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This presentation describes the goals, scope, and plans for oxidation testing of (primarily irradiated) AGR TRISO fuels and related materials (such as graphite and graphitic matrix material). This presentation will be given at the annual program review meeting for the Gas-cooled Reactor program hosted at INL starting on July 16.
To compare the chemical degradation of conventional zirconium alloy (Zry) cladding to advance silicon carbide (SiC) cladding in a post loss of coolant accident (LOCA) environment, new nuclear testing capabilities are necessary. The Transient Reactor Test (TREAT) Facility at Idaho National Laboratory (INL) has matured its transient fuel testing capabilities since its 2017 restart. The most recent experiment architecture is the Transient Water Irradiation System in TREAT (TWIST), which is designed to support qualification of accident tolerant fuels in light water reactors. INL has designed and analyzed a natural circulation steam flow modification for TWIST to produce prototypic conditions of cladding oxidation. The in-situ device will be electrically heated to drive natural circulation. Moreover, the SiC cladding requires heating above 1700 °C to observe failure, thus internal prototypic nuclear heating with radiation effects will be used. Thermal hydraulic analysis with RELAP5-3D (Reactor Excursion and Leak Analysis Program) estimated steam fluxes greater than 50 mg cm −2 s −1 can be achieved. These fluxes are adequate to test Zry cladding according to draft regulatory guides and to test SiC cladding according to past experiments.
This work presents the oxidation behavior of matrix graphite in air. Matrix graphite, graphite powder/flakes bonded by a small amount of non-graphitic carbon, surrounds coated fuel particles in order to form cylindrical fuel compacts (in prismatic core designs) or spheres (in pebble-bed reactor designs). This work focuses on oxidation tests conducted on two matrix graphite materials, one provided by Kairos Power and the other A3 matrix graphite. Some of the tests followed American Society for Testing and Materials (ASTM) oxidation testing standards using a vertical furnace system and others were performed in a thermogravimetric analyzer (TGA). It was determined that, at temperatures of 450 °C–700 °C, the oxidation rate of the Kairos matrix graphite follows the Arrhenius equation. In comparison with A3 matrix graphite, the Kairos matrix graphite shows better oxidation resistance at high temperatures (≥550 °C), but also a higher oxidation rate at low temperatures. Both the A3 matrix graphite and the Kairos matrix graphite materials may experience preferential oxidation of the partially graphitized binder. An oxygen penetration gradient was also observed when using the three characterization methods (i.e., optical microscope, x-ray tomography [XCT], and density profile by the lathe) enlisted in this research. In conclusion, the oxygen penetration depth increases with decreasing isothermal oxidation temperature, while the center of the oxidized samples (10% weight loss) remains almost untouched even at 500 °C.
Environmental barrier coatings (EBCs) are designed to protect SiCfiber/SiCmatrix ceramic matrix composites (CMCs) in turbine engines by mitigating wear in high-temperature water vapor environments. The failure of EBCs is frequently attributed to the accelerated oxidation of the silicon bond coating layer when exposed to high-temperature steam, leading to the formation of a thickened thermally grown oxide (TGO). TGO growth increases interfacial stress, weakens adhesion, and results in coating spallation. Understanding the impact of high-temperature oxidation of EBC systems is essential for developing accurate lifespan models for turbine components, although pressurized oxidation testing is extremely sparse in the open literature. In this work, oxidation tests were performed on rare earth silicate EBCs coated onto SiC substrates under increased pressure conditions. The coated specimens were tested at 1100°C, 1200°C, and 1300°C at both 1 atm and 10 atm total pressure in steam environments. Subsequent characterization focused on the microstructural evolution of the EBC/Si/SiC system. The experimental findings indicated that TGO behavior is dependent on high-pressure conditions, with elevated pressure leading to an increase in oxide scale thickness and modifications in its morphology.
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INL performed targeted oxidation tests to measure oxidation rates for samples of ET-10 and ETU-10 graphite under CRADA No. 21CRA22 Mod. 3, Annex A, “Tritium Testing to Support Kairos Power Advanced Reactor Demonstration” (04/02/2024). All testing was conducted within INL’s Carbon Characterization Laboratory (CCL) using test standard ASTM D7542-21 "Standard Test Method for Air Oxidation of Carbon and Graphite in the Kinetic Regime" [ASTM International, 2021]. Kairos Power provided all test specimens through its graphite vendor Ibiden, Inc. to INL and ASTM specimen specified dimensions. Information within this report only provides the Arrhenius oxidation rate plots as a function of temperature for each graphite grade tested. The raw mass loss per time data will be provided on the Nuclear Data Management and Analysis System (NDMAS) portal located on the INL information system.
