Gongyuan↗

Simulated laser-induced breakdown spectra of graphite and synthetic shergottite glass under Martian conditions

We report the results of a simulation of the laser-induced breakdown spectra of graphite and synthetic shergottite glass in an atmosphere similar to that of Mars using a 1-D, Lagrangian hydrodynamic model, a spherical geometry description of the laser ablation and plume expansion and a local thermodynamic equilibrium (LTE) approach for the emission spectra. We compare the LIBS spectra of two calibration targets on board of the Curiosity rover to the simulated ones calculated under nominally the same conditions as those encountered on Mars. The simulations provide an additional way, to laboratory based comparative studies, to better understand the effects of laser parameters and atmospheric pressures. We report on the effect of laser irradiance and ambient pressure on the electron and ion temperature, electron number density, and fluid velocity parameters characterizing the plasma. Lastly, we show the effects of laser irradiance and ambient pressure on the simulated emission spectra of graphite and shergottite and compare them to those acquired by ChemCam. The agreement between the two is good, particularly for the prominent emission lines.

74 ATOMIC AND MOLECULAR PHYSICS↗

Raman Scattering in a New Carbon Material

Samples of a new carbon material, Diamonite-B, were fabricated under high pressure from a commercial carbon black--identified as mixed fullerenes. The new material is neither graphite-like nor diamond-like, but exhibits electrical properties close to graphite and mechanical properties close to diamond. The use of Raman spectroscopy to investigate the vibrational dynamics of this new carbon material and to provide structural characterization of its short-, medium- and long-range order is reported. We also provide the results of investigations of these samples by high-resolution electron microscopy and X-ray diffraction. Hardness, electrical conductivity, thermal conductivity and other properties of this new material are compared with synthetic graphite-like and diamond-like materials, two other phases of synthetic bulk carbon.

Voronov, O. A.↗

Determination of preferential binder oxidation in HTGR matrix material subjected to high temperature steam

Graphitic matrix material encapsulates tristructural isotropic (TRISO) coated fuel particles and is a structural component for both pebble and cylindrical fuel compacts in high temperature gas reactor (HTGR) designs. In an off-normal event involving steam exposure, the matrix material is exposed to oxidants, leading to degradation of the fuel compact and subsequent exposure of the TRISO particle fuel to oxidizing species. This study presents microstructural characterization of matrix material after exposure to high temperature (1200°C), 48 kPa steam in which the evolved microstructure demonstrated nonuniform degradation. Subsequent Raman spectroscopy determined the nature of the remaining material post-exposure. Finally, the electron microscopy characterization suggests and Raman spectroscopic analysis confirms, under off-normal conditions, the carbonized phenolic resin binder is preferentially oxidized ahead of the graphite flake filler and is responsible for the nonuniform degradation and enhanced depth of attack.

36 MATERIALS SCIENCE↗

Hygrothermal properties of composites

The testing procedure and acceptance criteria for outgassing selection of materials to be used in spacecraft has been reviewed. Outgassing testing should be conducted according to ASTM Standard E 595-90. In general, materials with CVCM less than or equal to 0.10% and TML less than or equal to 1.00% are acceptable for space applications. Next, test data on several types of graphite-epoxy composite materials are presented over time at various relative humidity levels at room temperature for moisture absorption, and under vacuum at several temperatures for moisture desorption (outgassing). The data can be accurately represented by simple equations which are useful for materials characterization. Finally, a laser dilatometer systems of extremely high sensitivity and accuracy was assembled and used to measure the coefficient of thermal expansion (CTE) of several types of graphite-epoxy structures, culminating in the ability to perform loading and thermal expansion tests on a prototype optical bench.

Arsenovic, Petar↗

Energy Characterization of the UMD Electron Accelerator

Multiple different groups at Los Alamos National Laboratory have a cited interest in understanding the effects of ionizing radiation in materials. Of especial interest to the ISR division is understanding the effects in materials that are used in the space environment, where radiation is omnipresent and impossible to fully shield from. Development is under way to simulate the effects of radiation damage in detectors and electronics, primarily with particle transport codes such as Geant4 and RAMPART, a code that provides a user friendly interface to Geant4. However, these simulations need benchmarking to experimental tests, some of which have been performed at a variety of small electron accelerator facilities. One of these facilities is the Linear Electron Accelerator at the University of Maryland Radiation Facilities. This facility can provide electron beams on the order of 100 mA delivered in tight macropulse bunches, which allows for experiments where the behavior of electronics is monitored as a function of pulse number. While the beam rates per macropulse of this accelerator is monitored during an experiment via a current pick-off connected to a large graphite beamstop, the energy distribution of this electron beam is not measured during the experiment and has not been well characterized. The energy distribution of the beam is pertinent for these types of experiments, since dose is directly related to energy deposited in a medium. Further, these experiments are performed in open air and sample placement in the room can dictate what dose rate they receive per macropulse. We have created simulated dosemaps for the UMD vault room, but these simulations assume a given energy of the beam, both for calculating the dose and to simulate how much the beam diverges in the air. There have been two attempts now to characterize this accelerator beam energy with a plate type spectrometer, including the most recent experiment earlier this year to quantify the beam energy distribution. These results will also be compared to a dosimetry experiment performed by collaborators at the UMD facility, the details of which are described in Reference. Understanding the electron beam energy is important for future experiments, because the energy directly impacts the dose and radiation damage given to a sample and is important for properly simulating the electron beam when comparing simulation to experiment.

