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Summary of US DOE R&D Activities on Graphite Oxidation (2006–2021)

The objective of the international collaboration between United States Department of Energy (U.S.-DOE) and Generation IV International Forum (GIF) is the development of the next generation of nuclear energy systems. The current GIF Project Arrangement (PA) on Materials (2018-2022) was revised in 2019 and extended for another 10 years (2020-2030). The Work Package 1 (“Graphite”) of the extended Project Plan (PP) on Materials specifies technical tasks and High Level Deliverables for research and development (R&D) activities related to using graphite in fuel elements, reflectors, and support structures of Very High Temperature Reactors (VHTR). The graphite tasks include specification and acquisition, qualification and development of new grades, characterization of properties, and development of behavior models. Specifically, Task 1.4 (“Graphite Oxidation Behavior”) outlines planned activities related to acute oxidation by air and chronic oxidation by impurities in the helium coolant. A final report on experimental data regarding graphite oxidation behavior is scheduled for 2022 (deliverable 3.1.1.4.a). In preparation of this deliverable, this document summarizes the R&D activities funded by U.S.-DOE from 2006 (the inception of the VHTR system arrangement) through present (2021). This report is being submitted to the GIF Graphite Working Group (GWG) to serve as input for the GWG high-level deliverable to the Project Management Board (PMB) of PA on Materials. Besides U.S.-DOE, other organizations participating to Task 1.4 of the current PA on Materials are: European Commission’s Joint Research Center (JRC), Korea Atomic Energy Research Institute (KAERI), and Japan Atomic Energy Agency (JAEA). U.S.-DOE is the main contributor on graphite oxidation R&D, with 85 % commitment of total funding during 2018-2022.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Perspectives and challenges of ultra-high temperature ceramics for fusion plasma-facing applications

Ultra-high temperature ceramics (UHTCs) offer several potential advantages as plasma-facing components (PFCs) in fusion reactors due to their extreme melting points, tailorable thermal conductivity, and attractive unirradiated mechanical properties including fracture toughness comparable or superior to tungsten. Here, recent developments and material properties of UHTCs are briefly reviewed, along with an overview of limited studies on their responses to neutron irradiation and an evaluation of plasma-surface interactions. Five key research pathways, primarily focused on irradiation effects, for advancing UHTCs in PFC applications are discussed: (1) assessing irradiation effects on the coupled thermal–mechanical performance (2) addressing the lack of studies on irradiation, plasma-surface interactions, and their synergistic effects; (3) investigating high-temperature (>1000 °C) neutron irradiation effects critical for PFC performance; (4) optimizing multi-component UHTC compositions or composites to improve thermal or mechanical properties; (5) enhancing radiation resistance to mitigate microcracking and void swelling through strategies such as increasing sink strength by reducing grain size, introducing fine particles, and leveraging complex concentrated alloy concepts.

36 MATERIALS SCIENCE↗

Development and characterization of Nb3Sn/Al2O3 superconducting multilayers for particle accelerators

Abstract Superconducting radio-frequency (SRF) resonator cavities provide extremely high quality factors > 10 10 at 1–2 GHz and 2 K in large linear accelerators of high-energy particles. The maximum accelerating field of SRF cavities is limited by penetration of vortices into the superconductor. Present state-of-the-art Nb cavities can withstand up to 50 MV/m accelerating gradients and magnetic fields of 200–240 mT which destroy the low-dissipative Meissner state. Achieving higher accelerating gradients requires superconductors with higher thermodynamic critical fields, of which Nb 3 Sn has emerged as a leading material for the next generation accelerators. To overcome the problem of low vortex penetration field in Nb 3 Sn, it has been proposed to coat Nb cavities with thin film Nb 3 Sn multilayers with dielectric interlayers. Here, we report the growth and multi-technique characterization of stoichiometric Nb 3 Sn/Al 2 O 3 multilayers with good superconducting and RF properties. We developed an adsorption-controlled growth process by co-sputtering Nb and Sn at high temperatures with a high overpressure of Sn. The cross-sectional scanning electron transmission microscope images show no interdiffusion between Al 2 O 3 and Nb 3 Sn. Low-field RF measurements suggest that our multilayers have quality factor comparable with cavity-grade Nb at 4.2 K. These results provide a materials platform for the development and optimization of high-performance SIS multilayers which could overcome the intrinsic limits of the Nb cavity technology.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Nanohybrid of Cu2O-Ti3C2Tx as a Silver-Free MXene Sorbent for Iodine Gas Capture from Nuclear Waste