The performance of catalysts made out of Pt supported on TiO 2 thin films grown on SBA-15 (a silica mesoporous material) by atomic layer deposition (ALD) was characterized systematically by combining in situ infrared absorption spectroscopy (IR) with other techniques including electron microscopy and adsorption−desorption isothermal measurements. The titania films in the resulting high-surface-area catalysts were evenly distributed throughout the inner surface of the SBA-15 mesopores, and their thickness could be controlled at a submonolayer level, with 3 to 4 TiO 2 ALD cycles needed for the complete coverage of the silica sites. The titania films could be deposited either before or after adding the metal (Pt), which was dispersed in the form of small nanoparticles (NPs) approximately 4−6 nm in diameter, in order to exert some control on the density and nature of the Pt/TiO 2 interface sites. One important lesson deriving from this work is that such an order of deposition leads to significantly different catalysts in spite of the fact that most of their structural properties are similar. If the Pt is deposited on the titania films, the resulting metal NPs are slightly smaller than those grown on silica and display CO adsorption sites with lower surface Pt coordination numbers. On the other hand, when TiO 2 is deposited on the Pt/SBA-15 starting material, some titania grows on the metal and partially blocks its surface while also creating new interface sites where CO binds more weakly and displays lower C−O stretching frequencies. In terms of catalytic performance, the results from in situ IR CO site titration and kinetic measurements combined suggest a mechanism where CO first adsorbs on Pt atop sites and then migrates to Pt/TiO 2 interface sites, where oxidation takes place. Both types of sites appear to be similar in all the catalysts tested, but catalytic performance could be optimized by tuning their surface densities. Maximum catalytic activity was obtained when the TiO2 films were deposited first and with TiO 2 coverages of at least half a monolayer, that is, after at least 2 ALD cycles.
Environmental barrier coatings (EBCs) are required coatings for utilization of SiC/SiC ceramic matrix composite (CMC) components in gas turbines, where the EBC represents the life-limiting factor for such components. EBC/CMC systems have shown success in aero-engine applications with increased turbine inlet temperatures and improved efficiencies, which are achieved through higher temperature stability, lower density, and decreased reliance on cooling air compared to traditional superalloys. While industrial gas turbines (IGTs) do not currently utilize SiC/SiC CMCs, the current shift towards low-carbon or carbon-free fuel sources for power generation could result in a need for EBC/CMC components with higher temperature capabilities. In this work, three tasks were outlined to improve understanding of EBC lifetimes to encourage use in IGTs with carbon-free fuel such as hydrogen: 1. Define the bond coating oxidation kinetics and EBC failure criteria, 2. Measure thermal expansion coefficients of each layered material, and 3. Perform advanced characterization and modeling to assess EBC lifetimes. Cyclic steam oxidation tests were conducted on various EBC/Si/SiC chemistries and EBC/SiC architectures to define substrate oxidation kinetics and EBC failure modes. An open-source code was developed to quantify the undulating thermally grown oxide thickness with thousands of measurements from specimen cross-section images. Bond coating oxidation kinetics were determined and used to develop a kinetic and thermodynamic model for predicting EBC lifetimes. High-temperature Raman spectroscopy was utilized for determining the SiO 2 thermally grown oxide phase transformation as the life-limiting feature for EBCs. Model efforts supported the claim that the SiO 2 phase transformation causes elevated stress during thermal cycling with associated cracking that decreases the adhesion strength of the EBC, eventually resulting in coating spallation. The finite element model subroutine will be made publicly available upon internal review. Further development of an EBC lifetime model for IGTs involves definition of a critical SiO 2 thickness for EBC spallation and must also consider both environmental (gas velocity, pressure, etc.) and specimen (EBC dopants, layer architectures, etc.) effects into predicted bond coating oxidation kinetics for long-lifetime components.
