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At least 235 records · Page 13

The low temperature oxidation of lithium thin films on HOPG by O 2 and H 2 O

Lithiated graphite and lithium thin films have been used in fusion devices. In this environment, lithiated graphite will undergo oxidation by background gases. In order to gain insight into this oxidation process, thin (< 15 monolayer (ML)) lithium films on highly ordered pyrolytic graphite (HOPG) were exposed in this paper to O 2(g) and H 2 O (g) in an ultra-high vacuum chamber. High resolution electron energy loss spectroscopy (HREELS) was used to identify the surface species formed during O 2(g) and H 2 O (g) exposure. Auger electron spectroscopy (AES) was used to obtain the relative oxidation rates during O 2(g) and H 2 O (g) exposure. AES showed that as the lithium film thickness decreased from 15 to 5 to 1 ML, the oxidation rate decreased for both O 2(g) and H 2 O (g) . HREELS showed that a 15 ML lithium film was fully oxidized after 9.7 L (L) of O 2(g) exposure and Li 2 O was formed. HREELS also showed that during initial exposure (< 0.5 L) H 2 O (g) , lithium hydride and lithium hydroxide were formed on the surface of a 15 ML lithium film. Finally, after 0.5 L of H 2 O (g) exposure, the H 2 O (g) began to physisorb, and after 15 L of H 2 O (g) exposure, the 15 ML lithium film was not fully oxidized.

36 MATERIALS SCIENCE↗

From graphite-clay composites to graphene electrode materials: In-situ electrochemical oxidation and functionalization

Highlights: • Graphene was synthesized by electrochemical exfoliation of graphite-clay rods with different clay:graphite ratios. • In-situ electrochemical oxidation and functionalization were used in the exfoliated process. • Graphene thin-film electrodes were constructed for supercapacitors and lithium ion batteries. • This work provided a value-added way that can transform the low-purity graphite resources to graphene electrode materials. - Abstract: The development of cost- and time-effective methods to synthesize graphene materials is very urgent in order to promote its large-scale application in electrochemical energy storage devices. Herein, graphene materials were synthesized by the electrochemical exfoliation (electrochemical oxidation) of graphite-clay rods with different clay:graphite ratios in aqueous solution and in short reaction time (1 h). The dual role of electrochemical oxidation reaction was presented: (1) the electrochemical oxidation reaction facilitates the exfoliation of pencil graphite leads and in-situ forms functional groups on graphene; (2) the electrochemical oxidation reaction enhances the Faradaic reaction in supercapacitor. The in-situ electrochemical oxidation and functionalization methods can transform low purity graphite to high-value graphene electrode materials for supercapacitors and lithium ion batteries. The specific capacitances of exfoliated graphene are 20-time larger than that of graphite-clay composites. This work provided a value-added way that can transform the low-purity graphite resources to high performance graphene electrode materials.

36 MATERIALS SCIENCE↗

DETERMINATION OF EMISSIVITY OF MATERIALS.

During the third quarter of the contractual year of Contract NASW-104 for the determination of emissivity of materials, the emittance of nine specimens was measured at temperatures ranging up to 2200F and at pressures averaging 10(exp -8) mm Hg. The materials tested included columbium, columbium with an oxidized surface, molybdenum, graphite varnish on Type 310 stainless steel, stainless steel with an oxidized surface, and platinum black. In the spectral emittance rig, spectral as well as total emittance was measured on three specimens and total emittance only was measured on a fourth. In the total emittance rig, total emittance data was obtained on five specimens. Two of the specimens were endured. Investigations were made concerning the operational characteristics of both rigs in order to eliminate possible sources of error in the data. On the spectral emittance rig, tests were conducted to determine the exact magnitude of any error introduced in the spectral emittance values by beam intermixing resulting from imperfections in the optical system. On the total emittance rig, work was concentrated on the determination of the relative accuracy of the chromel-alumel and platinum-platinum 10% rhodium thermocouples used to measure the temperature of the specimen.