The capture of volatile radioiodine from nuclear fuel reprocessing off-gas streams remains a critical challenge due to the high volatility, long half-life of 129I, and biological uptake of iodide from the environment. Although silver-based sorbents provide strong iodine chemisorption, their high cost and regulatory classification as mixed radioactive-hazardous waste motivate the development of alternative materials. Here, we report a silver-free Cu2O-Ti3C2Tx MXene hybrid for iodine gas capture at 150 °C. Structural and compositional analyses confirm the formation of Cu2O nanoparticles on Ti3C2Tx nanosheets and their subsequent conversion to thermodynamically stable CuI upon static iodine gas exposure, achieving an iodine mass loading of up to 1115 mg/g. These results demonstrate the potential of Cu2O-Ti3C2Tx MXene as a copper-based alternative to silver sorbents for elevated-temperature iodine gas capture.

iodine gas capture↗

Progress and opportunities in corrosion mitigation in heat transfer fluids for next-generation concentrating solar power

Concentrating solar power (CSP) systems have gained considerable eminence in converting solar thermal energy into electrical power in recent years. According to the U.S. Department of Energy's Gen3 roadmap, the CSP system should operate > 700 °C, as its efficiency depends directly on the operating temperature of the heat transfer fluids (HTFs). A significant challenge, however, is the corrosion of containment materials by the HTFs that is exacerbated at the higher temperatures. A comprehensive review of the high temperature stable HTFs, their properties, corrosion mechanisms on different alloys, and corrosion mitigation measures is of much importance for directing a concerted research and development in the field, which forms the motivation for this compendium. First, molten salt HTFs and their thermophysical properties, along with liquid metals, are introduced. Corrosion of structural materials in different HTFs including molten salts, liquid metals, and supercritical carbon-di-oxide at various temperatures and the corrosion mechanisms are comprehensively reviewed. In addition, several corrosion mitigation methods are discussed. Finally, future directions for HTFs and corrosion mitigation methods in molten salts are proposed. As a result, the holistic review presented here will serve as the foundation for further research addressing relevant challenges and enabling the promise of achieving cost-competitive CSP.

14 SOLAR ENERGY↗

An Innovative Design of High-Temperature, Sensible Molten Salt Thermal Energy Storage Systems With Geopolymer Insulation

This project aims to mitigate the risks of the current molten salt TES tank designs. The goal is to create a more reliable and cost-effective TES by (1) developing a new material solution for internal thermal insulation and (2) by designing a concrete-based tank structure to eliminate metal-related issues (e.g., corrosion, thermomechanical failure, etc.). Firstly, the project aims to engineer a composite refractory insulation material that possesses sufficient thermal insulation properties without significantly sacrificing the resistance to salt permeation and mechanical strength, which is the major trade-off in traditional refractory insulation design. The primary objective is to perform materials design and optimization of the composite refractory to achieve the required thermal and mechanical properties as suitable internal insulation for molten salt TES. Secondly, the project aims to design a concrete-based TES system with conventional low- cost Portland cement serving as the primary tank structure and the aforementioned composite refractory as the internal thermal insulation and salt containment. The objective is to investigate the technical and economical feasibilities of concrete tanks for high- temperature molten salt storage applications.