Ir oxides are costly and scarce catalysts for oxygen evolution reaction (OER) in acid. There has been extensive interest in developing alternatives that are either Ir-free or require smaller amounts of Ir to drive the reactions at acceptable rates. One design strategy is to identify Ir-based mixed oxides that achieve similar performance while requiring smaller amounts of Ir. The obstacle to this strategy has been a very large phase space of the Ir-based mixed metal oxides, in terms of the metals combined with Ir and the different crystallographic structures of the mixed oxides, which prevents a thorough exploration of possible materials. In this work, we developed a workflow that uses machine-learning-aided Bayesian optimization in combination with density functional theory to make the exploration of this phase space plausible. This screening identified Mo as a promising dopant for forming acid-tolerant Ir-based oxides for the OER. We synthesized and characterized the Ir–Mo mixed oxides in the form of thin-film electrocatalysts with a known surface area. We show that these mixed oxides exhibited overpotentials ~30 mV lower than a pure Ir control while maintaining 24% lower Ir dissolution rates than the Ir control. Furthermore, these findings suggest that Mo is a promising dopant and highlight the promise of machine learning to guide the experimental exploration and optimization of catalytic materials.
Materials data is complex, and managing and storing materials data for use and reuse is a common challenge. An ontology-based data management framework can address these challenges through encoding data attributes and relationships in a flexible way. This presentation discusses the creation of an ontology for alloy oxidation test data and reviews the logic, structure and interoperability of the ontology.
Yttrium hydride is a promising material for a high-temperature neutron moderator in advanced micro and space reactors due to its high hydrogen density and relative thermal stability compared to other metal hydrides. However, yttrium hydride desorbs hydrogen rapidly at temperatures above 800°C, which is below the operational temperature range of some reactor designs. A hydrogen barrier coating of oxide on the hydride surface may inhibit hydrogen loss at 800°C and beyond, but the high-temperature compatibility between yttrium hydride and many oxides is currently unknown. The high-temperature compatibility of Al 2 O 3 , MgO, and Y 2 O 3 with YH 1.92 was examined by subjecting mixed oxide–hydride pellets to a 1200°C heat treatment then using a combination of diffractometry, microscopy, and spectroscopy to determine changes in the pellet composition as a result. Yttrium scavenged oxygen from both Al 2 O 3 and MgO to form Y 2 O 3 , resulting in significant loss of YH 1.92 . Yttrium reacted with reduced aluminum to form YAl 2 and several other compounds. Reduced magnesium volatilized above 1091°C and vacated the pellet. Only Y 2 O 3 did not appreciably react with YH 1.92 . Of the three oxides tested, only Y 2 O 3 was compatible with YH 1.92 at 1200°C based on the experimental criteria.
Pacific Northwest National Laboratory (PNNL) tested electrolyte coatings from Fuel Cell Enabling Technologies, Inc. (FCET) for use in solid oxide fuel cells (SOFCs). The key technology held by FCET is a process to deposit thin layers of oxide materials, less than 1 μm in thickness. The range of possible materials that can be deposited with their method is broad, but this project focused on the gadolinium-doped ceria (GDC) and yttria-stabilized zirconia (YSZ) electrolytes for SOFCs. Thin, gas tight electrolyte membranes have been a long-sought target in SOFC research. The thinner the electrolyte, the lower the cell resistance, and the higher performance of the cell (or the lower the operating temperature). A YSZ thickness of 1 μm would be a step change from the state-of-the-art, tape-cast electrolytes (~10 μm). An in-house prototype SOFC stack from FCET was first tested. The sealing geometry of the prototype stack was determined to be problematic, and testing shifted to button cells. Anode-supported solid oxide electrolysis cell (SOEC) button cells without an electrolyte layer were produced at PNNL and sent to FCET for coating with electrolyte. Three cells were tested with a gadolinium-doped ceria (GDC) electrolyte applied via spin coating. GDC was chosen for its conductivity at lower temperatures than YSZ. All three cells failed during initial reduction under hydrogen at 600°C. Testing then shifted to YSZ, which is the standard SOFC electrolyte. Several button cells were coated with YSZ and examined with scanning electron microscopy (SEM). A promising coating of ~1 mm thickness was observed under SEM. A similarly coated button cell was tested and failed similarly to previous tests during reduction at 600°C. The YSZ coating appeared dense and uniform in SEM analysis. The roughness of the underlying Ni/YSZ anode is on the order of 1 μm, and that may have compromised the gas-tightness of the coating. Further development is warranted to understand and refine the coating process. Thin YSZ applied via this spin-coating technique could be used as a low-cost, drop-in replacement in large-scale SOFC manufacturing processes, improving cell performance and lowering the cost per watt of SOFCs.