Emission↗

Mixed effects associated with air ingress in graphite channels

The next generation of nuclear power plants, such as Modular High Temperature Gas-Cooled Reactors (MHTGR), have passive safety design features to overcome transients during off-normal operation but it is unproven whether their safety systems will perform as per design requirements. The design and construction of a facility, to investigate the passive safety response of the complete reactor system will require significant resources. Therefore, a practical approach is to improve the understanding of this multi-physics or mixed effect problem in laboratory scale set-ups and computational models. The HTGR related separate effects experiments at academic institutions and other laboratories have been developed to provide validation data and complement computational efforts to identify critical issues related to passive safety design. There are several separate effect experimental studies currently under investigation or recently conducted by several academic institutions in U.S and throughout the world. The High Temperature Test Facility (HTTF) has been constructed at Oregon State University to conduct integral thermal-hydraulics experiments for the development of HTGRs. For Depressurized Conduction Cooling (DCC) experiments in HTTF, a mixture of nitrogen and helium gas is used to study internal natural convection up to 650?C. Similarly many other experimental studies have emphasized on HTGR core and plenum-to-plenum thermal-hydraulic behavior but with inert gases such as nitrogen or non-oxidizing solid substitutes for graphite. There is limited experimental data of mixed oxidation effects upon air ingress in nuclear grade graphite leading changes to thermal properties, heat generation due to chemical reactions and natural convection of air-helium mixture inside core at high temperatures (above 900?C). This work describes a unique experimental set-up developed by authors to conduct these mixed effect experiments. The current work is equally relevant to the designs well known by other names or geometries such as Very High Temperature Reactors (VHTRs) and Pebble Bed Modular Reactors (PBMRs). A common feature of HTGRs with passive safety design is that under certain accident conditions the decay heat is dissipated passively from the core by radiation/conduction/convection heat transport to the surrounding environment. Passive decay heat removal is one of the prime passive safety features of HTGRs and the heat conduction through the internal core region, graphite matrix, to the periphery is one of the major mechanisms of passive safety in HTGRs. The conduction and radiation heat transfer provide long-term heat removal but, during a Depressurized Loss of Forced Coolant (DLOFC) accident, the anticipated break in the coolant system will allow air ingress into the hot core region and can lead to graphite oxidation, which will negatively impact the core thermal behavior. In addition, air will also impact natural circulation of Helium and thus diminish the heat removal rate, which can further increase the graphite temperature. Therefore, both air ingress can eventually give rise to thermal instabilities and then to possible situations for breaching the safety envelope of TRISO fuel. This research summary is organized to present the background on oxidation studies, description of experimental setup and discussion of results in the following sections. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Kinetics and transport of hydrogen in graphite at high temperature and the effects of oxidation, irradiation and isotopics

The kinetics of uptake and desorption impact the performance of graphite as a vector for tritium in high-temperature fission reactors and in the blanket of fusion reactors. Graphite components in these reactors are exposed to temperatures > 500 °C and H 2 partial pressures of few Pa and desorption temperatures are limited to < 1600 °C; limited data is available at these conditions. Here we review the mechanisms for uptake in, transport and desorption of hydrogen from graphite at high temperature, compiling data on uptake rates, diffusion coefficients and activation energies and providing a discussion of the impact of irradiation, pre-oxidation and isotope. At FHR conditions, trapping impacts uptake rates, leading to a reduction in apparent diffusivity by 35 to 80% compared to higher partial-pressure uptake. Timelines for desorption are not clearly defined; extrapolating from available data, at 1150 °C desorbing 80% of tritium uptaken at FHR conditions may take from 100 to 10,000 h.

36 MATERIALS SCIENCE↗

Graphite-fiber-reinforced polyimide liners of various compositions in plain spherical bearings

A plain spherical bearing design with a ball diameter of 28.6 mm, a race length of 12.7 mm, and a 1.7-mm-thick, molded composite liner was evaluated. The liner material is a self-lubricating composite of graphite-fiber-reinforced polyimide resin (GFRPI). The liner is prepared by transfer molding a mixture of one part chopped graphite fiber and one part partially polymerized resin into the space between the bearing ball and the outer race and then completing the polymerization under heat and pressure. Several liner compositions were evaluated: two types of polyimide, condensation and addition; two types of graphite fiber, low and high modulus; and four powder additives - cadmium oxide, cadmium iodide, graphite fluoride, and molybdenum disulfide. The bearings were oscillated + or - 15 deg at 1 Hz for 20 kilocycles under a radial unit load of 29 MN sq m (4200 psi) in dry air at 25, 200, or 315 C. Both types of fiber and polyimide gave low friction and wear. A simple equation was developed to fit the wear-time data and adequately predicted wear to 100 kilocycles.

