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At least 307 records · Page 17

Characterization of radiation damage effects in high-energy neutrino target graphite using low-energy ions

Exposure of graphite targets to high intensity proton beams at neutrino production facilities causes changes in the target material that can result in a shortened operation lifetime. The dominant factors in this process are currently thought to be mechanical in nature resulting primarily from microstructural effects that lead to thermal and structural changes in bulk material properties. As currently planned beam facilities with increased proton energy and intensity begin to come online it will be important to thoroughly understand these processes, and ideally to be able to predict the effects of new beam designs on target properties. Direct analysis of targets exposed to existing high-energy proton beams is complicated by several factors, such as very limited access to proton beam facilities, high associated costs, irradiation times on the order of months, and the resulting radioactivity of irradiated samples that requires special facilities for post-irradiation examination. Much of the existing literature concerning irradiation damage in graphite has been focused on the needs of the nuclear engineering community, however high-energy proton targets operate in a much different environment. In comparison to graphite irradiated in a nuclear reactor, graphite used in proton beam targets receives a higher dose rate, have greater gas production, and experience short irradiation pulses as opposed to continuous irradiation. Low-energy ion irradiation offers a method of inducing similar levels of radiation damage to high-energy protons while avoiding many of the difficulties and limitations associated with high-energy proton beams and the corresponding activated specimen testing. My research described in this thesis focused on investigating how low-energy ion irradiation could be used to induce the same or similar types of microstructural alteration and mechanical property degradation as that seen in high-energy neutrino production target graphites by varying damage le vels and irradiation temperatures prior to post-irradiation characterisation.

43 PARTICLE ACCELERATORS↗

A Comparison of Solid Electrolyte Interphase Formation and Evolution on Highly Oriented Pyrolytic and Disordered Graphite Negative Electrodes in Lithium–Ion Batteries

The presence and stability of solid electrolyte interphase (SEI) on graphitic electrodes is vital to the performance of lithium-ion batteries (LIBs). However, the formation and evolution of SEI remain the least understood area in LIBs due to its dynamic nature, complexity in chemical composition, heterogeneity in morphology, as well as lack of reliable in situ/operando techniques for accurate characterization. In addition, chemical composition and morphology of SEI are not only affected by the choice of electrolyte, but also by the nature of the electrode surface. While introduction of defects into graphitic electrodes has promoted their electrochemical properties, how such structural defects influence SEI formation and evolution remains an open question. In this work, utilizing nondestructive operando electrochemical atomic force microscopy (EChem-AFM) the dynamic SEI formation and evolution on a pair of representative graphitic materials with and without defects, namely, highly oriented pyrolytic and disordered graphite electrodes, are systematically monitored and compared. Complementary to the characterization of SEI topographical and mechanical changes during electrochemical cycling by EChem-AFM, chemical analysis and theoretical calculations are conducted to provide mechanistic insights underlying SEI formation and evolution. The results provide guidance to engineer functional SEIs through design of carbon materials with defects for LIBs and beyond.

25 ENERGY STORAGE↗

Plasma exposures of a high-conductivity graphitic foam for plasma facing components

The plasma-surface interactions from samples of high-conductivity graphitic foam biased to 120 V and placed in 6–8 eV deuterium plasmas with densities as high as 10 19 m -3 were investigated at the PSI-2 linear plasma device in Jülich. Graphitic foam-plasma interactions were also studied at the Wendelstein 7-X (W7-X) stellarator in Greifswald by exposure to hydrogen and helium plasmas using the Jülich multi-purpose manipulator. The purpose was to explore the possibility of using the material in a plasma facing component, and initial results were encouraging. In W7-X, no measurable erosion or cracking was observed. The PSI-2 samples received a deuterium fluence of 5 × 10 25 m -2 resulting in an average erosion of 43 µm or about 5 mg per sample. Residual gas analysis (RGA) data were acquired to monitor sample outgassing. Laser-induced Breakdown Spectroscopy (LIBS) was used to measure deuterium retention in the porous foam. After exposure, the surfaces were characterized with scanning electron microscopy, energy dispersive x-ray analysis and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The graphitic foam has a thermal conductivity as high as 287 W/mK and is considered as a replacement to more exotic carbon fiber composites such as SepCarb NB31 or isotropic graphites like ATJ that are no longer produced but used in present-day tokamak experiments. Actively cooled monoblocks were made from the foam and underwent extensive materials characterization including infrared response studies at Oak Ridge National Laboratory. This material is under consideration for the proposed actively-cooled W7-X divertor scraper element.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Overview of Graphite Model Development

