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Identifying Challenges in Safeguards for Metallic Fuel Fabrication Facilities

As new advanced reactors gain popularity, there is an increasing interest in metallic fuel fabrication for fast reactors. While metallic fuels themselves are not a new idea, as many of the first reactors employed metallic fuels, new designs, compositions, and fabrication methods are appearing throughout the nuclear community. As the interest grows and facilities are constructed, both domestic and international safeguards will need to be heavily involved to support safeguards-by-design (SBD) measures from the start. This work compiles a review of historical and modern fuel types and fabrication methods, fabrication processes, safeguards gaps, and potential safeguards solutions. Metallic nuclear fuel types have been around for many decades and were included in some of the first reactors including the Experimental Breeder Reactor (EBR)-I and -II, the Fermi 1 reactor, the Integral Fast Reactor (IFR), and the Dounreay Fast Reactor (DFR). These reactors used various compositions including pure uranium (U) metal, U-zirconium (Zr) alloys, plutonium (Pu)-aluminum (Al) alloys, U-fissium (Fs) alloys, U-Pu-Zr alloys, and U-molybdenum (Mo) alloys [1, 2, 3, 4, 5]. These small alloying additions are included to improve the material properties of the pure U metal. The alpha-phase U (stable below 661C) suffers elongation in one direction causing grain boundary cracking and increasing creep rate due to irradiation growth, thermal cycling, and preferential crystal orientation. It is ideal to utilize the gamma-phase U (typically stable above 769C) by adding small amounts of alloying elements such as Zr or Mo to stabilize this phase down to room temperature [3]. Additionally, some research has been focused on U with transuranic (TRU) elements present, typically coming from the used fuel recycling process. Including these elements in fast reactor fuel can aid in the reduction of nuclear waste by burning minor long-lived actinides. However, the additions of TRU elements can cause concerns to arise when trying to fabrication or safeguard metallic fuels. A typical metallic fuel element is shown in Figure 1. Sodium is added into the cladding to create a thermal bond between the fuel slug and cladding wall. The fuel slug is then inserted and the end plug is welded on to the top of the fuel element. A gas plenum is left to create a headspace for gaseous fission products to escape rather than continue to build in the fuel itself [1, 5]. Other fuel element geometries exist as well, such as the Lightbridge twisted cruciform geometry shown in Figure 2 [6]. This design allows for better cooling performance and provides room for fuel rod swelling without impacting the fuel rod diameter. There are many different fabrication methods for metallic fuels, which is one of the many benefits of these fuel types. Many of these fabrication methods are relatively easy and cost-efficient. The most popular fabrication method is injection casting, sometimes called vacuum induction melting (VIM), shown in Figure 3 [4, 8, 9, 7, 10]. This method was largely used for EBR-II fuel fabrication. The injection casting system is contained inside of a vessel consisting of a Y2O3-coated graphite crucible surrounded by an induction coil with ZrO2-coated quartz molds suspended above the crucible. The fuel feedstock is placed inside of the graphite crucible and melted using the induction furnace. The induction furnace utilizes a dual frequency with the high frequency melting the feedstock and the low frequency causing stirring of the melted feedstock to form a homogeneous mixture. The mixture is heated to approximately 1600C in an argon environment. The vessel is evacuated and then the quartz molds are lowered into the graphite crucible containing the molten metal and the vessel is repressurized to inject the metal fuel upwards into the molds. The molds are removed and then shattered to release the fuel slugs. This fabrication method was used to fabricate 39,000 metallic fuel pins for EBR-II. While injection casting has been the most common metallic fuel fabrication method throughout the decades, many other methods have been explored including low-pressure gravity casting, microwave casting, continuous casting, centrifugal casting, coextrusion, and many others [11, 12, 8, 13, 14, 15]. Some of these methods aim to mitigate challenges that arise with americium (Am) volatilization during the casting process for TRU-containing fuel feedstocks, an issue with injection casting. Coextrusion is one of the methods explored at the Idaho National Laboratory (INL) and has been utilized for the initial fabrication tests of Lightbridge's unique fuels, as well as other metallic fuels with cladding coextruded. In this process, large billets are formed and machined and then inserted into a molten salt bath for approximately 30 minutes. The billets are then loaded into the extrusion press and extruded. This process can be seen in Figure 4 [15].