43 PARTICLE ACCELERATORS↗

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↗

Electrochemical carbon deposition from CO 2 in molten carbonates: substrate-dependent growth

Electrochemical carbon deposition from molten carbonate salts using inert electrodes and no additional catalyst is systematically examined. At sufficiently cathodic potentials, carbon formation occurs within 30 min and transitions from substrate-dependent nucleation to carbon-on-carbon growth. Although deposits formed on either mild-steel or graphite cathodes exhibit comparable thicknesses and salt contents, their macrostructures differ, reflecting differences in early-stage growth rates and surface chemistry. Characterization by ICP-OES, Raman spectroscopy, SEM/EDS, synchrotron powder X-ray diffraction, and C K-edge X-ray absorption near edge structure reveals that the as-deposited carbon is predominantly disordered sp 2 -bonded material. However, post-treatment reveals latent turbostratic ordering in select samples, indicating that short-range order is established during deposition but is obscured by an entrained electrolyte and kinetically formed amorphous phases. No anode-derived contamination is detected, and carbon grown on graphite cathodes shows minimal metallic impurities. These results clarify the role of cathode surface chemistry and provide pathways for controlling electrode-derived impurity incorporation and carbon structure in catalyst-free molten carbonate systems.

36 MATERIALS SCIENCE↗

Preparation of a uranium monocarbide anode and electrochemical characterization in molten LiCl-KCl-UCl 3

Porous uranium carbide (UC) pellets possessing moderate electrical conductivity were synthesized by reaction of UO 2 with graphite at temperatures up to 1550°C under rough vacuum. Conversions as high as 98% were achieved at soak times of 2-4 hours. The electrochemistry of the UC pellets in molten LiCl-KCl-6.5 wt% UCl 3 was explored using a variety of techniques including DC polarization methods, cyclic voltammetry, chronopotentiometry and bulk electrolysis. Here, the electrode reaction for anodic dissolution was found to be kinetically controlled by dissociation of UC to a transition state complex that was hypothesized to consist of a uranium atom partially complexed by chloride ions. Precise measurements of current efficiencies using chronopotentiometry indicated upper limits of 90.9 ± 3.4% and 98.3 +1.7/-3.7% for anode and cathode, respectively, when operating at anodic overpotentials near +300 mV. Bulk electrolysis of a UC pellet performed by passing 98% of the theoretical charge resulted in nearly complete recovery of its uranium content as highly pure metal at the cathode.

36 MATERIALS SCIENCE↗

Controlled growth, characterization and thermodynamic behavior of bismuth–tin nanostructures sheathed in carbon nanotubes

We report the controlled synthesis of bismuth–tin (Bi–Sn) nanostructures sheathed in graphitic shells that resemble carbon nanotubes (CNTs). Our approach is based on a simple catalytic chemical vapor deposition over a mixture of Bi{sub 2}O{sub 3} and SnO{sub 2} supplied as starting materials. Shape control of the nanostructures strongly relies on the weight ratio of Bi{sub 2}O{sub 3} and SnO{sub 2}. Sheathed nanoparticles and nanorods are formed at SnO{sub 2} to Bi{sub 2}O{sub 3} weight ratios of less than 4:1. They are composed of two separate crystals: rhombohedral Bi and tetragonal Sn{sub 19}Bi crystals. On the other hand, the sheathed nanowires are formed at SnO{sub 2} to Bi{sub 2}O{sub 3} weight ratios above 4:1. The nanowires have only tetragonal Sn{sub 19}Bi structure with a diameter of approximately 100 nm. Elementary analyses support the core/shell heterostructure of the resulting products. A favorable temperature for the Sn-rich Sn{sub 19}Bi nanowires is in the range of 700–800 °C, more specifically around 750 °C. Thermodynamic analysis reveals that the CNTs play a significant role in the protection of the Bi–Sn nanostructures during phase transition by temperature change. This simple and reproducible method may be extended to the fabrication of similar binary or ternary nanostructures. - Highlights: • Controlled growth of Bi–Sn nanostructures sheathed in CNTs relies on MSnO{sub 2}/MBi{sub 2}O{sub 3}. • Growth mechanism is based on catalytic reaction of C{sub 2}H{sub 2} over an oxide mixture. • Nanoparticles and nanorods consist of rhombohedral Bi and tetragonal Sn{sub 19}Bi. • A favorable temperature for the Sn{sub 19}Bi nanowires is in the range of 700–800 °C. • CNT acts as a protective barrier during phase change of the Bi–Sn nanostructures.