Overview of graphite model development. Discuss graphite in motel salt, potential degradation mechanisms, stress due to volumetric heating, and the role of different parameters. Also wear modeling, modeling salt infiltration into graphite, oxidation modeling, and the existing graphite models.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Dynamic Modeling and Characterization of Nuclear-grade Graphite

Idaho National Labs serves as the spearhead for many innovative energy solutions to the world's energy crisis. One such solution is the INL's Microreactor which is designed to deploy to extreme/remote environments where other sources of power are either unavailable or unreliable. In order to best design these energy solutions for their operational environments, it is crucial to understand how the design, components, and materials will respond to the environmental conditions. One key material in these innovative designs is a nuclear-grade graphite known as PCEA. This study examines the behavior of PCEA graphite under dynamic loading, similar to that which may occur in extreme environments. The objective is to characterize the dynamic behavior and produce an accurate, reliable constitutive model suitable for use in simulation tools such as INL's MOOSE. Graphite specimens were tested using a Split Hopkinson Pressure Bar (SHPB) to administer the dynamic compressive load. The SHPB was charged at various pressures to produce a range of strain rates on the material in compression. Data was acquired via strain gauges on the SHPB setup, from which stress, strain, and time data were collected. Analysis revealed the stress-strain behavior of the material as well as insights into the material behavior's relationship to strain rate. Further work must continue to characterize the various other dynamic behaviors of the material which will combine to create a substantially trustworthy constitutive model for this grade of nuclear-grade graphite. Ultimately, this will allow for realistic simulation of the material in reactor designs, allowing for prediction of design weaknesses and leading to improved designs for increased resilience, security, and reliability.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Analysis of the Stable Interphase Responsible for the Excellent Electrochemical Performance of Graphite Electrodes in Sodium-Ion Batteries

Considerable efforts have been exerted to understand the formation and properties of the solid electrolyte interphase (SEI) in sodium ion batteries. However, the puzzling existence and role of SEI behind the huge volume changes of the graphite electrodes need to be answered. Herein, the reason of how ether-derived SEI maintains excellent reversibility despite the huge volume changes during cycling is unraveled. Theoretical simulations and Fourier-transform infrared spectroscopy demonstrate the formation mechanism of an SEI between the graphite anode and electrolyte. Furthermore, the high mechanical tolerance of the ether-derived SEI is confirmed in atomic force microscopy. A depth profile of X-ray photoelectron spectroscopy points to a multilayer structure of the ether-derived SEI. The outer layer comprises organics (sodium alkoxide), while the inorganics (Na 2 CO 3 , NaF) in interior region are mixed with some organics. Notably, the presence of organics ensures the adaptability of the SEI to the volume expansion of graphite during cycling, and the concentrated distribution of inorganics improves the Young's modulus (resistance to deformation). Therefore, the graphite anode exhibits high cycle stability (96.6% capacity retention ratio at 1 A g –1 over 860 cycles) and efficiency (≈99.5%).

25 ENERGY STORAGE↗

Nominal Power Assimilation in Leningradskaya NPP No. 1 Unit After Service Life Characteristics Restoration of the Graphite Stack

The maximum graphite temperature upon increasing the reactor power in the No. 1 unit of the Leningradskaya NPP to 80% of the nominal value in November–December 2013 after the restoration of the service life characteristics of the graphite stack is presented. A comparative analysis is made of the temperature regime of the graphite stack at power equal to 80 and 100% of nominal value before and after restoration of the service life characteristics at nominal helium content in the gas mixture blown through the reactor space. A comparison is made of the maximum temperature of the graphite stack of the reactors in the No. 1 unit of the Leningradskaya NPP and No. 2 unit of the Kursk NPP upon startup and assimilation of the power after restoration of the service life characteristics. The effect of the restoration of the service life characteristics on the thermohydraulic regime of the fuel channels in the reactor is studied.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Numerical Modeling of RBMK-1000 Graphite Stack Distortion