14 SOLAR ENERGY↗

Multiphysics Simulation of the NASA SIRIUS-CAL Fuel Experiment in the Transient Test Reactor Using Griffin

After approximately 50 years, NASA is restarting efforts to develop nuclear thermal propulsion (NTP) for interplanetary missions. Building upon nuclear engine tests performed from the late 1950s to the early 1970s, the present research and testing focuses on advanced materials and fabrication methods. A number of transient tests have been performed to evaluate materials performance under high-temperature, high-flux conditions, with several more experiments in the pipeline for future testing. The measured data obtained from those tests are being used to validate the Griffin reactor multiphysics code for this particular type of application. Griffin was developed at Idaho National Laboratory (INL) using the MOOSE framework. This article describes the simulation results of the SIRIUS-CAL calibration experiment in the Transient Reactor Test Facility (TREAT). SIRIUS-CAL was the first transient test conducted on NASA fuels, and although the test was performed with a relatively low core peak power, the test specimen survived a temperature exceeding 900 K. Griffin simulations of the experiment successfully matched the reactor’s power transient after calibrating the initial control rod position to match the initial reactor period. The thermal-hydraulics model largely matches the time-dependent response of a thermocouple located within the experiment specimen to within the uncertainty estimate. However, the uncertainty range is significant and must be reduced in the future.

33 ADVANCED PROPULSION SYSTEMS↗

Synthetic Accessibility and Sodium Ion Conductivity of the Na8–x A x P2O9 (NAP) High-Temperature Sodium Superionic Conductor Framework

Advancement of solid-state electrolytes (SSEs) for all solid-state batteries typically focuses on modification of a known structural framework to improve conductivity, e.g., cation substitution for an immobile ion or varying the concentration of the mobile ions. Novel frameworks can be disruptive by enabling fast ion conduction aided by different structure and diffusion mechanisms, thereby unlocking optimal conductors with different properties. Herein, we perform a high-throughput survey of a structural framework for sodium ion conduction, Na8–x A x P2O9 (NAP), to understand the family’s thermodynamic stability, synthesizability, and ionic conduction. We show that the parent phase Na4TiP2O9 (NTP) undergoes a structural distortion (with accompanying conductivity transition) due to unstable phonons arising from pseudo-Jahn–Teller mode in the 1D titanium chains. Screening compounds in which Ti is substituted by other metals computationally reveal a number of candidates that are predicted to be low in formation energy and have high predicted ionic conductivities. High-throughput experimental and subsequent methodology optimization trials deliver one new compound, Na4SnP2O9 (NSP). X-ray diffraction (XRD), microscopy, and spectroscopy characterization indicate that the room-temperature structure of NSP is similar to the high-temperature, orthorhombic NTP phase but with some small unresolved structural differences. These uncharacterized structural details are speculated to limit the ion conductivity. Temperature-dependent XRD and electrochemical impedance spectroscopy indicate multiple coupled conductivity–structure transitions at a high temperature. We demonstrate the challenges with synthesis development and a priori identification of promising SSE phases as a major bottleneck in new (energy) materials development.

Chemical reactions↗

Vacancy-Dependent Diffusion Mechanism in Oxygen-Defective SrFeO 3 Perovskite Materials: First-Principles Density Functional Theory and Experimental Approach

Understanding oxygen diffusion at the atomic scale in SrFeO 3−δ perovskites is crucial for developing oxygen storage materials with optimal performance. Such materials are required to have high stability, corrosion resistance, and acceptable oxygen storage capacity at moderate operating temperatures and pressures. Here, in this study, we used first-principles density functional theory and thermogravimetric analysis to study the vacancy-dependent oxygen diffusion in oxygen-deficient SrFeO 3−δ (δ = 0, 0.065, 0.125, 0.25, 0.5) perovskites. The electronic structures, including the partial- and spin-resolved density of states, for different SrFeO 3−δ phases were calculated and compared with available experimental and theoretical results. By mapping the migration pathways, we investigated diffusion mechanisms and calculated the energy barriers for oxygen diffusion in cubic, orthorhombic, and brownmillerite phases of SrFeO 3−δ perovskites. Using the calculated energy barriers, we deduced the diffusion time scales and diffusion coefficients within SrFeO 3−δ . A diffusion coefficient on the order of 10 –8 m 2 /s was obtained for SrFeO 2.875 . We experimentally investigated the roles of temperature and oxygen partial pressures on the redox kinetics and deduced the kinetics rate and diffusion density, which agreed well with the calculated values for the density of diffusing oxygen vacancy in the lattice. Our results showed that the energy barrier tends to reduce at higher oxygen concentrations. Our results serve as an important guideline for designing oxygen storage materials with optimal redox kinetics.

