Results for “metal flux method” — Page 8

DOE OSTI2023

Determining the Effects of Neutron Irradiation on the Structural Integrity of Additively Manufactured Heat Exchangers for Very Small Modular Reactor Applications, DOE Final Report (Project # 19-16980)

Auburn University (AU) teamed with the University of Missouri Research Reactor (MURR) and Kansas State University (KSU) to determine how to best use laser-powder bed fusion (L-PBF) additive manufacturing (AM) methods for generating radiation resistant nickel-based superalloys, Inconel alloy 625 and 718, for special purpose reactor (SPR) or very small modular reactor (vSMR) heat-exchangers (HeXs). Compact, conformal, and durable HeXs that are tolerant of extreme environments are needed for supporting the technical maturity of next-generation, portable compact reactors. AM is an enabler for realizing this new wave of HeXs – providing a means to make customizable hot and cold stream architectures with novel flow path geometries (e.g., tortuous channels with non-uniform, asymmetric cross-sections) and reduced layer-to-layer contact resistance (i.e., no separate bonding procedure required). AM further enables a more time/cost efficient means for fabricating SPRs by reducing the number of suppliers required for HeX assembly and allowing for on-site HeX fabrication. The project aim has been to better understand how neutron irradiation affects the microstructure and properties of additively manufactured nickel-based superalloys, to accelerate their safe, reliable use in the modular reactor industry. The major objective was to qualify/quantify the microstructure and microhardness of nickel-based superalloys (including Inconel 718 and 625) additively manufactured via the L-PBF process in the neutron-dosed (irradiated) and non-irradiated states over a course of 3 years. Effects of build orientation during L-PBF and post-AM heat treatments on neutron resistance, microstructure and mechanical properties were also investigated. Neutron damage mechanisms via hardening were characterized. This project combined subject-matter experts in AM, mechanical/microstructure metallic part characterization, and neutron irradiation, as well as unique assets and capabilities at AU and MURR at MU, to ensure project results translated to effectively addressing known gaps in nuclear science and engineering. Parts were fabricated using L-PBF systems readily available at AU. Specimens were then irradiated using MURR facilities; a manipulator equipped hot cell was also used to measure material hardness after dosing. MURR, a 10 MW, light-water nuclear reactor, is the largest, highest powered, highest-flux university owned research reactor in the U.S. The major findings in this project provide evidence that AM can serve as an alternative way to build structural components for future advanced small modular reactors using advanced materials like Inconel 625 (IN625) or Inconel 718 (IN718). After full spectrum neutron irradiation, vertically as-built AM IN625 samples were observed to display better resistance towards radiation-induced-hardening defects relative to traditionally machined metals. A Vickers microhardness tester, using settings of 1 kgf and dwell time of 15 seconds per indentation, was used to measure hardness in this study. The as-built, vertically printed samples experienced 1.2% of radiation hardening vs. 5.25% radiation hardening observed in wrought IN625. Another set of IN625 and IN718 samples were exposed to fast neutron irradiation. It was observed that IN718 showed more resistance towards radiation hardening compared to IN625 samples indicating IN718 had a better performance. Results showed that the IN718 samples experienced less change (-2.5 to 3.24 %) in microhardness. On the other hand, IN625 samples underwent more (0.9 to 7.21%) change in microhardness after fast neutron irradiation. AM IN625 samples were irradiated using an ion (proton) beam in cyclotron. The mechanical properties of AM samples post irradiation were compared with wrought samples. The irradiated region on the samples were tested using nano-hardness indention. It was observed that the beam current and time used in this study generated an annealing effect and thus reduced the hardness of the samples. The sum of the project results provide precious insight into how one may minimize radiation hardening in AM materials while maintaining material property constraints. Results should assist engineers in selecting an appropriate heat treatment for AM nickel-based superalloys for increased radiation resistance. Results should increase confidence levels for adopting AM for building nuclear reactor components which perform the same or better than conventionally manufactured components. Fast neutron irradiation testing provided an accelerated means of obtaining radiation effects without making materials radioactive and difficult to handle.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