Engineering and detailed three-dimensional models of the RBMK-1000 graphite stack for modeling of its distortions caused by the appearance of longitudinal cracks in the blocks owing to the nonuniformity of the temperature and fluence distributions are described. As the neutron fluence accumulates and the limit longitudinal deflection of the graphite columns is reached, the graphite stack is repaired by cutting the graphite blocks. The developed models make it possible to evaluate the accumulation of deflection of the columns before and after repairs and the effectiveness of various repair schemes. The developed models are used to calculate the maximum deflection of the stack columns in the No. 1 unit of the Leningradskaya NPP for different operating conditions after repairs.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

SIMS and HR-XPS characterization of lithiated graphite from the magnetic fusion device RFX-mod

Lithium wall conditioning has improved the performance of many magnetic fusion devices. Li conditioning in the RFX-mod device was performed by: (1) a single Li pellet injector and (2) a multi-Li pellet injector during He plasma discharges; (3) a Li evaporator after He glow discharge cleaning and He plasma discharge exposure. This report compares the spatial and depth distributions of Li deposited on polycrystalline graphite witness samples at different locations in RFX-mod and the elemental and chemical compositions of the resulting surfaces. The sample surfaces were analyzed ex situ using secondary ion mass spectrometry (SIMS) and high-resolution X-ray photoelectron spectroscopy (HR-XPS). The results showed that Li pellet injection provided a relatively uniform toroidal coverage while Li evaporation produced highly localized Li deposition. A Li 1s HR-XPS peak at 56.5 eV binding energy (BE) characteristic of lithium-intercalated graphite was only observed with the sample exposed to Li evaporation. All of the samples exhibited a HR-XPS C 1s peak at 285.1–285.2 eV BE that is largely attributed to hydrogenated graphite. This finding suggests that hydrogenation of fresh graphite occurs during He plasma discharge exposures. Finally, our results have implications for density control and the selection of Li conditioning techniques in magnetic fusion devices.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

A macro-scale ruck and tuck mechanism for deformation in ion-irradiated polycrystalline graphite

A vein structure, which becomes more pronounced with increasing ion dose, was found on the surface of polycrystalline HOPG (highly oriented pyrolytic graphite) implanted by ex situ C + (up to 1.8 × 10 17 ions/cm 2 ), and in situ Ar + in a transmission electron microscope (TEM). These veins are found to be independent of the crystallographic orientations and are associated with the formation of pores. Underneath the veins, a triangular-shaped core was formed with the graphite platelet inside the core displaced up towards the surface. A macro-scale ‘ruck&tuck’ geometry was thus generated at these triangle structure boundaries. Progressive movement of dislocations along basal planes during irradiation was observed, and a mechanistic model was proposed on this basis to explain the vein formation. A small increase of c-spacing was observed with irradiation but it is believed that macro-scale vein formation plays a more vital role in the dimensional and property changes in polycrystalline graphite, especially when a stress gradient is present. Here, the model proposed also explains the change of thermal expansion in HOPG with irradiation. Together with Heggie’s ‘ruck&tuck’ and Barsoum’s ‘ripplocations’ models, the present model is considered to have provided an additional experimentally proven mechanism responsible for irradiation behaviour in graphite materials.

