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At least 343 records · Page 19

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DOE OSTI2022

Graphite Degradation Modeling and Analysis

A graphite component in a nuclear reactor core is subjected to variety of stresses and can experience degradation during normal and off-normal operation. Understanding how a graphite component will behave in service is essential to ensuring core structural stability and safe reactor operation. This report summarizes a graphite modeling tool currently under development at Idaho National Laboratory. The model incorporates several of the anticipated stresses during service and includes the effects of oxidation and irradiation prior to turnaround. This tool is intended to be used to help assess the design of graphite components by utilizing design code rules found in Section III, Division 5 of the American Society of Mechanical Engineering Boiler and Pressure Vessel Code. Specifically, the tool uses the methodologies found within the Full and Simplified assessments from Article HHA-3000 to verify that a graphite component has an acceptably low probability of failure.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Graphite Licensing (ASME) and Testing (ASTM) Technical Assistance

DOE ART Graphite R&D program is currently involved in developing the structural code for licensing the new High Temperature Reactor (HTR) designs through the ASME Boiler Pressure Vessel Code (BPVC). The basic structural design code for graphite core components has been written, approved, and within the BPVC since 2012. However, several areas within the graphite code remain to be improved, specifically the addition of material property changes resulting from environmental degradation (neutron flux and oxidation). The incorporation of this data, which can significantly affect the graphite components and alter the structural integrity of the core during operation, is proving to be an important activity. How this data will be incorporated within the code and how it will be used for license applications will be critical to a number of HTR applicants in the future. These modifications to the code must take into account the unique irradiation and oxidation response of the wide spectrum of available nuclear graphite grades currently under consideration for HTR applications. Additionally, the ASME BPVC requires material property testing within the expected operational conditions of the HTR core including neutron radiation flux, elevated temperatures, and after chronic/acute oxidation of the graphite components. Currently, no standardized graphite testing methods are approved for these environmental conditions. New American Society for Testing and Materials (ASTM) standardized tests for elevated temperature testing, small sample testing, and testing after oxidation must be developed to support the requirements within the ASME code.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NASA NTRS1980

Environmental effects on graphite fiber reinforced PMR-15 polyimide

Studies were conducted to establish the effects of thermo-oxidative and hydrothermal exposure on the mechanical properties of T300 graphite fabric reinforced PMR-15 composites. The effects of hydrothermal exposure on the mechanical properties of HTS-2 continuous graphite fiber composites were also investigated. The thermo-oxidative stability characteristics of T300 fabric and T300 fabric/PMR-15 composites were determined. Flexural strengths of specimens were determined. The useful lifetime of T300 fabric/PMR-15 composites in air at 316 C was found to be about 100 hours. The useful lifetimes in air at 228 and 260 C were determined to be 500 and 1000 hours, respectively. Absorbed moisture was found to reduce the elevated temperature properties of both the T300 fabricate and HTS-2 continuous fiber composites. The moisture effect was found to be reversible.

Serafini, T. T.↗

NASA NTRS1982

Environmental effects on graphite fiber reinforced PMR-15 polyimide

Serafini, T. T.↗

DOE OSTI2019

Separation of Phosphorus and Manganese from Steelmaking Slag by Selective Reduction

Steelmaking slag contains considerable amount of manganese (Mn) and phosphorus (P), and recycling them is an important issue. Since Mn is an alloy added to enhance the steel quality, while P is a harmful impurity in the steel product, they need to be separated for recycling. We have already found the possibility of separating Mn and P from steelmaking slag by selectively reducing P{sub 2}O{sub 5} and FeO while suppressing the reduction of MnO. As a fundamental study for the selective reduction of P from steelmaking slag, in this study, we vary the slag basicity, graphite mixing ratio, temperature, and crucible type to find the optimum condition. Artificial steelmaking slag with various compositions is synthesized and mixed with graphite powder in an Al{sub 2}O{sub 3} or a MgO crucible. The reduction is conducted at 1673 K, 1773 K, and 1873 K for 20 to 80 minutes. As a result, carbon saturated metal is formed from the slag, and the reduced metal and slag were separated easily. We find that a decrease in slag basicity suppressed the reduction rate of Mn while enhancing that of P. The activation energy for the reduction rate constant of P is found to be close to that of the diffusion of P in slag.