chemical looping with oxygen uncoupling (CLOU)↗

Process Intensification for Nanostructure Aluminum Extrusions

A new technology called Shear Assisted Processing and Extrusion (ShAPE™), pioneered at the Pacific Northwest National Laboratory (PNNL), has the potential to revolutionize the US extrusion industry. Maturation of the ShAPE™ process would create a new cross cutting US manufacturing technology that advances three key the objectives within AMO; namely, nanomaterials processing, process intensification, and materials for extreme and harsh environments. PNNL and SCM Metals Products, Inc. (SCM), a division of Kymera International, will collaborate to mature the ShAPE™ extrusion process beyond TRL 3 to increase the likelihood of its adoption by industry. PNNL’s custom (one-of-a-kind in the world) ShAPE™ machine will be used to extrude round rods of high strength aluminum alloy feedstock powder provided by SCM. As proof-of-concept, PNNL has previously extruded 5 mm diameter rods with SCM aluminum alloy powder AL-12.4TM. This project aims to scale up the process to a diameter of 25 mm while retaining the excellent mechanical properties achieved for the 5 mm diameter rods. The degree of process intensification with ShAPE™ will also be estimated. The primary objectives of this project are as follows. 1) Fabricate 25 mm diameter nanostructured extrusions in bulk, directly from AL-12.4TM aluminum alloy powder without the need for canning, degassing, compaction, and other intermediate steps typical of powder metallurgy extrusion. 2) Achieve a microstructure with an ultrafine grained (UFG <1 µm) aluminum matrix having refined and homogenously distributed nanoscale second phases. 3) Show that the ram force can be significantly reduced compared to conventional powder metallurgy extrusion of the same material and estimate the extent of process intensification that may be possible with ShAPE™. 4) Demonstrate improved high-temperature mechanical properties compared to conventional extrusion of the same material. The following tasks will be undertaken to achieve these objectives. PNNL will develop the die set and process parameters necessary to fabricate Al-12.4TM extrusions with a 25 mm diameter. Microstructural analysis will be performed by PNNL while mechanical testing will be conducted by SCM. With information learned from the process development and characterization, PNNL will perform an estimate of the degree of process intensification that may be possible with ShAPE™.

42 ENGINEERING↗

Evaluating Lithium-Lead Mixtures for Increased Tritium Breeding in Fusion Energy Blanket Systems: Exploring the Impact of Composition and Temperature

This project investigates hypo- and hyper-eutectic liquid lithium-lead (PbLi) mixtures as a coolant in fusion blanket systems, with a focus on testing the compatibility of compositions with better tritium breeding ratios (TBR). The 12-month study concentrates on static corrosion experiments, comparing silicon carbide (SiC) corrosion rates in Li-rich and eutectic Li-Pb mixtures, and examining interactions between Mo and PbLi. The research seeks to determine the maximum operating temperatures for this material combination, acknowledging the balance between Li-Pb melting temperature and achievable TBR to unlock new opportunities for blanket design. This work lays the groundwork for future collaboration between Kyoto Fusioneering and Oak Ridge National Laboratory (ORNL). Findings could enhance the TBR of fusion blanket designs, and impact fusion energy development by confirming material compatibility between different Li-Pb mixtures with SiC and Mo at higher temperatures, including at temperatures relevant for very high-temperature blankets (1,000 °C), which could enable higher electricity conversion efficiencies and commercial applications using process heat.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Polybenzimidazole-Based Polymer Electrolyte Membranes for High-Temperature Fuel Cells: Current Status and Prospects