36 MATERIALS SCIENCE↗

Unraveling compacted graphite evolution during solidification of cast iron using in-situ synchrotron X-ray tomography

In spite of many years of research, the physical phenomena leading to the evolution of compacted graphite (CG) during solidification is still not fully understood. In particular, it is unknown how highly branched CG aggregates form and evolve in the semi-solid, and how local microstructural variations at micrometer length scale affect this growth process. We present here the first time-resolved synchrotron tomography combined with a bespoke high-temperature environmental cell that allows direct observation of the evolution of CG and relates this dynamic process to the local surrounding microstructures in a cast iron sample during repeated melting and solidification. Distinct processes are identified for the formation of CG involving the nucleation, growth, development of branches and interconnection of graphite particles, ultimately evolving into highly branched graphite aggregates with large sizes and low sphericities. CG is found to nucleate with a spheroidal or a plate-like shape, developing branches induced by high carbon concentration, e.g. thin melt channels. Additionally, CG grows much faster than spheroidal graphite during subsequent cooling in solid state. The direct visualization of the dynamic solidification process provides unprecedented new insights into formation mechanisms of CG and correlating factors such as local microstructural variations, and guides the development of CG iron solidification models.

36 MATERIALS SCIENCE↗

Effect of microstructure and temperature on nuclear graphite oxidation using the 3D Random Pore Model

This work compared the 3D Random Pore Model (3D-RPM) with experimental and characterization data to systematically study the effect of nuclear graphite microstructure and air oxidation temperature. It is well known that oxidation-induced weight loss at elevated temperatures degrades graphite structure and properties; however, a fundamental understanding of the role of graphite microstructure is still unclear. In this work, three diverse grades of nuclear graphite—IG-110, NBG-18, and PCEA—were examined and tested at air oxidation temperatures of 600, 650, 700, and 750 °C following ASTM D7542. Here, the 3D-RPM reproduced the microstructure and temperature dependence of mass loss curves for these grades. For the first time, measurements and modeling were combined to show how bulk density and the amount and spatial distribution of open and closed porosity affects oxidation. IG-110 was less dense and had an open pore network that is finer and more uniformly spread, and showed fastest oxidation. PCEA porosity was less uniform and showed less oxidation, while NBG-18 was more dense, had the least fine and uniform porosity, and showed the slowest oxidation. In general, oxidation proceeds faster if open porosity is more uniformly distributed and can incrementally access closed pore surface area with more ease.

36 MATERIALS SCIENCE↗

Analytical models of hydrogen transport in graphite

The importance of graphite-hydrogen chemical reactions to fusion, fission, and hydrogen storage applications, combined with the rapidly evolving knowledge on the underlying mechanisms, has led to the development of multiple models to describe hydrogen transport in graphite. Significant differences exist among these models, resulting from discrepancies in the modeling assumptions, intended degree of fidelity, and conditions of applicability. This paper attempts at reconciling these apparent differences by providing a comprehensive description of the constitutive equations governing hydrogen transport in graphite at high-temperature, identifying outstanding gaps in knowledge, illustrating how these different models approach them, and proposing alternative analytical formulations grounded on experimental results from hydrogen-graphite studies. Governing equations, closing relations, and simplifying assumptions are discussed for hydrogen transport at the inter-granular and intra-granular level, accompanied by compiled experimental data and illustrated energy diagrams associated to the proposed transport mechanisms. Analytical formulations are provided to reproduce competing hypotheses on the mechanisms, supporting the development of a range of computational models that can enable resolution of outstanding knowledge gaps through comparative testing against experimental data.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Novel pyrolytic boron nitride coating to reduce graphite interactions in molten fluoride salt

Future salt reactors like the Fluoride-salt-cooled-High Temperature Reactor require varying material flavors. Graphite is required for neutron moderation and potential fuel forms, while structural metals are required for containment. Studies show graphite/metal interactions exist when both materials share a salt medium. These interactions may accelerate the corrosion of the metal and change the surface of graphite materials. A novel pyrolytic boron nitride coating on graphite is investigated for reducing graphite/metal interactions. Finally, this is the first known application of such a coating, and salt exposure tests reveal the pyrolytic boron nitride coating reduces the interactions between stainless steel and uncoated graphite.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Kinetic study of the hydrogen charging reaction on the graphite e in aqueous solution and in room temperature ionic liquid (RTIL)