DOE OSTI2024

Pre-Transient Characterization of Historic EBR-II Pins for Transient Testing

Current interest in sodium-cooled fast reactor (SFR) designs, such as TerraPower’s Natrium Reactor, has highlighted the need for advanced reactor fuel technology development. Modern U-Zr and U- Pu-Zr pin designs are primary candidates to fuel SFRs and boast high fuel utilization capacity, increased fuel-cladding compatibility, and improved safety through inherent feedback mechanisms. Despite over 60 years of metallic fuel irradiation, uncertainties exist in the performance of the fuel system, particularly under transient overpower (TOP) and loss of flow (LOF) scenarios. Throughout historical testing within the Experimental Breeder Reactor II (EBR-II) and the Fast Flux Test Facility (FFTF), fuel behavior has demonstrated benign response to transient reactor conditions; however, accurate predictions of failure thresholds to inform operational limitations rely heavily on fuel composition, burnup, and irradiation history. In expanding TOP and LOF testing, the Transient Heat sink Overpower Response (THOR) Capsule will be used to test modern fuel technologies in a static sodium environment in the Transient Reactor Test (TREAT) Facility. The THOR capsule is highly instrumented and will provide time-dependent thermal behavior of SFR fuel pins subjected to accident conditions within TREAT. The THOR-Metallic (THOR- M) campaign aims to validate and expand historical TOP and LOF testing on high burnup U-Zr and U-Pu- Zr fuel alloys previously irradiated in EBR-II by running the rods to failure. This contribution focuses primarily on the pre-transient engineering-scale destructive and non- destructive characterization that has been conducted on both the test and sibling pins used for the TOP and LOF tests. All pins underwent visual examination, neutron radiography, element contact profilometry, and precise gamma scan. The sibling pins used for each test were further analyzed using gas assay, sampling, and recharge analysis (GASR), and optical microscopy. The results from each technique confirmed that the fuel pins were intact and devoid of any atypical developments when compared to historical data. Additionally, the analyzed measurements establish a baseline for comparison to post-transient analysis. Key fuel behaviors quanitifed include axial elongation of the fuel column, diametral strain of the pin, patterns in fluff structure geometry, changes in axial isotope distribution, evolution of constituent redistribution, porosity, and fission gas release. The pre-transient measurements and changes attributed to transient behavior from post-transient measurement will be compared to historical data to capture the behavioral dependence on composition, burnup, and irradiation history. Results from this work advance the initiatives of the THOR-M campaign, which aid in informing fuel performance models and establishing safety criteria for SFR operational limits. The novel combination of test environment, in-situ instrumentation, and comprehensive suite of characterization methods provides greater understanding of transient fuel behavior. Overall, information on the time and condition of pin failure for high burnup U-Pu-Zr will greatly expand the limited existing TOP and LOF test data.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2024

