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DOE OSTI2023

Exploring the $A$-V-Sb landscape beyond $A$$\mathrm{V_3}$ $\mathrm{Sb_5}$: A case study on the $\mathrm{KV_6}$ $\mathrm{Sb_6}$ Kagome compound

Kagome compounds have garnered attention in the past few years for their intriguing magnetic properties arising from spin frustration dictated by the geometry of the Kagome sublattice. In this paper, we highlight the success of the unconventional hydride route for the fast and easy synthesis of the Kagome compound $\mathrm{KV_6}$ $\mathrm{Sb_6}$. Here, high-temperature in situ powder x-ray diffraction (PXRD) studies proved to be useful in hinting at the existence of $\mathrm{KV_6}$ $\mathrm{Sb_6}$, identifying its synthesis conditions, and understanding the reaction mechanism. The crystal structure for $\mathrm{KV_6}$ $\mathrm{Sb_6}$ was determined from high-resolution PXRD data. The compound has a layered structure [$R\overline{3}m, a = 5.5318$ (9) Å, $c = 34.23$ (3)Å 3 $Z = 3$] at room temperature] and features a Kagome bilayer of V atoms. $\mathrm{KV_6}$ $\mathrm{Sb_6}$ is isostructural to the previously reported $\mathrm{RbV_6}$ $\mathrm{Sb_6}$ and $\mathrm{CsV_6}$ $\mathrm{Sb_6}$ compounds. $\mathrm{KV_6}$ $\mathrm{Sb_6}$ is thermally stable in vacuum up to 1173 K, as evident from the high-temperature in situ PXRD and differential scanning calorimetric analysis. Investigation of magnetic properties for $\mathrm{KV_6}$ $\mathrm{Sb_6}$ between 2 and 300 K reveals temperature-independent paramagnetism and an absence of superconductivity, like the Rb and Cs analogs. Furthermore, we compare the magnetic properties of K V 3 Sb 5 , another ternary Kagome compound, synthesized via two different methods: the hydride route and the traditional route from elements. Low-temperature transport property measurements of $\mathrm{KV_6}$ $\mathrm{Sb_6}$ indicate metallic behavior and an intrinsically low thermal conductivity of $\mathrm{1.0 W K^-1}$ $\mathrm{m^-1}$ at 300 K. The layered structure of $\mathrm{KV_6}$ $\mathrm{Sb_6}$ makes it an attractive candidate for deintercalation and doping studies to tune both magnetic and transport properties, laying a foundation for further studies.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Plasma Facing Component Characterization and Correlation With Plasma Conditions in Lithium Tokamak Experiment-β

Lithium coatings in the Lithium Tokamak eXperiment (LTX) led to flat temperature profiles. The flat temperature profiles were observed along with a hot, low density edge, implying a broad, collisionless scrape-off layer (SOL). Additionally, in vacuo X-ray photoelectron spectroscopy (XPS) measurements established that lithium coatings evaporatively deposited onto high-Z plasma facing components (PFCs) became oxidized while retaining the ability to achieve good plasma performance long after lithium was applied to the PFCs. Longstanding theory predicted flat temperature profiles with low recycling walls, which was presumed to be due to hydrogen binding with elemental lithium to form lithium hydride. The presence of oxidized lithium, however, raised questions regarding the exact mechanism of hydrogen retention in LTX. To investigate these questions, the upgraded facility LTX- β includes a new sample exposure probe (SEP) for more detailed in vacuo analysis of PFC samples. The SEP is equipped with a vacuum suitcase capable of transporting samples representative of the LTX- β outer midplane PFCs to a stand-alone XPS system while maintaining pressures lower than the LTX- β base vacuum to limit the contamination between sample exposure and analysis. The low-energy resolution XPS system used in past experiments could only enable the determination of elemental percentages on the PFC sample surfaces. Because the new XPS system has higher energy resolution, it is more direct to assign chemical compounds to the measured binding energies. This capability has been confirmed by comparing XPS data from PFC test samples with measurements using a commercial high-resolution XPS system. Quartz crystal microbalances (QCMs) were used to quantify the thickness of the deposited lithium on the LTX- β PFCs. This article describes the application of the SEP to characterize the PFC surfaces using XPS and their relationship to plasma conditions.