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Stress Distribution During Deformation of Polycrystalline Aluminum by Molecular-Dynamics and Finite-Element Modeling

In this paper, a multiscale modelling strategy is used to study the effect of grain-boundary sliding on stress localization in a polycrystalline microstructure with an uneven distribution of grain size. The development of the molecular dynamics (MD) analysis used to interrogate idealized grain microstructures with various types of grain boundaries and the multiscale modelling strategies for modelling large systems of grains is discussed. Both molecular-dynamics and finite-element (FE) simulations for idealized polycrystalline models of identical geometry are presented with the purpose of demonstrating the effectiveness of the adapted finite-element method using cohesive zone models to reproduce grain-boundary sliding and its effect on the stress distribution in a polycrystalline metal. The yield properties of the grain-boundary interface, used in the FE simulations, are extracted from a MD simulation on a bicrystal. The models allow for the study of the load transfer between adjacent grains of very different size through grain-boundary sliding during deformation. A large-scale FE simulation of 100 grains of a typical microstructure is then presented to reveal that the stress distribution due to grain-boundary sliding during uniform tensile strain can lead to stress localization of two to three times the background stress, thus suggesting a significant effect on the failure properties of the metal.

Yamakov, V.↗

The assessment of metal fiber reinforced polymeric composites

Because of their low cost, excellent electrical conductivity, high specific strength (strength/density), and high specific modulus (modulus/density) short metal fiber reinforced composites have enjoyed a widespread use in many critical applications such as automotive industry, aircraft manufacturing, national defense, and space technology. However, little data has been found in the study of short metal fibrous composites. Optimum fiber concentration in a resin matrix and fiber aspect ratio (length-to-diameter ratio) are often not available to a user. Stress concentration at short fiber ends is the other concern when the composite is applied to a load-bearing application. Fracture in such composites where the damage will be initiated or accumulated is usually difficult to be determined. An experimental investigation is therefore carefully designed and undertaken to systematically evaluate the mechanical properties as well as electrical properties. Inconel 601 (nickel based) metal fiber with a diameter of eight microns is used to reinforce commercially available thermoset polyester resin. Mechanical testing such as tensile, impact, and flexure tests along with electrical conductivity measurements is conducted to study the feasibility of using such composites. The advantages and limitations of applying chopped metal fiber reinforced polymeric composites are also discussed.

Chung, Wenchiang R.↗

Combining Hard with Soft Materials in Nanoscale Under High-Pressure High-Temperature Conditions

Nano-composites with a primary nanocrystalline ceramic matrix and a secondary nanocrystalline material (metal or semiconductor) were synthesized by infiltration of an appropriate liquid into ceramic compacts under pressures of up to 8 GPa and temperatures of up to 2000 K. The purpose of our work is to obtain nanocomposites which constitute homoger?ous mixtures of two phases, both forming nano- grains of about 10 nm in size. The high pressure is used to bring the porosity of the compacted powders down to the nano-scale and force a given liquid into the nano-sized pores. The advantage of the infiltration technique is that, in a single, continuous process, we start with a nanocrystalline powder, compress it to form the matrix of the composite, and crystallize and/or synthesize a second nanomaterial in the matrix pores. The key limitation of this technology is, that the pores in the matrix need to stay open during the entire process of infiltration. Thus the initial powder should form a rigid skeleton, otherwise the so-called self-stop process can limit cr block a further flow of the liquid phase and hinder the process of the composite formation. Therefore powders of only very hard ceramic materials like diamond, Sic, or Alz03, which can withstand a substantial external load without undesired deformation, can be used as the primary phase. With this technique, using diamond and S i c ceramic powders infiltrated by liquid metals (AI, Zn, Sn, Ag, Au) and semiconductors (Si, Ge, GaAs, CdTe), we obtained nano-composites with the grain size in the range of 10 - 30 nm. Our work addresses the key problem in manufacturing bulk nanocrystalline materials, i.e. preservation of nano-scale during the fabrication process. In this paper we discuss basic technical and methodological problems associated with nano-infiltration based on the results obtained for Zn-Sic composites.