Pre-Transient Characterization of Historic EBR-II Pins for Transient Testing

Current interest in sodium-cooled fast reactor (SFR) designs, such as TerraPower’s Natrium Reactor, has highlighted the need for advanced reactor fuel technology development. Modern U-Zr and U- Pu-Zr pin designs are primary candidates to fuel SFRs and boast high fuel utilization capacity, increased fuel-cladding compatibility, and improved safety through inherent feedback mechanisms. Despite over 60 years of metallic fuel irradiation, uncertainties exist in the performance of the fuel system, particularly under transient overpower (TOP) and loss of flow (LOF) scenarios. Throughout historical testing within the Experimental Breeder Reactor II (EBR-II) and the Fast Flux Test Facility (FFTF), fuel behavior has demonstrated benign response to transient reactor conditions; however, accurate predictions of failure thresholds to inform operational limitations rely heavily on fuel composition, burnup, and irradiation history. In expanding TOP and LOF testing, the Transient Heat sink Overpower Response (THOR) Capsule will be used to test modern fuel technologies in a static sodium environment in the Transient Reactor Test (TREAT) Facility. The THOR capsule is highly instrumented and will provide time-dependent thermal behavior of SFR fuel pins subjected to accident conditions within TREAT. The THOR-Metallic (THOR- M) campaign aims to validate and expand historical TOP and LOF testing on high burnup U-Zr and U-Pu- Zr fuel alloys previously irradiated in EBR-II by running the rods to failure. This contribution focuses primarily on the pre-transient engineering-scale destructive and non- destructive characterization that has been conducted on both the test and sibling pins used for the TOP and LOF tests. All pins underwent visual examination, neutron radiography, element contact profilometry, and precise gamma scan. The sibling pins used for each test were further analyzed using gas assay, sampling, and recharge analysis (GASR), and optical microscopy. The results from each technique confirmed that the fuel pins were intact and devoid of any atypical developments when compared to historical data. Additionally, the analyzed measurements establish a baseline for comparison to post-transient analysis. Key fuel behaviors quanitifed include axial elongation of the fuel column, diametral strain of the pin, patterns in fluff structure geometry, changes in axial isotope distribution, evolution of constituent redistribution, porosity, and fission gas release. The pre-transient measurements and changes attributed to transient behavior from post-transient measurement will be compared to historical data to capture the behavioral dependence on composition, burnup, and irradiation history. Results from this work advance the initiatives of the THOR-M campaign, which aid in informing fuel performance models and establishing safety criteria for SFR operational limits. The novel combination of test environment, in-situ instrumentation, and comprehensive suite of characterization methods provides greater understanding of transient fuel behavior. Overall, information on the time and condition of pin failure for high burnup U-Pu-Zr will greatly expand the limited existing TOP and LOF test data.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2021

Complex Dirac-like Electronic Structure in Atomic Site-Ordered Rh 3 In 3.4 Ge 3.6

We report the synthesis via an indium flux method of a novel single-crystalline compound Rh 3 In 3.4 Ge 3.6 that belongs to the cubic Ir 3 Ge 7 structure type. In Rh 3 In 3.4 Ge 3.6 , the In and Ge atoms preferentially occupy, respectively, the 12d and 16f sites of the Im3¯m space group, thus creating a colored variant of the Ir 3 Ge 7 structure. Like the other compounds of the Ir 3 Ge 7 family, Rh 3 In 3.4 Ge 3.6 shows potential as a thermoelectric, displaying a relatively large power factor, PF ~ 2 mW/cm K 2 , at a temperature T ~ 225 K, albeit showing a modest figure of merit, ZT = 8 x 10 -4 , because of the lack of a finite band gap. These figures might improve through a use of chemical substitution strategies to achieve band gap opening. Remarkably, electronic band structure calculations reveal that this compound displays a complex Dirac-like electronic structure relatively close to the Fermi level. The electronic structure is composed of several Dirac type-I and type-II nodes, and even Dirac type-III nodes that result from the touching between a flat band and a linearly dispersing band. Here, this rich Dirac-like electronic dispersion suggests the possibility to observe experimentally Dirac type-III nodes and study their role in the physical properties of Rh 3 In 3.4 Ge 3.6 and related Ir 3 Ge 7 -type materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Advanced Fuels Campaign Execution Plan