Polymer electrolyte membrane fuel cells (PEMFCs) expect a promising future in addressing the major problems associated with production and consumption of renewable energies and meeting the future societal and environmental needs. Design and fabrication of new proton exchange membranes (PEMs) with high proton conductivity and durability is crucial to overcome the drawbacks of the present PEMs. Acid-doped polybenzimidazoles (PBIs) carry high proton conductivity and long-term thermal, chemical, and structural stabilities are recognized as the suited polymeric materials for next-generation PEMs of high-temperature fuel cells in place of Nafion® membranes. This paper aims to review the recent developments in acid-doped PBI-based PEMs for use in PEMFCs. The structures and proton conductivity of a variety of acid-doped PBI-based PEMs are discussed. More recent development in PBI-based electrospun nanofiber PEMs is also considered. The electrochemical performance of PBI-based PEMs in PEMFCs and new trends in the optimization of acid-doped PBIs are explored.

25 ENERGY STORAGE↗

NLR CSP Optical Facilities: Illuminating the Path Forward Through Innovation and Impact: Agreement 38490

This initiative is a multi-faceted project at the National Laboratory of the Rockies (NLR) aimed at strengthening its Concentrating Solar Power (CSP) Optical Facilities to advance the development of low-cost, high-performance materials for solar and other applications. The project's strategy is built on three pillars: strategic stakeholder engagement, diligent facility maintenance and utilization, and the development of new research capabilities. The overarching goal is to ensure the facilities remain state-of-the-art resources for industry and academia, thereby accelerating the conversion of concentrated sunlight into energy. A key driver of the project is an international Advisory Board, which provides critical guidance on research priorities and industry needs, leading to new collaborations and secured funding. This external engagement, combined with proactive outreach to industry partners, ensures the lab's work remains aligned with real-world challenges, including materials durability and performance certification. Significant efforts in facility maintenance have addressed challenges with aging infrastructure. Notable achievements include the complete refurbishment of the hail-damaged Ultra-Accelerated Weathering System (UAWS) and the successful replacement of a failing 15-year-old Lambda 1050 spectrophotometer with a new-generation model, substantially upgrading material characterization capabilities. These maintenance activities were complemented by achieving a prestigious ISO 9001:2015 certification for the Advanced Optical Materials Labs, formally recognizing the quality and reliability of NLR's measurement capabilities. Despite these successes, challenges remain, including high demand for the High Flux Solar Furnace (HFSF) and intermittent failures of other key instruments. The project has delivered major advancements in research techniques and capabilities. At the Flatirons campus, a new indoor laboratory, was established to house advanced deflectometry and photogrammetry systems for heliostat characterization. For on-sun testing, a novel, actively cooled turning mirror was developed for the HFSF, enabling more realistic testing of particle receivers and components. A collaboration with Virginia Tech successfully demonstrated the high-temperature durability of a new solar absorber coating through extensive cyclic testing. Concurrently, new modeling took place to better predict material degradation on rough, fractal surfaces. In summary, this project has systematically enhanced NLR's CSP Optical Facilities through strategic upgrades, rigorous maintenance, and stakeholder-guided research. By overcoming equipment failures, budgetary constraints, and logistical hurdles, the project has reinforced NLR's role as a central hub for CSP innovation and materials testing. Future work will focus on securing diverse funding, expanding collaborations, and continuing to provide the critical infrastructure needed to accelerate the development and deployment of next-generation technologies.

14 SOLAR ENERGY↗

Stretchable and Self‐Healable Semiconductive Composites Based on Hydrogen Bonding Cross‐linked Elastomeric Matrix

Abstract Semiconductors with both high stretchability and self‐healing capability are highly desirable for various wearable devices. Much progress has been achieved in designing highly stretchable semiconductive polymers or composites. The demonstration of self‐healable semiconductive composite is still rare. Here, an extremely soft, highly stretchable, and self‐healable hydrogen bonding cross‐linked elastomer, amide functionalized‐polyisobutylene (PIB‐amide) is developed, to enable a self‐healable semiconductive composite through compounding with a high‐performance conjugated diketopyrrolopyrrole (DPP‐T) polymer. The composite, consisting of 20% DPP‐T and 80% PIB‐amide, shows record high crack‐onset strain (COS ≈1500%), extremely low elastic modulus (E≈1.6 MPa), and unique ability to spontaneously self‐heal atroom temperature within 5 min. Unlike previous works, these unique composite materials also show strain‐independent charge mobility. An in‐depth morphological study based on multi‐model techniques indicate that all composites show blending ratio‐ and stretching‐independent fibril‐like aggregation due to the strong hydrogen bond in elastomer to enable the unique stable charge mobility. This study provides a new direction to develop highly healable and electronically stable semiconductive composite and will enable new applications of stretchable electronics.