Maan, Anurag↗

DOE OSTI2023

Reductive chemistry of pyrrolic macrocycles: A PCET dichotomy between metal and ligand

Proton-coupled electron transfer (PCET) is central to the reactivity of porphyrins. The coupling of the electron to the proton is central to a porphyrin’s ability to catalyze energy conversion reactions of which the hydrogen evolution reaction (HER) is exemplary. To understand the mechanistic details of the PCET chemistry of porphyrins and related macrocyclic congeners, we have designed hangman constructs that allow a proton, placed in the secondary coordination sphere (off of the hangman backbone), to be coupled to redox transformations at the macrocycle. For metals whose reduction potentials are positive of the porphyrin macrocycle, such as Co and Fe, HER catalysis is confined to PCET transformations of the metal center where the active catalyst for HER is a reduced metal hydride. Alternatively, the reduction potentials of Ni, Zn, and 2H (freebase) porphyrins allow for redox non-innocence of the macrocycle; here the active “hydridic” catalyst is a phlorin, which gives rise to elaborate HER reaction sequences. Beyond HER catalysis, redox non-innocence of Ni, Zn, and 2H porphyrins and related compounds has been informative for providing detailed mechanistic insight into the multi-site PCET hydrogenation of olefinic bonds of the macrocycle. This mini-review unravels the PCET dichotomy between the metal and macrocycle in promoting HER catalysis and novel chemical transformations that give rise to unusual macrocyclic structures.

Chemistry↗

DOE OSTI2023

tih_vqe [SWR-23-32]

This software supports the paper, "Exploring the scaling limitations of the variational quantum eigensolver with the bond dissociation of hydride diatomic molecules," published in the International Journal of Quantum Chemistry, whose abstract is as follows: Materials simulations involving strongly correlated electrons pose fundamental challenges to state-of-the-art electronic structure methods but are hypothesized to be the ideal use case for quantum computing. To date, no quantum computer has simulated a molecule of a size and complexity relevant to real-world applications, despite the fact that the variational quantum eigensolver (VQE) algorithm can predict chemically accurate total energies. Nevertheless, because of the many applications of moderately-sized, strongly correlated systems, such as molecular catalysts, the successful use of the VQE stands as an important waypoint in the advancement toward useful chemical modeling on near-term quantum processors. In this paper, we take a significant step in this direction. We lay out the steps, write, and run parallel code for an (emulated) quantum computer to compute the bond dissociation curves of the TiH, LiH, NaH, and KH diatomic hydride molecules using VQE. TiH was chosen as a relatively simple chemical system that incorporates d orbitals and strong electron correlation. Because current VQE implementations on existing quantum hardware are limited by qubit error rates, the number of qubits available, and the allowable gate depth, recent studies have focused on chemical systems involving s and p block elements. Through VQE + UCCSD calculations of TiH, we evaluate the near-term feasibility of modeling a molecule with d-orbitals on real quantum hardware. We demonstrate that the inclusion of d-orbitals and the use of the UCCSD ansatz, which are both necessary to capture the correct TiH physics, dramatically increase the cost of this problem. We estimate the approximate error rates necessary to model TiH on current quantum computing hardware using VQE+UCCSD and show them to likely be prohibitive until significant improvements in hardware and error correction algorithms are available.

Graf, Peter↗

DOE OSTI2021

Evaluation of Thermal Neutron Scattering Cross Sections for CaH 2

Solid metal hydrides have long been considered viable moderators for nuclear reactor designs due to their moderating ratios, hydrogen densities, high dissociation temperatures, and mechanical properties. CaH 2 is an orthorhombic saline-hydride that has recently been investigated and shows promise for use as a moderator in microreactors. At present, there is no Thermal Scatting Law (TSL) evaluation for CaH 2 in the ENDF/B-VIII.0 database. An evaluation does exist in the JEFF-3.3 database, performed by Serot, however it was limited by the implemented methods and thus both drastically over-predicts the incoherent elastic contribution and completely ignores the coherent elastic contribution to scattering from the metal ions. The thermal neutron scattering cross sections of CaH 2 are evaluated in this work to establish accurate data for use in reactor design. The present evaluation corrects the inaccuracies of the JEFF-3.3 data, and yields three distinct libraries: Ca in CaH 2 , H 1 in CaH 2 , and H 2 in CaH 2 .