36 MATERIALS SCIENCE↗

DOE OSTI2015

Minimum critical values for various fissile media with very low content of plutonium mixed in different kinds of matrix - 14340

For materials slightly contaminated by fissile nuclides (such as radioactive sludge), it could be useful to take into account the low fissile density in order to define the nuclear criticality safety limits (mass, volume,...) when this density is lower than the one of the optimally moderated fissile-water mixture (e.g. 30 g/dm{sup 3} for {sup 239}Pu). In such a case, if the material is modelled by the usual fissile-water mixture only, the fissile medium still contains a void fraction when the optimal moderation ratio is reached. Then, the question is to know whether modeling the other elements of the material can impact the nuclear criticality safety limits, in particular when they are good scattering elements. This paper aims at studying the impact of replacing the void fraction in plutonium fissile media, with various apparent densities, by different kinds of matrix containing scattering elements. Minimum critical values (mass, volume, diameter and thickness) have been determined for plutonium media, composed of 100 % {sup 239}Pu, with densities of 2, 5.8 and 7.3 g/dm{sup 3} in different kinds of matrix containing scattering elements (graphite, carbon, alumina, silica, magnesia, fluorite and calcium oxide). Different contents of the aforementioned scattering elements in the fissile media were studied and additional moderation was ensured by water. The results highlight that minimum critical values are lower when considering a fissile medium containing graphite, carbon, silica, alumina and magnesia with additional water moderation, compared to plutonium-water mixture only with the same low fissile apparent density. However, there is still a benefit of crediting density (critical values for a low fissile density are still higher than critical values without a density control). (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2021

Probing basal planes and edge sites in polygranular nuclear graphite by gas adsorption: Estimation of active surface area

Polygranular nuclear graphite, manufactured at 2800–3000 °C from a carbonized filler and binder mix, has high graphitization degree, crystalline structure close to perfect graphite, and about 20% porosity. The pore surfaces expose large regions of rough, defective prismatic edges of graphite crystallites which are the locus of graphite materials surface sites active for oxidation, chemisorption, and electron transfer. However, we show that high-resolution N 2 and Kr first monolayer adsorption on polygranular graphite (P/P 0 < 0.015) occurs in many ways like adsorption on graphitized carbon blacks. This proves the presence of energetically homogeneous basal planes domains in graphite porosity, which was not fully acknowledged before. Using classical analysis methods (Langmuir, Hill-de Boer, adsorption potential distribution) we quantity the basal plane area (BPA) of several polygranular graphite types and correlate it with their microstructure. Finally, we propose that gas adsorption is uniquely positioned to reliably estimate the active surface area of graphite by subtracting BPA from the BET total surface area. Direct estimation based on adsorption is preferable to indirect calculations based on microstructural information.

36 MATERIALS SCIENCE↗

NASA NTRS1980

Properties of PMR polyimide composites made with improved high strength graphite fibers

Recent graphite fiber developments have resulted in high strength, intermediate modulus graphite fibers having improved thermo-oxidative resistance. These improved fibers, obtained from various commercial suppliers, were used to fabricate PMR-15 and PMR-11 polyimide composites. Studies were performed to investigate the effects of the improved high strength graphite fibers on composite properties after exposure in air at 600 F. The use of the more oxidatively resistant fibers did not result in improved performance at 600 F. Two of the improved fibers were found to have an adverse effect on the long-term performance of PMR composites. The influence of various factors such as fiber physical properties, surface morphology and chemical composition are also discussed.

Vannucci, R. D.↗

DOE OSTI2021

Review of Graphite Properties Relevant to Micro-Reactor Design

Microreactors are advanced reactors that are designed to be small, scalable, and portable with up to 20 MW power. These reactors could operate independently, or as part of a microgrid, without need of a frequent refueling. Micro-reactors are designed to be deployable to provide electric power in remote locations, therefore providing greater flexibility. Several micro-reactors are under development in the US. These reactors are based on advanced gas-cooled or heat-pipe concepts. While Graphite can be found in various applications, some high-temperature reactors plan to employ Graphite in their core components due to its role as a moderator and its ability to maintain its structural integrity when subjected to elevated temperatures and high neutron fluence. Although there is significant experience with use of Graphite in nuclear applications, there are still unknowns that should be addressed. Graphite properties depend on the graphite type and affected by the fabrication procedures. Material properties are functions of the temperature and irradiation dose. The fundamental properties also affected by the oxidation environment. Therefore, in-depth understanding of graphite properties, including the effect of irradiation, oxidation and other influencing parameters are required to evaluate the design accurately. This draft aims to provide a comprehensive review of material properties for Graphite relevant to micro reactor design. For this work, two distinct grades of graphite were considered, namely IG-110 and Mersen-2114. Physical, thermal, and mechanical properties for these grades were comparatively evaluated. The properties that are discussed in this draft aim to serve as a basis for design and safety analysis.