Sliney, H. E.↗

Investigation of Ceramic, Graphite, and Chrome-plated Graphite Nozzles on Rocket Engine

The use of ceramic material for rocket nozzles and the effectiveness of preventing oxidation and erosion of graphite nozzles by chrome-plating the internal surface were investigated. A supported ceramic nozzle, cracked by initial operation, was operated a second time without further cracking or damage. Chrome-plating the internal surface of graphite nozzles effectively prevented oxidation and erosion that occurred during operation with unprotected graphite.

CERAMICS↗

Electrochemical behavior and separation of iodide in molten LiF-NaF-KF melt

This work studied the electrochemical behavior of iodide in molten LiF-NaF-KF mixture and the separation of iodide from the molten salt at 973 K using a graphite working electrode. The cyclic voltammetry (CV) and chronoamperometry (CA) measurements indicated an anodic passivation layer was formed on the graphite electrode in this melt and the layer blocked the charge transfer across the electrolyte/electrode interface. However, the added I- ions could pass through the passivation layer and were oxidized at the graphite electrode. The characterization of the obtained products proved that iodide ions was efficiently oxidized to I2 gas during electrolysis. Furthermore, the graphite anode showed excellent stability without any obvious change in dimensions after electrolysis, which showed the high current efficiency of I2 evolution reaction. Thus, the graphite electrode was possible to be served as an excellent anode to separate other anions (such as Br) from molten fluoride salts.

36 MATERIALS SCIENCE↗

Boron Carbide Synthesis in Low-Voltage DC Electric Arc Initiated in Open Air

We describe a method of obtaining ultrafine boron carbide (B{sub 13}C{sub 2}) powder using the effect of a dc electric arc on a mixture of initial reactants containing carbon and boron. A peculiarity of the proposed method is that it can be implemented using arc discharge operating in open air without any vacuum equipment and protective inert gas atmosphere. X-ray diffraction data showed that the synthesized product in the general case contained three crystalline phases: boron carbide (B{sub 13}C{sub 2}), graphite (C), and boron oxide (B{sub 2}O{sub 3}). Electron-microscopic examination showed that the average size of boron carbide particles ranged from ~50 nm to ~2 μm.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Graphite Microstructural Characterization Using Time-Domain and Correlation-Based Ultrasonics

Among techniques that have been used to determine elastic modulus in nuclear graphites, ultrasonic methods have enjoyed wide use and standards using contacting piezoelectric tranducers have been developed to ensure repeatability of these types of measurements. However, the use of couplants and the pressures used to effectively couple transducers to samples can bias measurements and produce results that are not wholly related to the properties of the graphite itself. In this work, we have investigated the use of laser ultrasonic methods for making elastic modulus measurements in nuclear graphites. These methods use laser-based transmitters and receivers to gather data and do not require use of ultrasonic couplants or mechanical contact with the sample. As a result, information directly related to the elastic responses of graphite can be gathered even if the graphite is porous, brittle and compliant. In particular, we have demonstrated the use of laser ultrasonics for the determination of both Young’s modulus and shear modulus in a range of nuclear graphites including those that are being considered for use in future nuclear reactors. These results have been analyzed to assess the contributions of porosity and microcracking to the elastic responses of these graphites. Laser-based methods have also been used to assess the moduli of NBG-18 and IG-110 where samples of each grade were oxidized to produce specific changes in porosity. These data were used to develop new models for the elastic responses of nuclear graphites and these models have been used to infer specific changes in graphite microstructure that occur during oxidation that affect elastic modulus. Specifically, we show how ultrasonic measurements in oxidized graphites are consistent with nano/microscale oxidation processes where basal plane edges react more readily than basal plane surfaces. We have also shown the use of laser-based methods to perform shear-wave birefringence measurements and have shown how these measurements can be used to assess elastic anisotropy in nuclear graphites. Using models developed in this program, ultrasonic data were interpreted to extract orientation distribution coefficients that could be used to represent anisotropy in these materials. This demonstration showed the use of ultrasonic methods to quantify anisotropy and how these methods provide more detailed information than do measurements of thermal expansion – a technique commonly used for assessing anisotropy in nuclear graphites. Finally, we have employed laser-based, ultrasonic-correlation techniques in attempts to quantify aspects of graphite microstructure such as pore size and distribution. Results of these measurements indicate that additional work must be performed to make this ultrasonic approach viable for quantitative microstructural characterization.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Solar tests of aperture plate materials for solar thermal dish collectors

In parabolic dish solar collectors, walk-off of the spot of concentrated sunlight is a hazard if a malfunction causes the concentrator to stop following the Sun. Therefore, a test program was carried out to evaluate the behavior of various ceramics, metals, and polymers under solar irradiation of about 7000 kW/sq m. (peak) for 15 minutes. The only materials that did not slump or shatter were two grades of medium-grain extruded graphite. High purity, slip-cast silica might be satisfactory at somewhat lower flux. Oxidation of the graphite appeared acceptable during tests simulating walk-off, acquisition (2000 cycles on/off Sun), and spillage (continuous on-Sun operation).