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2026

How nitrogen and oxygen shape SRF cavity performance

Nitrogen and oxygen-based surface treatments have revolutionized the performance of superconducting radiofrequency (SRF) cavities, enabling them to reach higher gradients and lower losses. However, the exact mechanisms by which these treatments improve cavity performance remain largely unknown. This work provides new insights into the role of nitrogen and oxygen in SRF cavity performance by using time-of-flight secondary ion mass spectrometry (TOF-SIMS) to precisely quantify the concentrations and depth profiles of these impurities within niobium cutouts. We correlate these impurity profiles with detailed cavity performance measurements, including surface resistance and quality factor, and compare our findings with predictions from BCS theory. The results demonstrate that while both nitrogen and oxygen enhance performance, ten times more oxygen is required to achieve the same reduction in BCS resistance as interstitial nitrogen. We present a potential model in which the observed variation arises from nitrogen's greater effectiveness in trapping hydrogen, thus reducing the formation of niobium hydrides and enhancing superconducting gap.

Hu, Hannah [Chicago U.]↗

DOE OSTI2020

Tritium Pressure Enhancement on the TPBAR Cladding by Physical Processes at the Getter

Tritium for the U.S. nuclear weapon stockpile is produced in tritium producing burnable absorber rods (TPBARs) inserted into Tennessee Valley Authoritys (TVA) light-water nuclear reactors. The rods are stainless steel tubes with a permeation barrier coating and internal components that generate and contain the tritium. The TPBAR incorporates a Ni-plated Zircoloy getter tube to capture tritium and prevent it from reaching the rod cladding and permeating into the environment. Under the conventional view of getter behavior, the tritium pressure outside the getter tube is expected to be limited to the equilibrium vapor pressure of Zr hydride at the temperature of the rod as long as the total hydrogen concentration remains below the capacity of the hydride. Since the tritium pressure is higher within the rod core, this behavior relies on the thin getters ability to hold off a differential tritium pressure. The effective tritium pressure on the cladding can also be enhanced by isotope exchange. Hydrogen ingress through the cladding from the reactor coolant creates a hydrogen pressure on the outer surface of the getter that can exchange with tritium, allowing the tritium partial pressure to increase toward this hydrogen gettering pressure. The goal of this work was to use laboratory-scale experiments to examine these mechanisms and create a model of getter behavior that describes tritium transport within the TPBAR. A third mechanism wherein the concentration at the outer surface of the getter is increased by the temperature gradient within the getter tube wall (the Soret effect) is not experimentally tested but is captured in the model. While not conclusively demonstrated by the experiments due to low pressure, high temperature, and small gap volume conditions, the model shows that when combined, the three mechanisms can explain both the magnitude and time dependence of the tritium release observed for reactor fuel assemblies with TPBARs. The model also shows how various modifications of the TPBAR design can reduce this tritium release into the environment.

07 ISOTOPE AND RADIATION SOURCES↗

DOE OSTI2020

SR19016 - Characterization of AM Materials for SRTE Service

This project addresses several issues and challenges for the use of AM produced components in the tritium facility. It will evaluate the effect of low level hydrogen and tritium exposure on the mechanical and chemical characteristics of Arcam A2X Electron Beam Powder Bed Fusion Produced (EPBF) Ti-6AI-4V by printing tensile samples and testing them in the as printed, machined, and hydrogen exposed conditions. Hydrogen uptake will be measured using an Eltra Hydrogen-Oxygen- Nitrogen analyzer. Hydride response will be measured using a Seiffert's apparatus and determining the effects of various surface treatments on the hydriding susceptibility. Tools, fixtures, and other objects will be deigned and printed for use in the AM lab and tritum facility and for other groups that support the tiritum mission.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2020

Improved Performance of Cu(InGa)(SeS) 2 PV Modules Using the Reaction of Metal Precursors. Final Report