Palosz, B.↗

Salt‐in‐Salt Reinforced Carbonate Electrolyte for Li Metal Batteries

Abstract The instability of carbonate electrolyte with metallic Li greatly limits its application in high‐voltage Li metal batteries. Here, a “salt‐in‐salt” strategy is applied to boost the LiNO 3 solubility in the carbonate electrolyte with Mg(TFSI) 2 carrier, which enables the inorganic‐rich solid electrolyte interphase (SEI) for excellent Li metal anode performance and also maintains the cathode stability. In the designed electrolyte, both NO 3 − and PF 6 − anions participate in the Li + ‐solvent complexes, thus promoting the formation of inorganic‐rich SEI. Our designed electrolyte has achieved a superior Li CE of 99.7 %, enabling the high‐loading NCM811||Li (4.5 mAh cm −2 ) full cell with N/P ratio of 1.92 to achieve 84.6 % capacity retention after 200 cycles. The enhancement of LiNO 3 solubility by divalent salts is universal, which will also inspire the electrolyte design for other metal batteries.

Liu, Sufu↗

Salt‐in‐Salt Reinforced Carbonate Electrolyte for Li Metal Batteries

Abstract The instability of carbonate electrolyte with metallic Li greatly limits its application in high‐voltage Li metal batteries. Here, a “salt‐in‐salt” strategy is applied to boost the LiNO 3 solubility in the carbonate electrolyte with Mg(TFSI) 2 carrier, which enables the inorganic‐rich solid electrolyte interphase (SEI) for excellent Li metal anode performance and also maintains the cathode stability. In the designed electrolyte, both NO 3 − and PF 6 − anions participate in the Li + ‐solvent complexes, thus promoting the formation of inorganic‐rich SEI. Our designed electrolyte has achieved a superior Li CE of 99.7 %, enabling the high‐loading NCM811||Li (4.5 mAh cm −2 ) full cell with N/P ratio of 1.92 to achieve 84.6 % capacity retention after 200 cycles. The enhancement of LiNO 3 solubility by divalent salts is universal, which will also inspire the electrolyte design for other metal batteries.

25 ENERGY STORAGE↗

Treatment of low strains and long hold times in high temperature metal fatigue by strainrange partitioning

A procedure for treating creep-fatigue for low strainranges and long hold times is outlined. A semi-experimental approach, wherein several cycles of the imposed loading is actually applied to a specimen in order to determine the stable hysteresis loop, can be very useful in the analysis. Because such tests require only a small fraction of the total failure time, they are not inherently prohibitive if experimental equipment is available. The need for accurate constitutive equations is bypassed because the material itself acts to translate the imposed loading into the responsive hysteresis loops. When strainrange partitioning has been applied in such cases very good results have been obtained.

Manson, S. S.↗

Electrocatalytic water oxidation performance in an extended porous organic framework with a covalent alliance of distinct Ru sites

The rational synthesis of durable, earth-abundant efficient electrocatalysts for the oxygen evolution reaction (OER) from water is one of the most important routes for storing renewable energy and minimizing fossil fuel combustion. The prime hurdles for effectively utilizing commercial RuO 2 as (OER) electrocatalysts are its very low stability, catalyst deactivation, and high cost. In this work, we explored a Ru-integrated porous organic polymer (Ru@Bpy-POP) by a facile one-pot Friedel–Crafts alkylation strategy between redox-active (Ru(demob) 3 Cl 2 ) and a carbazole unit, which is composed of unique features including an extended framework unit, isolated active sites, and tunable electrode kinetics. Ru@Bpy-POP can serve as a bridge between a Metal–Organic Framework (MOF) and POP-based catalytic systems with a balanced combination of covalent bonds (structural stability) and open metal sites (single site catalysis). Ru@Bpy-POP, deposited on a three-dimensional nickel foam electrode support, exhibits a promising electrocatalytic OER activity with an ultra-low ruthenium loading compared to a benchmark RuO 2 catalyst, providing an overpotential of about 270 mV to reach 10 mA cm –2 in an alkaline medium. Moreover, a high current density of 248 mA cm –2 was achieved for the Ru@Bpy-POP catalyst at only 1.6 V (vs. RHE), which is much higher than 91 mA cm –2 for commercial RuO 2 . The robust, albeit highly conjugated, POP framework not only triggered facile electro-kinetics but also suppressed aggregation and metallic corrosion during electrolysis. In particular, the benefits of covalent integration of distinct Ru sites into the framework can modulate intermediate adsorption and charge density, which contributes to its exceptional OER activity. All of the critical steps involved in OER are complemented by Density Functional Theory (DFT) calculations, which suggest that electrocatalytic water oxidation proceeds from a closed-shell configuration to open-shell electronic configurations with high-spin states. Finally, these open-shell configurations are more stable than their closed-shell counterparts by 1 eV, improving the overall catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deactivation by Potassium Accumulation on a Pt/TiO 2 Bifunctional Catalyst for Biomass Catalytic Fast Pyrolysis