42 ENGINEERING↗

DOE OSTI2015

High Temperature Gas-cooled Reactor (HTGR) Graphite Pebble Fuel: Review of Technologies for Reprocessing

This report reviews literature on reprocessing high temperature gas-cooled reactor graphite fuel components. A basic review of the various fuel components used in the pebble bed type reactors is provided along with a survey of synthesis methods for the fabrication of the fuel components. Several disposal options are considered for the graphite pebble fuel elements including the storage of intact pebbles, volume reduction by separating the graphite from fuel kernels, and complete processing of the pebbles for waste storage. Existing methods for graphite removal are presented and generally consist of mechanical separation techniques such as crushing and grinding chemical techniques through the use of acid digestion and oxidation. Potential methods for reprocessing the graphite pebbles include improvements to existing methods and novel technologies that have not previously been investigated for nuclear graphite waste applications. The best overall method will be dependent on the desired final waste form and needs to factor in the technical efficiency, political concerns, cost, and implementation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2018

High-Density Ultra-small Clusters and Single-Atom Fe Sites Embedded in Graphitic Carbon Nitride (g-C 3 N 4 ) for Highly Efficient Catalytic Advanced Oxidation Processes

Ultra-small metal clusters have attracted great attention owing to their superior catalytic performance and extensive application in heterogeneous catalysis. However, the synthesis of high-density metal clusters is very challenging due to their facile aggregation. In this work, one-step pyrolysis was used to synthesize ultra-small clusters and single-atom Fe sites embedded in graphitic carbon nitride with high density (iron loading up to 18.2 wt %), evidenced by high-angle annular dark field-scanning transmission electron microscopy, X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and 57 Fe Mössbauer spectroscopy. The catalysts exhibit enhanced activity and stability in degrading various organic samples in advanced oxidation processes. The drastically increased metal site density and stability provide useful insights into the design and synthesis of cluster catalysts for practical application in catalytic oxidation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

High Temperature Gas-cooled Reactor (HTGR) Graphite Pebble Fuel: Review of Technologies for Reprocessing

This report reviews literature on reprocessing high temperature gas-cooled reactor graphite fuel components. A basic review of the various fuel components used in the pebble bed type reactors is provided along with a survey of synthesis methods for the fabrication of the fuel components. Several disposal options are considered for the graphite pebble fuel elements including the storage of intact pebbles, volume reduction by separating the graphite from fuel kernels, and complete processing of the pebbles for waste storage. Existing methods for graphite removal are presented and generally consist of mechanical separation techniques such as crushing and grinding and chemical techniques through the use of acid digestion and oxidation. Potential methods for reprocessing the graphite pebbles include improvements to existing methods and novel technologies that have not previously been investigated for nuclear graphite waste applications. The best overall method will be dependent on the desired final waste form and needs to factor in the technical efficiency, political concerns, cost, and implementation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NASA NTRS2004

Reference standard for carbonaceous impurity measurements in carbon nanotubes

Near-infrared spectroscopy is a convenient tool for measuring nanotube / carbonaceous impurities ratios in carbon nanotube samples. These measurements are based on separation of contributions from nanotubes and impurities to the near-infrared absorption of samples dispersed in DMF, and sample purity is expressed relative to some reference sample. In the current work we produced a reference standard for NIR measurements using purified laser nanotubes. The sample was oxidized slowly using a Temperature Programmed Oxidation (TPO) setup in 2% oxygen / 98 % helium atmosphere. In these conditions, the sample oxidized in several steps, which were attributed to carbonaceous impurities, nanotubes and graphitic shells based on TEM and Raman observations. Stopping oxidation at 625 C (this temperature is sample-specific) allowed us to produce a sample with no carbonaceous impurities and well-defined ratio of nanotubes, graphite and metal catalyst. Since carbonaceous impurities no longer hold nanotubes and particles together, further centrifuging allowed us to remove particles and use this sample as a reference standard in NIR measurements.

Nikolaev, Pavel↗

NASA NTRS2004

Reference standard for carbonaceous impurity measurements in carbon nanotubes.