This project “Improved Performance of Cu(InGa)(SeS) 2 PV Modules using the Reaction of Metal Precursors” was a partnership led by the Institute of Energy Conversion (IEC) at the University of Delaware with Columbia University and the Molecular Foundry at the Lawrence Berkeley National Laboratory. The aim was to develop pathways to improve Cu(InGa)(SeS) 2 (CIGSS) thin film photovoltaic modules using processes compatible with low manufacturing cost. The CIGSS approach investigated was a two-step process including deposition of metal precursor films following by reaction in hydride gases utilizing IEC’s novel reactor. The process was similar to that under commercial development by the project’s industry partner Stion. When Stion went out of business mid-project the focus changed to a rapid thermal process considered more commercially viable. Approaches to improve the performance of solar cells using the reacted films focused on two material innovations. First, the overall Ga content was increased to increase the operating voltage, which is desirable for scale-up to commercial modules. Second, the processing and performance advantages arising from Ag alloying were investigated. Advanced characterization guided process and material development including control of relative composition gradients. Research on the formation of Cu-Ga-In metal precursors utilized sputtering deposition which is normally used in commercial applications. The work resulted in processes for deposition of precursor stacks with increased relative Ga content and effects of deposition parameters on morphology and phase composition were established. It was shown that the metal precursor films have comparable phase composition and morphology so subsequent reaction follows from the same starting point. The addition of Ag to the metal precursors gave more uniform morphology and improved adhesion of reacted films which enable higher reaction temperature for faster processing. A novel outcome was the discovery of a previously undocumented material phase in sputter-deposited and evaporated Ag-Cu-In-Ga thin films. Hydride gas reaction processes including time-temperature-concentration profiles were developed for different precursor compositions. This enables control of composition profiles to engineer through-film gradients for solar cell optimization with characterization and simulations used to correlate measured film composition profiles to measurements of devices. In particular, the gradient of sulfur at the front of the CIGSS film was found to be critical. The simulations guided process development leading to improved reproducibility of devices improved performance with higher Ga content and higher voltage. With Ag-alloyed precursors, the reaction pathways leading were determined. A significant finding was that Ag-alloying increases the reaction rate to completely convert precursor films to the final chalcopyrite which could enable reduced reaction time to benefit manufacturability. To maintain potential commercial viability, the process under investigation was refocused to a rapid thermal process that could potentially be incorporated into an in-line process for manufacturing. Precursors with different composition were capped with an extra selenium layer and reacted in hydrogen sulfide 5-15 minutes, compared to typically 2 hours in the previous multi-step batch process. Critical RTP parameters were identified to control the reaction. Further optimization would be needed for high efficiency solar cells but pathways to high quality devices with further optimization and improved heating uniformity were developed. The project also developed new optoelectronic characterization approaches with a focus on development and application of spatial- and time-resolved photoluminescence and a custom mapping photoluminescence microscope built. It was shown how critical electronic transport properties strongly depend on the chemical composition of the material and that a wide range of samples show inhomogeneity on a length scale larger than the grains in the films. Additionally, two-photon excitation capability was developed to distinguish bulk vs surface losses. The project advances the state-of-the -art for precursor reaction processes in several ways that could impact manufacturing. This includes validation of approaches to increase voltage and establishment of model-guided control to form optimal composition profiles. The application of process control approaches with knowledge of phase formation and reaction pathways can be critically valuable in designing a large-scale process.

14 SOLAR ENERGY↗

DOE OSTI2021

Design of Efficient Molecular Electrocatalysts for Water and Carbon Dioxide Reduction Using Predictive Models of Thermodynamic Properties