Jaffe, L. D.↗

Oxidation of Silicon Carbide with Atomic Oxygen through the Passive-to-Active Transition

The inelastic and reactive scattering dynamics of O( 3 P) atoms on a 6H-silicon carbide (SiC) surface were investigated as a function of temperature with a molecular beam-surface scattering technique that employed a rotatable mass spectrometer detector. One set of experiments used a pulsed hyperthermal beam that produced ~8 km s –1 O atoms, and another set of experiments used a continuous beam that contained O atoms with a nominal velocity of ~2 km s –1 . When exposed to the relatively low-flux, pulsed hyperthermal O-atom beam, a passive oxide layer on the SiC that formed at lower temperatures decomposed as the temperature increased above 1673 K. Instead of entering an active oxidation regime, a graphitic layer formed on the surface and largely protected the underlying SiC from incoming O atoms. Investigation of the oxide decomposition without O-atom bombardment revealed volatile Si and SiO products at the moment that the oxide decomposed, implying that Si sublimation occurs concurrently with oxide decomposition. In the experiment with the continuous (higher flux) O-atom beam, volatile SiO and CO products were observed after the passive oxide decomposed, indicating that active oxidation was reached. Finally, the results of this study provide evidence for the importance of Si sublimation within the active oxidation regime. Above the passive-to-active transition temperature, Si sublimation is an ongoing process, and continuous active oxidation will only occur if sufficient oxygen reacts with the surface to produce SiO more quickly than a graphitic layer can form. Thus, accurate models of SiC ablation by atomic oxygen must account for multiple competing mechanisms that depend on the surface temperature and incident O-atom flux.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spatially-resolved lithiation dynamics from operando X-ray diffraction and electrochemical modeling of lithium-ion cells

In this study, energy dispersive X-ray diffraction is used to profile the time evolution of ordered Li x C 6 phases in solid electrodes of lithium-ion cells charged at rates between 0.2 and 4.7C (where 1C corresponds to full discharge in 1 h). The methods for quantifying lithium concentration in these phases from the acquired diffraction patterns are described. Compact expressions for time-dependent concentration gradients in the solid electrodes using orthogonal polynomial expansions are presented. Experimentally, these gradients persisted in lithiated graphite electrodes even after the cells rested at open-circuit for over 9 h. A multiphase electrochemical model of graphite intercalation captured many of the observed behaviors, including the progression of phase transitions and the persistent gradients at zero current. However, the magnitude of concentration gradients in both the oxide cathode and graphite anode is underestimated by the model, even at moderate currents.

25 ENERGY STORAGE↗

Molecular beam epitaxy growth of SrO buffer layers on graphite and graphene for the integration of complex oxides

Here, we report the successful growth of high-quality SrO films on highly-ordered pyrolytic graphite (HOPG) and single-layer graphene by molecular beam epitaxy. The SrO layers have (001) orientation as confirmed by X-ray diffraction (XRD) while atomic force microscopy measurements show continuous pinhole-free films having rms surface roughness of <1.5 Å. Moreover, transport measurements of exfoliated graphene, after SrO deposition, show a strong dependence between the Dirac point and Sr oxidation. As a result, the SrO is leveraged as a buffer layer for more complex oxide integration via the demonstration of (001) oriented SrTiO3 grown atop a SrO/HOPG stack.