Electrochemical impedance spectroscopy and other electrochemical methods were used to study the kinetics of hydrogen entry into porous, isotropic graphite and a single crystal graphite surfaces upon cathodic hydrogen charging and to calculate the hydrogen adsorption efficiencies. This model was first applied to graphite in an aqueous, alkaline solution, then in a room-temperature ionic liquid (RTIL), and, ultimately will be applied to FliNaK molten salt systems in future work. The results demonstrate that our model accurately describes the entry of hydrogen into graphite in harsh environments, which are important for the development of molten salt reactors (MSRs).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sustainable Li-ion anode material from Fe-catalyzed graphitization of paper waste

We report a novel method for the conversion of paper towel waste to biographite anode material is developed and optimized for use in Li-ion batteries. The surge in demand for Li-ion battery anode materials coupled with the unsustainable and inefficient methods of producing battery-grade graphite necessitate alternative carbon feedstocks and graphitization technologies. Paper waste (PW) is identified as a suitable carbon feedstock for iron-catalyzed graphitization due to its sustainability, low cost, low ash content, and ample supply for the intended end use. A Box Behnken experimental design for statistical optimization is pursued for untreated and pre-carbonized PW with factors of temperature (1100-1300 °C), hold time (1-5 h), and iron catalyst loading (0.5-1.5x fixed carbon content) with biographite crystal size as the primary response variable. Temperature and iron catalyst loading are found to be significant factors, whereas hold time is found to be insignificant. Reversible capacities of the biographite anodes are found to be 340-355 mAh g-1 with 99% capacity retention over 100 cycles, indicating good electrochemical performance relative to commercial graphite anodes. The initial Coulombic efficiency of untreated and pre-carbonized biographites, however, are 77% and 75%, respectively, suggesting parasitic reactions including electrolyte decomposition.

25 ENERGY STORAGE↗

Understanding particle size effect on fast-charging behavior of graphite anode using ultra-thin-layer electrodes

Extreme fast charging (≤ 15 min) of lithium-ion batteries is highly desirable to accelerate mass-market adoption of electric vehicles. However, significant capacity fading, as well as safety issues due to the lithium plating caused by the fast charging rate, limit its implementation. In this study, we investigated the fast-charging capability of graphite materials with various particle sizes. To eliminate the Li + ion concentration gradient effect across the thickness of the electrode, ultra-thin-layer graphite electrodes were developed to investigate the "real" fast-charging capability of graphite at the particle level. Electrochemical assessments as well as microscopic characterizations revealed that smaller particles exhibited superior fast-charging performance, featuring enhanced capacity reversibility, faster charging rate, and less lithium plating under the same fast-charging conditions. It is shown that small-particle graphite (mean radius of 3.3 μm) could withstand a 4C charge (to 80 % state-of-charge) without plating, with minimal plating occurring at 6C. Thicker particles exhibited plating at lower C-rates. Since the experimental data could not directly explain whether intra-particle diffusion limitations or interfacial reaction limitations dominated the plating mechanism, the pseudo-2-dimensional model was used to evaluate the most likely plating mechanism. The model suggested that particle-level diffusion is the dominant mechanism contributing to plating at high rates. Finally, this work provides comprehensive insights into the particle size effects on fast-charging capability, offering a better understanding of fast-charging behavior and valuable guidance for designing optimal electrode architecture for high-rate lithium-ion batteries.

25 ENERGY STORAGE↗

Strength characterization of solar-synthesized cylindrical graphite carbon–carbon composites

The present work describes a new morphology of cylindrical graphite synthesized in a unique manner by direct solar decomposition of methane and reports the mechanical properties of its manifestation in woven carbon–carbon composites. Whereas traditional carbon–carbon composites are formed via epoxy impregnation, the deposited material in the process presented here conformally follows the existing shape and orientation of individual carbon fibers. Through this process, cylindrical graphite fibers are synthesized that possess superior strength due to their graphitic layers that amalgamate into interlocked pathways between disparate fibers. Here, strength measurements, taken in tandem with Raman, XRD, and SEM, paint a picture of the shift from cloth to composite behavior via graphitization of the original substrate combined with sheets of graphene coalescing into a unified composite, with a notable improvement in elastic modulus from 0.19 to 2.66 GPa.

Carbon–carbon composite↗