Objectives: 1) To design and synthesize water soluble transition metal complexes that function as electrocatalysts for the reduction of water to hydrogen or carbon dioxide to formate 2) To experimentally measure thermochemical properties, such as hydride donor ability, and use these quantities to optimize catalyst performance in solutions of varying pH 3) To incorporate results from detailed mechanistic and kinetic studies to direct improvements in catalyst design 4) To use thermochemical data from objective 2 to generate predictive models for the properties of new complexes to apply to the development of catalysts for other reductive reactions, with an emphasis on carbon dioxide reduction to methanol Description: Wide-spread implementation of renewable but intermittent energy sources, such as solar, requires the development of efficient methods for energy storage. The high energy density of chemical bonds makes chemical fuels an ideal solution for energy storage. Hydrogen and reduced carbon compounds have been proposed as ideal candidates for chemical fuels. However, the generation of chemical fuels from electricity requires competent electrocatalysts. The proposed research focuses on developing electrocatalysts for the reduction of water to hydrogen, and carbon dioxide to formate. Both products can be used directly as an energy carrier in fuel cells, or as a reductant for more saturated chemical fuels. Hydrogen is the most common fuel used in current commercial fuel cells. Additionally, there is interest in formic acid as a liquid carrier for hydrogen because of its increased storage density and ease of dehydrogenation. Formate is also an intermediate in the sequential reduction of CO 2 to methanol, another potential chemical fuel with high energy storage density. Despite the utility of formate as a chemical fuel or precursor, there are very few examples of electrocatalysts for its production from CO 2 , and even fewer demonstrate high product selectivity. In heterogeneous catalysis, the Sabatier principle is used to generate volcano curves that describe optimal thermochemical properties for key intermediates that result in peak catalytic activity. In most cases, such as hydrogen production and oxidation, the most favorable metals (Pt, Re, Rh, and Ir) are rare and expensive. Molecular inorganic complexes provide an opportunity to use electronic and steric ligand effects to tune the critical thermodynamic parameters of abundant metals to values comparable to key surface intermediates on precious metals. This principle will be applied to the design of aqueous homogeneous catalysts for the reduction of H 2 O and CO 2 optimized to function at specific pH ranges. The critical intermediate in both of these reactions is a metal hydride. The strength of this bond, or hydricity (ΔGH - ) dictates the overall thermodynamics of the reduction of H + to H 2 and the sequential reduction of C1 substrates, such as CO 2 , CO, and H 2 CO (the latter to CH 3 OH). ΔGH - will be systematically measured for a series of first row metal complexes to form predictive models for metal and ligand electronic effects. Benefits and Outcomes: This approach addresses thermodynamic requirements essential for energy-efficient catalyst design and transition state barrier considerations for faster catalysis. The advancements made from this research will include the discovery of efficient, stable, and fast catalysts for hydrogen and formate generation from electricity. The ability to store energy efficiently is critical to the widespread use of renewable energy schemes. This provides a viable solution to produce high energy density fuels for stationary and mobile energy applications. The fundamental research conducted is also directly applicable to the design of catalysts for the generation of further reduced products such as methanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Fundamental Studies of Tritium Formation and Diffusivity in Pure and Defective Zircaloy-4 Getters

Zirconium (Zr) and its alloys are used as fuel cladding in nuclear reactors. These materials have their low absorption cross-section for thermal neutrons and have good mechanical and thermal properties. In addition, they are used as tritium getters in tritium-producing burnable absorber rods (TPBARs), in the form of nickel-plated Zircaloy-4 tubes. To produce 3 H, the breading blankets such as lithium aluminate are irradiated in pressurized water. 3 H produced in this process is captured by the getter and 3 H reacts chemically with Zr to form metal hydride (ZrTx). The precipitation of metal hydride results in not only the volume increase and hydrogen embrittlement of zircaloy but also changes in getter’s chemical properties. This degrades the getter’s performance. Therefore, understanding the behavior of 3 H (such as diffusion and solubility) in zircaloy is important to understand getter performance.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2022

Predicting and Controlling Corrosion (Abbreviated Final Report)

Corrosion accumulates significant replacement costs in the transportation, utility, manufacturing, and infrastructure sectors. It also underpins several of LLNL’s core missions in stockpile stewardship, defense, and energy security. Whereas most corrosion and aging models are empirically parameterized to describe well-defined conditions late in the reaction, the factors that determine the early stages of corrosion—during which mitigation could be most impactful— are poorly understood. This project addressed the critical need for new approaches to predict the kinetics of corrosion initiation based on firm physical and chemical understanding. The activities encompassed degradation of relevant metals in both hydrogen-rich and environmental corrosion scenarios. The team integrated state-of-the-art multiscale simulation, in situ characterization, and data science within three technical thrusts: hydriding of Ti alloys; aqueous corrosion of Al and Ni-Cr alloys; and degradation of additively manufactured 316L stainless steel. In each case, novel capabilities were developed to identify and track the impacts of key atomistic, compositional, and microstructural features on the metal systems. For hydriding, protocols were developed to tightly integrate multiscale models, advanced multimodal characterization, and machine learning to determine how hydrogen interacts with native passivating surface oxides and nucleates new undesired phases, shedding new light on the critical role of grain boundaries, interfaces, and atomically disordered regions. For aqueous corrosion, the project demonstrated methods to predict dissolution rates of metal surfaces in corrosive solutions, to measure and understand microstructural and grain orientation effects on corrosion susceptibility, and to investigate competing growth and dissolution kinetics of surface oxides. For additively manufactured metals, analysis using state-of-the-art microscopy techniques revealed the role of specific heterogeneities invoked during laser processing, including cellular structure, dislocations, and precipitates, on corrosion susceptibility. In addition to new capabilities and understanding, the project provided an avenue for workforce development, as well as key partnerships with stakeholders in corrosion science.