Biomass-derived feedstocks bring significant challenges to the longevity of the catalysts used for their conversion, and alkali metals, for example, K, in the feedstock have been widely ascribed as one of the important factors causing catalyst deactivation. To address this challenge, it is critical to understand the mechanism of catalyst deactivation caused by K accumulation to guide the improvement of catalysts and processes and the development of catalyst regeneration strategies. In this work, we report a deep understanding of the impact of K on a bifunctional Pt/TiO 2 catalyst, which is an efficient catalyst for the ex situ catalytic fast pyrolysis of biomass. We simulated the K-poisoning of Pt/TiO 2 catalysts by purposely loading different amounts of K (100-6000 ppm by weight) on the catalysts. A series of characterization approaches, including scanning transmission electron microscopy, Fourier transform infrared spectroscopy, and chemical titration, were combined with a kinetic assessment of multiple probe reactions to elucidate the mechanism of Pt/TiO 2 deactivation by K accumulation. At low K loadings (<800 ppm), K preferentially poisons the strong Lewis acid sites, leading to significantly reduced activity for acid-catalyzed alcohol dehydration. However, acetone condensation is less sensitive to the poisoning of strong Lewis acid sites. Reactions that occur on Pt sites or at the metal-support interface, including alkene hydrogenation, m-cresol hydrodeoxygenation (HDO), and CO oxidation, were not impacted. At high K loadings (>800 ppm), K starts to accumulate on the Pt-TiO 2 interfacial area, poisoning the interfacial active sites for HDO and CO oxidation reactions. We further found that the poisoning of the Pt/TiO 2 catalyst by K is reversible, and water washing can successfully remove the accumulated K and recover the activities for both alcohol dehydration and m-cresol HDO reactions.

09 BIOMASS FUELS↗

Characterization of Embedded Sensors in Stainless Steel Test Articles and Design/Planning for MAGNET Testing

The nuclear industry is pursuing microreactors that can be factory assembled and deployed to remote regions for reliable power generation. One class of microreactors uses a monolithic metal core block coupled to heat pipes for heat rejection, which results in significant thermal stresses in the monolithic structures. This work describes the initial characterization and test plan for evaluating stainless steel test articles fabricated with embedded sensors for measuring heat pipe performance limits, as well as spatially distributed temperatures and strains during electrically heated thermal testing. The electrically heated testing will be performed in the non-nuclear Microreactor Agile Non-Nuclear Testbed and Single Primary Heat Extraction and Removal Emulator facilities located at Idaho National Laboratory. The goals of these tests are to (1) accurately monitor temperature and strain distributions that result from differential thermal expansion in the test articles and (2) quantify heat rejection limits of heat pipes as a function of operating temperature and working fluid during steady-state and transient operations. More generally, the ability to monitor component and system health during microreactor operation is attractive for providing a high sensor density to inform a limited number of microreactor operators to ultimately reduce operation and maintenance costs and move toward semi-autonomous operation. This report discusses the characterization of embedded thermocouples and fiber optic sensors in relevant test articles, including cylindrical pipes and hexagonal monolithic test articles for heat pipe-based reactors. The sensors were embedded by placing them in machined channels and then building up additional material by using ultrasonic additive manufacturing (UAM). UAM is a solid-state welding process that uses downward pressure and a lateral scrubbing motion to bond thin metal foils to a base material layer by layer. The ultrasonic welding process relies on the plastic deformation of the metal—as opposed to typical melting and solidification—to break oxide scales and bond the metal layers. The characterization of these embedded sensors included evaluating fiber optic signal attenuation, observing residual strain in the fibers, investigating microstructural and mechanical aspects, and demonstrating the sensors under various thermal loads and acoustic vibrations. Post-embedding characterization showed a fine grain structure (<1 μm) near the interfaces of the bonded foils as a result of severe deformation from the welding process. A large increase in hardness was observed at the foil interfaces and the fiber/matrix interface compared with the bulk matrix. Even when compared with the SS304 interfaces, the higher hardness observed around the embedded fiber suggests a higher degree of deformation due to the soft metal coating around the silica fiber core. The distributed fiber-optic temperature sensors and embedded thermocouples reliably measured temperature distributions during steady-state and transient thermal testing. The embedded fiber-optic sensors reliably measured strain during both transient and steady-state testing and properly identified resonant frequencies during acoustic testing.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Mechanical properties, failure mechanisms, and scaling laws of bicontinuous nanoporous metallic glasses