36 MATERIALS SCIENCE↗

Optical properties of graphene-based materials in transparent polymer matrices

Different aspects of graphene-based materials (GBMs) and GBM-nanocomposites have been investigated due to their intriguing features; one of these features is their transparency. Transparency of GBMs has been of an interest to scientists and engineers mainly with regard to electronic devices. In this study, optical transmittance of structural, purpose-made nanocomposites reinforced with GBMs was analyzed to lay a foundation for optical microstructural characterization of nanocomposites in future studies. Two main types of GBM reinforcements were studied, graphene oxide (GO) and graphite nanoplates (GNPs). The nanocomposites investigated are GO/poly(vinyl alcohol), GO/sodium alginate, and GNP/epoxy with different volume fractions of GBMs. Together with UV-visible spectrophotometry, image-processing-assisted micro and macro photography were used to assess the transparency of GBMs embedded in the matrices. The micro and macro photography methods developed were proven to be an alternative way of measuring light transmittance of semi-transparent materials. It was found that there existed a linear relationship between light absorbance and a volume fraction of GBMs embedded in the same type of polymer matrices, provided that the nanocomposites of interest had the same thicknesses. This suggests that the GBM dispersion characteristics in the same type of polymer are similar and any possible change in crystal structure of polymer due to different volumetric contents of GBM does not have an effect on light transmittance of the matrices. The study also showed that the same types of GBMs could display different optical properties in different matrix materials. The results of this study will help to develop practical microstructural characterization techniques for GBM-based nanocomposites.

36 MATERIALS SCIENCE↗

SAM Code Development for Source Term Modeling in Fluoride-salt-cooled High-temperature Reactors

The SAM code is under development and supported by DOE-NE’s Nuclear Energy Advanced Modeling and Simulation program as a modern system-level modeling and simulation tool for advanced non-light water reactor safety analyses. These advanced reactor concepts incorporate novel and improved approaches to achieve safety and economic feasibility. Many concepts leverage higher operating temperatures for improved efficiency with a variety of coolants and structural materials to support those needs. Such design choices may also pose unique radiological source term risks. There are continuous efforts to incorporate new physics and phenomena relevant to advanced reactor concepts, including capabilities to enable system-level source term modeling. The Pebble-Bed Fluoride-salt-cooled High-temperature Reactor (PB-FHR) is a promising candidate among advanced nuclear reactor concepts with its improved passive safety characteristics and high thermal efficiency. In addition to past efforts to support the development and utilization of SAM for PB-FHR safety analysis, the species transport modeling capabilities in SAM have been extended to simulate source term phenomena in concepts like the PB-FHR. The PB-FHR concept utilizes pebble-form TRISO fuel and FLiBe salt coolant to provide robust barriers to the release of almost all fission products and radiological source terms. However, tritium poses a unique radiological risk due to its significant production from neutron interactions with 6 Li and 9 Be in the FLiBe as well as its high mobility at elevated temperatures where it can permeate through structural metals. Secondly, the use of graphite at elevated temperatures poses the risk of oxidation damage to any structural components or fuel pebbles that are exposed to accidental air ingress. This report summarizes progress made in modeling these phenomena in SAM, which leverages the system-level multi-physics thermal hydraulic simulation to support an effective engineering-scale source term modeling capability. A tritium transport model is developed to simulate the various transport pathways in FHR and MSR concepts and is presented through verification and validation examples as well as demonstrations simulating experimental test loops and reference plant FHR models. A graphite oxidation model is also introduced to calculate local oxidation rates and is presented with initial validation results.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Low temperature chemical processing of graphite-clad nuclear fuels

A reduced-temperature method for treatment of a fuel element is described. The method includes molten salt treatment of a fuel element with a nitrate salt. The nitrate salt can oxidize the outer graphite matrix of a fuel element. The method can also include reduced temperature degradation of the carbide layer of a fuel element and low temperature solubilization of the fuel in a kernel of a fuel element.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Development of CdO-graphite-Ag coatings for gas bearings to 427 C

Graphite is one of the most commonly known lubricants. Its effectiveness in a range between room temperature (RT) and 540 C is reportedly improved by adding cadmium oxide. CdO-graphite powder in a gas carrier has been used in numerous applications that rely on dry lubrication. A coating of this composition was developed and successfully tested in foil air bearings for long periods up to a temperature of 427 C and at a normal contacting load (during starting and stopping) of 14 kPa based on bearing projected area. The addition of ultra-fine silver to the CdO-graphite has improved the coating endurance. At 427 C, the CdO-graphite-Ag coating performed better than CdO-graphite without silver, both for extended periods at 14 kPa loading and for limited periods at 35 kPa. At 288 C, the coating was tested for an extended period up to 28 kPa and has also successfully completed high-speed shock tests to an acceleration level of 100g.

Bhushan, B.↗