08 HYDROGEN↗

DOE OSTI2020

Evaluation of Increased Peak Temperatures for Spent Fuel Cladding Performance during Dry Storage (Rev.1)

NUREG-2214, “Managing Aging Processes in Storage (MAPS) Report,” (2019) documents the technical basis for age-related degradation mechanisms on spent nuclear fuel assemblies during dry storage operations. The technical bases have been reviewed, and hoop cladding stress calculations were conducted using the Fuel Analysis under Steady-state and Transients (FAST) code at elevated normal condition temperatures of 425°C and 450°C, and at an off-normal and accident conditions temperature of 600°C. The NUREG-2214 conclusions are substantiated by the referenced literature. The calculations demonstrate that the aging mechanisms primarily driven by hoop stress such as hydride reorientation, delayed hydride cracking, thermal and athermal (low-temperature) creep, and localized mechanical overload are either not credible or do not compromise the fuel assembly’s performance for increased peak normal condition temperatures of 425°C or 450°C during the up to 60-year dry storage period. Other aging mechanisms considered are also not credible for compromising the fuel assembly’s performance during 60-year dry storage with a peak temperature of 400ºC as specified in ISG – 11 Rev. 3, and the same is indicated for the increased peak normal condition temperatures of 425°C or 450°C.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2023

High-Burnup Spent Fuel Data Project: Sister Rod Final Phase II Test Plan

The Sibling Pin test campaign is a Department of Energy (DOE) research activity within the Spent Fuel and Waste Science and Technology (SFWST) program that is tasked with characterization of high burnup (HBU) fuel in support of the High Burnup Spent Fuel Data Project. Of the 25 fuel rods in the Sibling Pin inventory, approximately 9 rod lengths have been consumed during the first phase (Phase I) of the test campaign leaving approximately 16 rod lengths for the second phase (Phase II) of testing. This plan outlines the Phase II testing and the motivations for performing these tests. Priorities for Phase II testing are based on previously identified knowledge gaps, lessons-learned from Phase I work, the original objectives of the High Burnup Spent Fuel Data Project and the Sibling Pin test campaign, and input from external stakeholders. The priorities for Phase II testing are to obtain data to characterize the effects of annealing on cladding mechanical properties and fuel rod performance, to quantify the creep behavior of cladding materials and fuel rods and the effects of creep deformations on the performance of cladding and fuel rods, and to gather data to support the final closure of the hydride reorientation and radial hydride induced embrittlement gap for HBU fuel rods.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2024

Report on RIA Relevant Modified Burst Testing of ATF Cladding Materials

The mechanical performance of accident-tolerant fuel (ATF) cladding candidates in light-water reactors (LWRs) must be similar to or better than that of current conventional nuclear fuel claddings to reduce dose to the public and ensure a that the core coolable geometry is maintained during a postulated reactivity-initiated accident (RIA) in light-water reactors (LWRs). During an RIA event, the rapid thermal expansion of nuclear fuel can deform the cladding once the fuel–cladding gap closes. In some cases, the pellet–cladding mechanical interaction (PCMI) can induce mechanical failure in ATF candidates. Thus, the mechanical response of ATF cladding must be investigated by mimicking the conditions of RIA and potentially performing Transient Reactor Test (TREAT) experiments to establish or verify the safety envelope. The work presented in this report investigated the failure behavior of as-received, hydrided, and chromium-coated (Cr-coated) Zircaloy-4 (Zry-4) cladding tube under strain-driven mechanical conditions, mimicking postulated RIA loading conditions. Mechanical testing was performed at 300°C via modified burst test (MBT) equipment with pulse width control previously developed under the Department of Energy’s (DOE’s) Advanced Fuel Campaign (AFC). The mechanical strains were determined using 2D digital image correlation (DIC) techniques. The base Zry-4 acquired by Cameco Inc. was in stress-relieved annealed (SRA) condition. Because of the observed large deformation of the cladding tubes, the failure strain definition was updated for the MBT, which can also be applied to other tube tests where significant bulging (out-of-plane deformation) is present. The failure strain was determined to be affected by the speed of the test or the RIA event. As the RIA-like event duration decreased from 75 to 15 ms, the failure strain decreased 5, 7 and 1% for as-received, hydrided, and Cr-coated specimens, respectively. Fractography on the Cr-coated specimens indicated the presence of two failure mechanisms: (i) crenulation at the outer surface of the coating due to the tensile tractional forces along with coatings grain microstructure and (ii) formation of critical defect at the coating/cladding interface that initiated coating rupture after severe plastic deformation of the Zry- 4 substrate. Based on the MBT results and fractography observations, performing mechanical property testing at high strain rates—in particular on Cr-coated tubes—and semi-integral TREAT experiments are required future efforts to ensure ATF cladding performance during transients. The testing recommended would also inform the development of long-term generalized cladding technologies.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2023