Molecular dynamics simulations are employed to study the mechanical properties of nanoporous Cu x Zr 1-x metallic glasses (MGs) with five different compositions, x = 0.28, 0.36, 0.50, 0.64, and 0.72, and porosity in the range 0.1 < Φ < 0.7. Results from tensile loading simulations indicate a strong dependence of Young's modulus, E, and Ultimate Tensile Strength (UTS) on porosity and composition. By increasing the porosity from Φ = 0.1 to Φ = 0.7, the topology of the nanoporous MG shifts from closed cell to open-cell bicontinuous. The change in nanoporous topology enables a brittle-to-ductile transition in deformation and failure mechanisms from a single critical shear band to necking and rupture of ligaments. Genetic Programming (GP) is employed to find scaling laws for E and UTS as a function of porosity and composition. Here, a comparison of the GP-derived scaling laws against existing relationships shows that the GP method is able to uncover expressions that can predict accurately both the values of E and UTS in the whole range of porosity and compositions considered.

36 MATERIALS SCIENCE↗

Environmental remediation with functional aerogels and xerogels

Several different types of aerogel and/or xerogel scaffolds have been demonstrated as effective sorbents for the capture and immobilization of radionuclides in gaseous form [e.g., iodine gas or I2(g), Xe] as well as ionic form (e.g., Ce4+, Cs+, I–, IO3-, Rb+, Sr2+, 99Tc7+, and U6+). These scaffolds have unique properties, which include high specific surface areas, high pore volumes, varieties of pore sizes, and functionalities that provide methods for binding radionuclides through physisorption, chemisorption, or a combination thereof. This combination of properties and functionalities make these types of materials ideal scaffolds for use as sorbents for capturing radionuclides. The primary base materials that will be discussed in this chapter include Ag0-functionalized silica aerogels, Ag+-impregnated aluminosilicate aerogels, Ag0-functionalized aluminosilicate aerogels, metal-impregnated (non-Ag) aluminosilicate aerogels and xerogels, sulfide-based aerogels, and carbon-based aerogel composites. For the capture of I2(g), the materials reported herein show some of the highest iodine loadings ever reported for inorganic sorbents. For the capture of ionic species, these materials also show promise to be some of the next generations of materials for active radionuclide remediation. This progress report will describe how these materials are fabricated, the general properties of these materials, as well as an overview of how they have been used for different applications in environmental remediation of radionuclides.

aerogel, xerogel, iodine, radionuclide remediation↗

Constructing Highly Porous Low Iridium Anode Catalysts Via Dealloying for Proton Exchange Membrane Water Electrolyzers