The Advanced Fuels Campaign (AFC) Execution Plan outlines the strategy, mission, scope, near-term and long-term goals, structure, and organization associated with nuclear fuels and materials research, development, and demonstration activities within the Department of Energy’s (DOE) Nuclear Fuel Cycle and Supply Chain (NFCSC) program. NFCSC has been given responsibility to identify and mature advanced fuel technologies for the DOE using a science-based approach, focused on developing a fundamental understanding of nuclear fuels and materials to drive development of integrated nuclear fuel and materials technology. This science-based approach combines theory, experiments, and multiscale modeling and simulation to achieve a predictive understanding of relevant behaviors ranging from fuel fabrication processes (and their resulting fuel microstructures) through fuel/cladding performance under irradiation (in contrast to more empirical, observation-based approaches frequently used in fuel performance modeling and fuel qualification). The traditional scope of AFC includes the evaluation and development of multiple fuel forms to support two fuel cycle options: once-through and full recycle. The word “fuel” is used generically to include conventional fuels, transmutation targets, and any associated cladding or duct materials. The once-through fuel cycle addresses advanced light water reactor fuels with enhanced performance, extended burnup, and reduced waste generation. In fiscal year (FY) 2012, AFC’s scope expanded to include research, development, and demonstration (RD&D) for light water reactor (LWR) fuels with enhanced accident tolerance. Fuel fabrication activities include the development of innovative methods to enhance process efficiencies, reduce waste, and improve control over as-fabricated fuel microstructural properties to achieve desired in-reactor performance. Using modern modeling and simulation approaches, the objective is to predict fresh fuel properties given the feedstock characteristics and fabrication process parameters. The performance-related activities include small-scale, in-reactor, and out-of-reactor phenomenological testing (distinct from, but synergistic with, integral prototypic testing) and extensive, quantitative characterization (focusing on characterization of fuel and cladding materials at the scale of microstructure) both before and after testing. Larger-scale, prototypic experiments are conducted in concert with phenomenological testing to drive a Fuel Development and Qualification program, incorporating a fundamental understanding of fuel behavior performance characteristics. Then, using the tools developed under the productive science-based approach, fuels will be optimized to meet specific performance requirements, thereby minimizing the need to repeatedly perform large-scale, integral experiments over a wide parametric range as a means of experimental exploration. Two significant initiatives are underway within AFC. First, a gap analysis completed in early FY 2019 identified critical irradiation testing needs that are lacking within the national light water reactor (LWR) fuels testbed since the shutdown of the Halden Reactor in 2018. The identified gaps are for instrumented, prototypic testing of LWR fuels, especially under boiling water reactor conditions, ramp conditions, and conditions leading to fuel failure; these needs exist for supporting current LWR fuels and their possible extension to higher burnups, but are especially urgent relative to near-term development and qualification of accident-tolerant fuels. Recommendations that resulted from the Halden Gap Analysis focused on enhancements at Advanced Test Reactor (ATR) and Transient Reactor Test Facility (TREAT) to fill gaps in testing capabilities relative to these needs. Second, a concerted effort to develop and demonstrate a systematic approach to accelerating the development, testing, and qualification of new fuel systems has been initiated. This is highlighted by a test strategy that combines the considerable advances in multiscale, mechanistic fuel modeling of recent years with a MiniFuel separate effects test program in the High Flux Isotope Reactor (HFIR) and a Fission Accelerated Steady-state Testing (FAST) semi-integral accelerated test program in ATR. This approach is being tested/demonstrated using the metallic fuel system, but if successful it is expected to be extensible to multiple fuel types and diverse applications. This document includes an overview of the NFCSC program, a definition of science-based development of nuclear fuels, near-term goals for Advanced LWR fuels (ALFs), and longer-term goals for Advanced Reactor Fuels (ARFs) RD&D. This includes the activities that will be conducted to achieve success toward the grand challenge, as well as the goals and milestones to be achieved over the next few decades of research and development. Long-term goals are based on the DOE Office of Nuclear Energ