36 MATERIALS SCIENCE↗

Extreme fast charge aging: Effect of electrode loading and NMC composition on inhomogeneous degradation in graphite bulk and electrode/electrolyte interface

Empowering extreme fast charging (XFC) requires a comprehensive understanding of its application with advanced anode and cathode materials in lithium-ion batteries. No report exists for the full extent of limitations for the anode with crosstalk effect from paired cathode as well as Li plating due to electrode loading under XFC. In this study, a combination of cell testing and multiple length characterization is used to investigate XFC aging mechanism in cells with a low loading of 1.5 mAh cm -2 and high loading of 2.5 mAh cm -2 for graphite (Gr)/Ni-rich LiNi x Mn y Co 1-x-y O 2 (NMCs). Operando XRD mappings show 1.5 mAh cm -2 loadings result in higher strain in graphite for all three cathode types. Among the three NMC cathodes, the graphite from NMC532 and NMC811 cells show comparable strain. Scanning electron microscopy (SEM) images show distinct differences between 6-C-charged anodes in two loadings. Significantly increased electrode thickness can be seen due to more damage in the graphite bulk and accumulation of the electrolyte decomposition products in electrode pores. X-ray photoelectron spectroscopy (XPS) reveals both cathode chemistry and Li plating influence the non-uniform SEI composition on graphite surface. We report higher Ni content in NMC811 promotes the higher levels of salt decomposition on the SEI and formation of higher mass of electrolyte aging products.

25 ENERGY STORAGE↗

In-situ study of the carbon gasification reaction of highly oriented pyrolytic graphite promoted by cobalt oxides and the novel nanostructures appeared after reaction

Cobalt interaction and its effects on carbon-based systems at the nanoscale have recently attracted much attention in different fields, such as catalysis of carbon nanotubes or graphene and graphite nano-patterning taking advantage of its ferromagnetic behavior. Experiments performed in our laboratories show how the re-oxidation process of two equivalent monolayers of CoO deposited on highly oriented pyrolytic graphite at 400 °C leads to the formation of nanochannels at lower temperature than using other methods. Here we present the in-situ characterization of the carbon gasification reaction that drives this process by means of near ambient pressure X-ray photoelectron spectroscopy performed at the ALBA synchrotron facility. The reason why this reaction takes place at such low temperature compared to other methods is due to the weakening of the carbon σ bonds by the initial CoO wetting layer formed at the early stages of growth on the graphite surface. Besides nanochannels, ex-situ atomic force microscopy measurements also show the appearance of two more kinds of nanostructures: nano-strips and nano-rings. The appearance of these nanostructures reveals the impressive modification of the surface after the re-oxidation process mediated by the cobalt oxide.

36 MATERIALS SCIENCE↗

Effect of structural disorder on quantum oscillations in graphite

We have studied the effect of structural disorder on the de Haas van Alphen and Shubnikov de Haas quantum oscillations measured in natural, Kish, and highly oriented pyrolytic graphite samples at temperatures down to 30 mK and at magnetic fields up to 14 T. The measurements were performed on different samples characterized by means of x-ray diffractometry, transmission electron microscopy, and atomic-force microscopy techniques. Our results reveal a correlation between the amplitude of quantum oscillations and the sample surface roughness.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

The coupled neutronics and thermo-fluid dynamics design characteristics of the XE-100 200 MW{sub TH} reactor - 18552

The Xe-100 is a high temperature helium-cooled, graphite moderated, pebble bed reactor with a 10 times through, multi-pass (MEDUL=MEhrfacDUrchLauf) fueling scheme. The design, characterized as a Generation IV reactor, is based on proven technology that has been demonstrated a number of times both experimentally and as commercial reactors. This proven foundation ensures high levels of design and technical readiness. In the overview provided of the design it is shown how the excess reactivity is limited by continuous refueling, whilst the selected core power density will ensure passive heat removal. In this way the intrinsic safety design features of a typical GEN IV design are guaranteed. It is shown that no upset event will lead to a significant amount of radiological release. The coupled core neutronic and thermo-fluid dynamics design for the Xe-100 is performed with the VSOP-A system of codes. For the equilibrium core, VSOP results demonstrate that the spherical fuel powers (maximum 1.9 kW) and operational temperatures (<900 deg. C) fall well within the envelope of the design criteria. Adequate reactivity control and long-term, cold shutdown are provided by two separate, diversely-actuated systems, while the overall negative reactivity temperature coefficient is illustrated over the total operational range. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