Iridium (Ir) is the most active and durable anode catalyst for the oxygen evolution reaction (OER) for proton exchange membrane water electrolyzers (PEMWEs). However, their large-scale applications are hindered by high costs and scarcity of Ir. Lowering Ir loadings below 1.0 mgcm -2 causes significantly reduced PEMWE performance and durability. Therefore, developing efficient low Ir-based catalysts is critical to widely commercializing PEMWEs. Herein, an approach is presented for designing porous Ir metal aerogel (MA) catalysts via chemically dealloying IrCu alloys. In this study, the unique hierarchical pore structures and multiple channels of the Ir MA catalyst significantly increase electrochemical surface area (ECSA) and enhance OER activity compared to conventional Ir black catalysts, providing an effective solution to design low-Ir catalysts with improved Ir utilization and enhanced stability. An optimized membrane electrode assembly (MEA) with an Ir loading of 0.5 mg Ir cm -2 generated 2.0 A cm -2 at 1.79 V, higher than the Ir black at a loading of 2.0 mg Ir cm -2 (1.63 A cm -2 ). The low-Ir MEA demonstrated an acceptable decay rate of ≈40 µV h -1 during durability tests at 0.5 (>1200 h) and 2.0 A cm -2 (400 h), outperforming the commercial Ir-based MEA (175 µV h -1 at 2.0 mg Ir cm -2 ).

36 MATERIALS SCIENCE↗

Molecular dynamics simulation of vacancy and void effects on strain-induced martensitic transformations in Fe-50 at.% Ni model concentrated solid solution alloy

Strain-induced martensitic transformations can improve the strength and ductility of some face centered cubic (FCC) metals and alloys. Irradiation-induced defects such as vacancies, dislocation loops, and voids activate martensitic transformations over a wider range of mechanical loading conditions than in pristine material. Furthermore, the mechanisms underlying irradiation-enabled martensite transformations remain unclear. In this work, we use molecular dynamics simulations to study the effect of vacancies and voids on strain-induced martensitic transformations in a model concentrated solid solution alloy Fe-50 at.% Ni. It has been found that single vacancies have no resolvable effect on the transformation because they reduce the stacking fault energy by a relatively insignificant margin and do so only if the vacancy is located on the stacking fault plane. Voids, however, activate the martensite transformation through shear strain accumulation around the void due to dislocation pileup. The larger the void, the more pronounced this effect.

36 MATERIALS SCIENCE↗

Mechanistic Insights toward Accelerated Selenium-Catalyzed Allylic and Propargylic C–H Amination

Catalytic allylic and propargylic C–H aminations present valuable opportunities for the late-stage modification of pharmacophores in drug discovery. However, modern methodology is limited by reliance on expensive transition metal catalysts or slow reactivity. While selenium-catalyzed methods avoid some of these issues, in their current state, they require high catalyst loadings (15 mol %), superstoichiometric quantities of the amine and oxidant source, and long reaction times. Furthermore, our understanding of the mechanism remains incomplete: e.g., what is the catalytically active species, how is the precatalyst converted to it, and what is the role of the ligand? Here, in this paper, we report an N-heterocyclic carbene selenide (NHC-Se) that allows for substantially reduced loadings of selenium without sacrificing reaction time, improves conversions and yields for challenging substrates, and even exhibits the capacity to catalyze 1,4-allylic diamination of alkenes. To understand the origin of the enhanced activity compared to the state-of-the-art NHC-Se precatalyst, we conducted a mechanistic study that supports ligand-free selenium diimide as the active enophile in these systems, while the NHC-derived byproducts, like the corresponding urea, facilitate turnover. We also isolate and structurally characterize NHC-Se mono- and diimido species and explore their mechanistic role. Thus, this work advances C–H amination methodology, our understanding of its mechanistic underpinnings, and selenium chemistry at large.

allylic amination↗

Resistively loaded coplanar waveguide for microwave measurements of induced carriers

We describe the use of a coplanar waveguide (CPW) whose slots are filled with a resistive film, a resistively loaded CPW (RLCPW), to measure two-dimensional electron systems (2DESs). The RLCPW applied to the sample hosting the 2DES provides a uniform metallic surface serving as a gate to control the areal charge density of the 2DES. As a demonstration of this technique, we present measurements on a Si metal–oxide–semiconductor field-effect transistor and a model that successfully converts microwave transmission coefficients into conductivity of a nearby 2DES capacitively coupled to the RLCPW. We also describe the process of fabricating the highly resistive metal film required for fabrication of the RLCPW.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