Assessment of Materials-Based Options for On-Board Hydrogen Storage for Rail Applications

The objective of this project was to evaluate material- and chemical-based solutions for hydrogen storage in rail applications as an alternative to high-pressure hydrogen gas and liquid hydrogen. Three use cases were assessed: yard switchers, long-haul locomotives, and tenders. Four storage options were considered: metal hydrides, nanoporous sorbents, liquid organic hydrogen carriers, and ammonia, using 700 bar compressed hydrogen as a benchmark. The results suggest that metal hydrides, currently the most mature of these options, have the highest potential. Storage in tenders is the most likely use case to be successful, with long-haul locomotives the least likely due to the required storage capacities and weight and volume constraints. Overall, the results are relevant for high-impact regions, such as the South Coast Air Quality Management District, for which an economical vehicular hydrogen storage system with minimal impact on cargo capacity could accelerate adoption of fuel cell electric locomotives. The results obtained here will contribute to the development of technical storage targets for rail applications that can guide future research. Moreover, the knowledge generated by this project will assist in development of material-based storage for stationary applications such as microgrids and backup power for data centers.

08 HYDROGEN↗

DOE OSTI2023

Dislocation line tension model to improve understanding of the effects of hydrogen on the deformation of structural materials

Decarbonization efforts highlight hydrogen as an attractive alternative to fossil fuels, but its tendency to embrittle structural metals demands careful consideration when designing hydrogen infrastructure. Moreover, the mechanisms by which hydrogen degrades these materials are still being elucidated. The current work develops new computational tools to quantify the different contributions of hydrogen to the energy barrier of cross-slip, a key deformation mechanism. Novel features are implemented to a line tension model, which include the use of non-singular dislocation interactions, character-dependent dislocation energies and simulations of the constriction configurations. A new molecular dynamics technique is developed to calculate the interaction energy between the partials of a dissociated dislocation via fixing the centers of mass of the regions below and above the Shockley partials and performing time-averaged calculations. Hydrogen is found to impact the stacking fault width of dislocations in different ways depending on their characters: it decreases for dislocations with a character θ > 30°, remains unchanged for θ = 30° and increases for θ < 30°. The latter regime is a newly identified mechanism by which hydrogen inhibits cross-slip. Moreover, formation of nano-hydrides is predicted to occur around screw dislocations for high hydrogen concentrations, a phenomenon previously identified only in dislocations with an edge component. If nano-hydrides develop, their influence extending the equilibrium stacking fault width and increasing both the constriction and cross-slip energy barriers dominate over all other hydrogen contributions. The theory and tools developed will pave the way towards a comprehensive understanding of hydrogen-dislocation interactions in structural metals.

08 HYDROGEN↗

DOE OSTI2024

An Analytical Tool to Evaluate Defect Thermodynamics of (La,Ba)Fe1-xMxO3-δ Perovskites for Solid-Oxide Cell Applications

A modeling tool of the defect thermodynamics of (La,Ba)Fe1-xMxO3-δ perovskites which includes energetic information about oxygen vacancy formation, hydration, hydride formation, and charge disproportionation reactions has been developed1. This tool incorporates defect energies and entropies expressed as sixth order polynomial functions to allow refinements of the defect reaction equilibrium constants in the thermodynamic analysis. Calculation of (La,Ba)Fe1-xMxO3-δ Brouwer diagrams as a function of pO2/pH2O and pH2/H2O in a range of temperatures of interest is facilitated by this modeling tool. The results obtained can provide direct guidance how the electronic and ionic defect concentrations of the triple conducting perovskite materials can be used to optimize performance of solid oxide cells for energy applications. The impact of magnetic and electronic structures of the perovskites on the defect reaction energies and entropies as obtained from density function theory modeling and the role played by hydride defect species will also be discussed.

Lee, Yueh-Lin↗