Near-infrared spectroscopy is a convenient tool for measuring nanotube/carbonaceous impurities ratios in carbon nanotube samples. These measurements are based on separation of contributions from nanotubes and impurities to the near-infrared absorption of samples dispersed in DMF, and sample purity is expressed relative to some reference sample. In the current work we produced a reference standard for NIR measurements using purified laser nanotubes. The sample was oxidized slowly using a Temperature Programmed Oxidation (TPO) setup in 2% oxygen/98% helium atmosphere. In these conditions, the sample oxidized in several steps, which were attributed to carbonaceous impurities, nanotubes and graphitic shells based on TEM and Raman observations. Stopping oxidation at 625 C (this temperature is sample-specific) allowed us to produce a sample with no carbonaceous impurities and well-defined ratio of nanotubes, graphite and metal catalyst. Since carbonaceous impurities no longer hold nanotubes and particles together, further centrifuging allowed us to remove particles and use this sample as a reference standard in NIR measurements.

Nikolaev, Pavel↗

DOE OSTI2023

Degradation and Modeling of Large-Format Commercial Lithium-Ion Cells as a Function of Chemistry, Design, and Aging Conditions

Demand for large-format (>10 Ah) lithium-ion batteries has increased substantially in recent years, due to the growth of both electric vehicle and stationary energy storage markets. The economics of these applications is sensitive to the lifetime of the batteries, and end-of-life can either be due to energy or power limitations. Despite this, there is little information from cell manufacturers on the sensitivity of cell degradation to environmental conditions or battery use. This work reports accelerated aging test data from four commercial large-format lithium-ion batteries from three manufacturers, with varying design (thickness, casings, ...), chemistry (lithium-iron-phosphate (LFP) or lithium-nickel-manganese-cobalt-oxide positive electrodes (NMC), with graphite (Gr) negative electrodes), and capacity (50 to 250 Amp hours). The tested LFP|Gr cell is found to be relatively insensitive to cycling conditions like temperature or voltage window, while NMC|Gr cells have varying sensitivity. Degradation trends are further investigated by training predictive models: simple polynomial trend lines, a semi-empirical reduced-order model, and an empirical reduced-order model identified using machine-learning based on symbolic regression. Calendar and cycle life are simulated over a variety of conditions to directly compare the various batteries. Cell size and thickness are found to substantially impact sensitivity to temperature during cycle aging, while electrode chemistry impacts depth-of-discharge sensitivity. Real-world battery lifetime is evaluated by simulating residential energy storage and commercial frequency containment reserve systems in several U.S. climate regions. Predicted lifetime across cell types varies from 7 years to 20+ years, though all cells are predicted to have at least 10 year life in certain conditions.

battery lifetime↗

DOE OSTI2024

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↗

DOE OSTI2019

Challenges and opportunities towards fast-charging battery materials

Extreme fast charging, with a goal of 15 minutes recharge time, is poised to accelerate mass market adoption of electric vehicles, curb greenhouse gas emissions and, in turn, provide nations with greater energy security. However, the realization of such a goal requires research and development across multiple levels, with battery technology being a key technical barrier. The present-day high-energy lithium-ion batteries with graphite anodes and transition metal oxide cathodes in liquid electrolytes are unable to achieve the fast-charging goal without negatively affecting electrochemical performance and safety. Here we discuss the challenges and future research directions towards fast charging at the level of battery materials from mass transport, charge transfer and thermal management perspectives. Additionally, we highlight advanced characterization techniques to fundamentally understand the failure mechanisms of batteries during fast charging, which in turn would inform more rational battery designs.

25 ENERGY STORAGE↗

DOE OSTI2021

Electrochemical ion insertion from the atomic to the device scale

Electrochemical ion insertion involves coupled ion–electron transfer reactions, transport of guest species and redox of the host. The hosts are typically anisotropic solids with 2D conduction planes but can also be materials with 1D or isotropic transport pathways. These insertion compounds have traditionally been studied in the context of energy storage but also find extensive applications in electrocatalysis, optoelectronics and computing. Recent developments in operando, ultrafast and high-resolution characterization methods, as well as accurate theoretical simulation methods, have led to a renaissance in the understanding of ion-insertion compounds. In this Review, we present a unified framework for understanding insertion compounds across timescales and length scales ranging from atomic to device levels. Using graphite, transition metal dichalcogenides, layered oxides, oxyhydroxides and olivines as examples, we explore commonalities in these materials in terms of point defects, interfacial reactions and phase transformations. We illustrate similarities in the operating principles of various ion-insertion devices, ranging from batteries and electrocatalysts to electrochromics and thermal transistors, with the goal of unifying research across disciplinary boundaries.

36 MATERIALS SCIENCE↗