Solid oxide electrolyzer (SOE) technology is an emerging method for hydrogen production, noted for its superior electrical efficiency. Despite the significant progress made in recent years, the broad development of SOE technology is often constrained by the necessary and extensive "skill of the craft" required to successfully test simple single cell test articles. This may be linked to the dearth of practical and pragmatic guidance within the literature for safe, reliable, and performant test equipment and test procedures. Researchers at the Idaho National Laboratory (INL) have been actively testing SOEs ranging from button cells to stacks up to 500 kW, in collaboration with industry and other national laboratories. Based on operational experience, INL has developed system design procedures that ensure safe and reliable operation of SOE systems with the level of support required for each test. This paper presents key aspects of SOE stack and system testing, including safe design procedures, balance of plant components design, and specific implementations at INL. Practical design details of reactants, heat, and power management are presented along with lessons learned from the SOE test facility operations at INL.
The Hanford site has approximately 54 to 56 million gallons of radioactive mixed waste stored in 156 unretrieved underground storage tanks. The Hanford Waste Treatment and Immobilization Plant (WTP) is being built to treat and immobilize the tank waste. The baseline method for immobilization of Low Activity Waste (LAW) through the WTP is vitrification, but additional immobilization capacity is needed to supplement the initial LAW melters. An alternative cementitious waste form is being investigated for that future immobilization method. However, one impediment to a cementitious waste form is the presence of Land Disposal Restricted (LDR) organic chemicals in tank waste, which are regulated on a concentration based standard in the final waste form. Hence, if the quantity of organics in LAW is high enough, they must be destroyed or removed to make a waste form compatible with disposal in a mixed low level waste landfill. This work evaluates potential avenues for treatment of LDR organics to eliminate the impediment and permit possible use of a cementitious waste form. Vacuum evaporation testing to remove LDR organics consisted of preparing a non-radioactive LAW simulant, spiking that simulant with organic chemicals, and evaporating the mixture via differential distillation. The apparatus was a laboratory-scale vacuum evaporator operated at 60 ±5 torr absolute (vacuum evaporation). The LAW simulant represented the liquid expected to be retrieved from the Hanford tank farms at approximately 4.0 M [Na+] total sodium ion concentration. The concentration of the organic chemicals added was significantly higher than typically found in the tank waste samples since the higher levels were necessary to assist in analytical measurement and tracking of the spiked species.
The Hanford site has approximately 56 million gallons of radioactive mixed waste stored in 156 unretrieved underground storage tanks. The Hanford Waste Treatment and Immobilization Plant (WTP) is being built to treat and immobilize the tank waste. The baseline method for immobilization of Low Activity Waste (LAW) through the WTP is vitrification, but additional immobilization capacity is needed to supplement the initial LAW melters. An alternative cementitious waste form is being investigated for that future immobilization method. However, one impediment to a cementitious waste form is the presence of Land Disposal Restricted (LDR) organic chemicals in tank waste, which are regulated on a concentration-based standard in the final waste form. Hence, if the quantity of organics in LAW is high enough, they must be destroyed or removed to make a waste form compatible with disposal in a mixed low level waste landfill. This work evaluates potential avenues for treatment of LDR organics to eliminate the impediment and permit possible use of a cementitious waste form.
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A high enthalpy and low-cost Hypersonic Test Facility (HTF), which employs nitrous oxide to generate clean air-like gas; and a method of decomposing nitrous oxide in the presence of a catalyst in a catalytic decomposition chamber in a HTF.
Lignin is composed of phenylpropanoid monomers linked by ether and carbon-carbon bonds to form a complex heterogeneous structure. Bond-specific studies of lignin-modifying enzymes (LMEs; e.g., laccases and peroxidases) are limited by the polymerization of model lignin substrates and repolymerization of cleavage products. Here we present a high throughput platform to screen LME activities on four tagged model lignin compounds that represent the β-O-4’, β-β’, 5–5’, and 4-O-5’ linkages in lignin. We utilized nanostructure-initiator mass spectrometry (NIMS) and model lignin compounds with tags containing perfluorinated and cationic moieties, which effectively limit polymerization and condensation of the substrates and their degrading products. Sub-microliter sample droplets were printed on the NIMS chip with a novel robotics method. This rapid platform enabled characterization of LMEs across a range of pH 3–10 and relative quantification of modified (typically oxidized), cleaved, and polymerized products. All tested enzymes oxidized the four substrates and cleaved the β-O-4’ and β-β’ substrates to monomeric products. We discovered that the active pH range depended on both the substrate and the enzyme type. This has important applications for biomass conversion to biofuels and bioproducts, where the relative percentages of different bond types in lignin varies depending on feedstock and chemical pretreatment methods.