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2024

Advanced Fuels Campaign Execution Plan

The Advanced Fuels Campaign (AFC) Execution Plan outlines the strategy, mission, scope, near-term and long-term goals, structure, and organization associated with nuclear fuels and materials research, development, and demonstration activities within the Department of Energy’s (DOE) Nuclear Fuel Cycle and Supply Chain (NFCSC) program. NFCSC has been given responsibility to identify and mature advanced fuel technologies for the DOE using a science-based approach, focused on developing a fundamental understanding of nuclear fuels and materials to drive development of integrated nuclear fuel and materials technology. This science-based approach combines theory, experiments, and multiscale modeling and simulation to achieve a predictive understanding of relevant behaviors ranging from fuel fabrication processes (and their resulting fuel microstructures) through fuel/cladding performance under irradiation (in contrast to more empirical, observation-based approaches frequently used in fuel performance modeling and fuel qualification). The traditional scope of AFC includes the evaluation and development of multiple fuel forms to support two fuel cycle options: once-through and full recycle. The word “fuel” is used generically to include conventional fuels, transmutation targets, and any associated cladding or duct materials. The once-through fuel cycle addresses advanced light water reactor fuels with enhanced performance, extended burnup, and reduced waste generation. In fiscal year (FY) 2012, AFC’s scope expanded to include research, development, and demonstration (RD&D) for light water reactor (LWR) fuels with enhanced accident tolerance. Fuel fabrication activities include the development of innovative methods to enhance process efficiencies, reduce waste, and improve control over as-fabricated fuel microstructural properties to achieve desired in-reactor performance. Using modern modeling and simulation approaches, the objective is to predict fresh fuel properties given the feedstock characteristics and fabrication process parameters. The performance-related activities include small-scale, in-reactor, and out-of-reactor phenomenological testing (distinct from, but synergistic with, integral prototypic testing) and extensive, quantitative characterization (focusing on characterization of fuel and cladding materials at the scale of microstructure) both before and after testing. Larger-scale, prototypic experiments are conducted in concert with phenomenological testing to drive a Fuel Development and Qualification program, incorporating a fundamental understanding of fuel behavior performance characteristics. Then, using the tools developed under the productive science-based approach, fuels will be optimized to meet specific performance requirements, thereby minimizing the need to repeatedly perform large-scale, integral experiments over a wide parametric range as a means of experimental exploration. Two significant initiatives are underway within AFC. First, a gap analysis completed in early FY 2019 identified critical irradiation testing needs that are lacking within the national light water reactor (LWR) fuels testbed since the shutdown of the Halden Reactor in 2018. The identified gaps are for instrumented, prototypic testing of LWR fuels, especially under boiling water reactor conditions, ramp conditions, and conditions leading to fuel failure; these needs exist for supporting current LWR fuels and their possible extension to higher burnups, but are especially urgent relative to near-term development and qualification of accident-tolerant fuels. Recommendations that resulted from the Halden Gap Analysis focused on enhancements at Advanced Test Reactor (ATR) and Transient Reactor Test Facility (TREAT) to fill gaps in testing capabilities relative to these needs. Second, a concerted effort to develop and demonstrate a systematic approach to accelerating the development, testing, and qualification of new fuel systems has been initiated. This is highlighted by a test strategy that combines the considerable advances in multiscale, mechanistic fuel modeling of recent years with a MiniFuel separate effects test program in the High Flux Isotope Reactor (HFIR) and a Fission Accelerated Steady-state Testing (FAST) semi-integral accelerated test program in ATR. This approach is being tested/demonstrated using the metallic fuel system, but if successful it is expected to be extensible to multiple fuel types and diverse applications. This document includes an overview of the NFCSC program, a definition of science-based development of nuclear fuels, near-term goals for Advanced LWR fuels (ALFs), and longer-term goals for Advanced Reactor Fuels (ARFs) RD&D. This includes the activities that will be conducted to achieve success toward the grand challenge, as well as the goals and milestones to be achieved over the next few decades of research and development. Long-term goals are based on the DOE Office of Nuclear Energ

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2020

Tuning the Morphology and Electronic Properties of Single-Crystal LiNi 0.5 Mn 1.5 O 4-δ : Exploring the Influence of LiCl–KCl Molten Salt Flux Composition and Synthesis Temperature