Chemistry↗

Make Selenium Reactive Again: Activating Elemental Selenium for Synthesis of Metal Selenides Ranging from Nanocrystals to Large Single Crystals

The inertness of elemental selenium is a significant obstacle in the synthesis of selenium-containing materials at low reaction temperatures. Over the years, several recipes have been developed to overcome this hurdle; however, most of the methods are associated with the use of highly toxic, expensive, and environmentally harmful reagents. As such, there is an increasing demand for the design of cheap, stable, and nontoxic reactive selenium precursors usable in the low-temperature synthesis of transition metal selenides with vast applications in nanotechnology, thermoelectrics, and superconductors. Herein, a novel synthetic route has been developed for activating elemental selenium by using a solvothermal approach. By comprehensive 77 Se NMR, Raman, and infrared spectroscopies and gas chromatography–mass spectrometry, we show that the activated Se solution contained HSe – , [Se–Se] 2– , and Se 2– ions, as well as dialkyl selenide (R 2 Se) and dialkyl diselenide (R–Se–Se–R) species in dynamic equilibrium. This also corresponded to the first observation of naked Se 2 2– in solution. The versatility of the developed Se precursor was demonstrated by the successful synthesis of (i) the polycrystalline room-temperature modification of the β-Ag 2 Se thermoelectric material; (ii) large single crystals of superconducting β-FeSe; (iii) CdSe nanocrystals with different particle sizes (3–10 nm); (iv) nanosheets of PtSe 2 ; and (v) mono- and dibenzyl selenides and diselenides at room temperature. In conclusion, The simplicity and diversity of the developed Se activation method holds promise for applied and fundamental research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of the Annealing Temperature on the Local Se Distribution and Optical Properties in CdSexTe1-x Solar Cells by Multimodal X-ray Microscopy

The introduction of Se in CdTe solar-cell absorbers has led to multiple beneficial effects in the devices, including an increased short-circuit current and an extended charge-carrier lifetime. A critical manufacturing step of CdSexTe1-x solar cells is CdCl2 annealing at high temperatures, during which Se diffuses through the absorber layer. Understanding the local Se distribution in the absorber and its impact on optical properties of the material is key for the further development of this thin-film solar cell technology. In a multimodal x-ray scanning microscopy approach, we investigated the impact of the annealing temperature of CdSexTe1-x solar cells on the Se distribution and on optical characteristics of the material. For this purpose, we exploited an upgraded x-ray excited optical luminescence (XEOL) detection unit that enables simultaneous spectrally and temporally resolved XEOL mapping at synchrotron facilities that are ideal for studying thin-film solar-cell materials with hard x-rays featuring high penetration depth and lateral resolution.

14 SOLAR ENERGY↗

Microstructure and 77K mechanical properties of electron beam welded Cu101- Inconel 625 joints

In developing large-scale next-generation superconducting radio frequency (SRF) linear accelerators using superconducting films on Cu, the design and development of dissimilar welding and joining metals, such as Cu to Inconel, stainless steel, and Nb, are essential. In this talk, we present the development of procedures for electron-beam welding of Cu¿Inconel 625 and evaluation of the microstructure and 77K mechanical properties of the weld and base material in the welded condition and heat treatments in the 750°C ¿950°C heat treatment range. The results will be presented in the context of developing joining techniques for low-temperature applications where high conductivity and strength, vacuum hygiene, and magnetic properties of the material need consideration. The methods presented here are being deployed to thin film SRF Cu cavities at Jefferson Lab. Acknowledgment: This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Nuclear

Khanal, Bashu↗