Single-crystal materials have played a unique role in the development of high-performance cathode materials for Li batteries due to their favorable chemomechanical stability. The molten salt synthesis method has become one of the most prominent techniques used to synthesize single-crystal layered and spinel materials. In this work, the molten salt synthesis method is used as a technique to tune both the morphology and Mn 3+ content of high-voltage LiNi 0.5 Mn 1.5 O 4 (LNMO) cathodes. The resulting materials are thoroughly characterized by a suite of analytical techniques, including synchrotron X-ray core-level spectroscopy, which are sensitive to the material properties on multiple length scales. Furthermore, the multidimensional characterization allows us to build a materials library according to the molten salt phase diagram as well as to establish the relationship among synthesis, material properties, and battery performance. The results of this work show that the Mn 3+ content is primarily dependent on the synthesis temperature and increases as the temperature is increased. Additionally, the particle morphology is mostly dependent on the composition of the molten salt flux, which can be tailored to obtain well-defined octahedrons enclosed by (111) facets, plates with predominant ($11\tilde{2}$) facets, irregularly shaped particles, or mixtures of these. The electrochemical measurements indicate that the Mn 3+ content has a larger contribution to the battery performance of LNMO than do morphological characteristics and that a significant amount of Mn 3+ could become detrimental to the battery performance. However, with similar Mn 3+ contents, morphology still plays a role in influencing the battery cycle life and rate performance. The insights of molten salt synthesis parameters on the formation of LNMO, with deconvolution of the roles of Mn 3+ and morphology, are crucial to continuing studies in the rational design of LNMO cathode materials for high-energy Li batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Role of Eu-Doping in the Electron Transport Behavior in the Zintl Thermoelectric Ca 5-x-y Yb x Eu y Al 2 Sb 6 System

A series of Eu-doped Zintl compounds belonging to theCa 5-x-y Yb x Eu y Al 2 Sb 6 (x = 0, 1.12; 0 ≤ y ≤ 0.63(2)) system have been successfully synthesized by both the arc-melting and the molten Pb-flux methods. All of the five title compounds initially crystallized in the Ca 5 Ga 2 As 6 -type phase (space group Pbam, Z = 2, Pearson code oP26) and maintained their original structure even after the post-heat treatment, unlike the recently reported n-type Zintl analogues in the Ca 5-x-y Yb x RE y Al 2 Sb 6 (RE = Pr, Nd, Sm) systems, which underwent a phase transition from the Ca 5 Ga 2 As 6 -type to the Ca 5 Al 2 Bi 6 -type phase after annealing. This research aimed to understand the origin of the structural preference of the title Ca 5-x-y Yb x Eu y Al 2 Sb 6 system, whether it was affected by the valence electron count or the cationic size. Electrical transport property measurements showed an increase in electrical conductivities and a decrease of Seebeck coefficients for Ca 4.89(1) Eu 0.11 Al 2 Sb 6 , Ca 4.82(1) Eu 0.18 Al 2 Sb 6 , and Ca 4.62(1) Eu 0.38 Al 2 Sb 6 , compared to the parental compound Ca 5 Al 2 Sb 6 . Hole effect measurements proved that these changes should be attributed to the reduced carrier concentration and enhanced carrier mobility. The comprehensive density functional theory calculations including electron density map analysis for the hypothetical model Ca 4.5 Eu 0.5 Al 2 Sb 6 revealed that the polarity between Al and Sb forming the anionic frameworks decreased as the Eu-dopants were introduced, which eventually affected the carrier mobility in the anionic frameworks. Thermal conductivity measurements proved that the Eu-doping successfully lowered the lattice thermal conductivity because of the enhanced atomic disordering. In conclusion, the magnetization measurements for Ca 4.37(2) Eu 0.63 Al 2 Sb 6 showed a typical Curie–Weiss behavior with weak antiferromagnetic nearest-neighbor interactions with θ p = -5.07 K.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Synthesis of cobalt grown from Co-S eutectic in high magnetic fields

Samples of Co were grown directly in the ferromagnetic state under equilibrium conditions using a cobalt sulfide flux. Magnetic fields up to 9 T were applied during growth, and isolated Co products exhibit progressively elongated morphologies, from cubes to rectangular rods to needle-like tendrils with poorly-defined facets. The degree of elongation of the major axis was found to correlate with magnetic field direction, strength, and gradient. Two-dimensional X-ray diffraction data indicate some level of polycrystalline-like samples, and quantitative analyses (Le Bail and Rietveld) of the one-dimensional data confirm the presence of hcp and fcc phases. The magnetic responses indicate a partial alignment of the magnetic easy-axis of the hcp phase along the magnetic field present during growth.

36 MATERIALS SCIENCE↗