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Elimination of NO Pollutant in Semi-enclosed Spaces over Sodium-promoted Cobalt Oxyhydroxide (CoOOH) by Oxidation and Adsorption Mechanism

Low concentrations of NOx accumulated in air in semi-enclosed spaces is a severe health hazard, but its efficient removal at low cost is a grand challenge. A simple method in preparing CoOOH for low-concentration NO removal at room temperature is described here. The samples are synthesized by oxidizing Co(OH)2 to CoOOH with different oxidants (Na2S2O8, O2 and H2O2). Among them, CoOOH prepared by Na2S2O8 (Co-NS) shows remarkable performance for NO abatement, while the samples synthesized by and H2O2 (Co-HO) and O2 (Co-OG) have no apparent NO removal capacity. It is found that the Co-NS material contains a higher concentration of residual Na, which contributes to the decreased crystallinity and increased concentrations of surface active species (Co2+, active oxygen) for NO storage. Following NO storage, the material can be readily regenerated by water washing. The authors from East China University of Science and Technology acknowledge support from National Basic Research Program of China (2013CB933200), National Natural Science Foundation of China (21577035, 21577034), Commission of Science and Technology of Shanghai Municipality (15DZ1205305) and 111 Project (B08021). Aiyong Wang acknowledges the China Scholarship Council for the Joint-Training Scholarship Program with the Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the US DOE under contract DE-AC05-76RL01830. FG is supported by the U.S. DOE/Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office.

NOx abatement, NOx adsorber, ambient temperature, ↗

Physics-Driven Construction of Compact Primitive Gaussian Density Fitting Basis Sets

We present a model-assisted density fitting (MADF) basis set generator, an algorithm for generating primitive atomic Gaussian density fitting (DF) basis sets (DFBSs) from a contracted Gaussian orbital basis set (OBS). The MADF algorithm produces DFBSs suitable for accurate robust DF approximation of 2-particle interactions in mean-field and correlated electronic structures. The algorithm is designed to (a) saturate the OBS product space by a large regularized set of primitive solid-harmonic Gaussian shells with nonuniform distribution of exponents, followed by (b) pruning of the shells according to their contributions to the 2- body energy of a correlated atomic ensemble. Building the DFBS generator model almost exclusively on mathematical and physical principles allows one to limit the number of parameters that control the density fitting error to three, with a single set of parameters sufficient for computations with all basis cardinal numbers, with and without correlation of core electrons, with and without scalar and spin-dependent relativistic effects, spanning almost all of the Periodic Table. Performance assessment included basis sets up to quadruple-ζ quality from several major basis set families, using molecules composed of main-group, d-block, and f-block elements. The resulting DF errors in Hartree−Fock and second-order MP2 energies (with relativistic all-electron treatments, when appropriate) were on the order of 20 and 10 μE h per electron, respectively.

Approximation↗

High Yield Xray Imager Final Design Review

The High Yield Xray Imager (HYXI) is a new NIF target diagnostic system currently under development. The goal of HYXI is to provide high-fidelity, high temporal resolution x-ray imaging capability on high yield NIF implosions at 10MJ and above. The HYXI instrument design concept is based on the combination of two technologies that have been successfully utilized at the NIF on previous instruments, electron pulse-dilation and hybrid-CMOS sensor imaging. The combination of these two techniques will give HYXI sufficient data quality to ascertain differences in hot spot formation dynamics between high and low yield implosions. This information will highlight the critical hot spot conditions needed for ignition and burn. The HYXI design leverages the successful operation of the PDIXI x-ray imager at the NIF on multi MJ yield shots. A new radiation tolerant CMOS imaging array (HYPERION) is being developed to eliminate the significant background noise which limits the data quality of PDIXI. We successfully placed the contract with Advanced hCMOS Systems (AHS) to develop the HYPERION sensor, which fulfils our criteria to place long lead time item procurements by end of FY24. The HYXI Final Design Review was completed at the end of Q4 FY24 (Sep 24 th and Sep 30 th ). The HYXI project is a multi-year effort with a phased approach to be bring up system functionality over time in parallel with the development and fabrication effort of the HYPERION CMOS imaging array. In Phase 1, time-integrated x-ray images on NIF DT experiments will be collected starting in Q3 FY25. In Phase 2 of the project, time-resolved imaging with HYXI utilizing a spare microchannel plate detector back-end will begin in Q3 FY26. Phase 3 concludes the project with the installation of the HYPERION sensor array and the final performance qualification of the HYXI instrument which is scheduled for Q3 FY27 as discussed in the PDR and MRT report on this project in FY23.

42 ENGINEERING↗

Strain-associated nanoscale fluctuating lithium transport within single-crystalline LiNi 1/3 Mn 1/3 Co 1/3 O 2 cathode particles

Solid-state lithium diffusion dynamics are critical for the rate capability and longevity of Li-ion batteries. Conventionally, nanoscale lithium diffusion within individual battery particles has been simplified as being primarily driven by concentration gradients, despite the associated processes inducing local lattice expansion, contraction, and strain fields. Using operando scanning transmission soft X-ray microscopy with high spatial resolution and chemical sensitivity to track nanoscale intraparticle lithium transport, and post-cycling Bragg coherent diffraction X-ray imaging to directly reveal three-dimensional intraparticle strain fields, we uncover strain-associated lithium transport dynamics within single-crystalline LiNi 1/3 Mn 1/3 Co 1/3 O 2 (scNMC) particles during cycling. Contrary to the expected thermodynamic solid-solution behavior of scNMC, our observations reveal near-uniform but fluctuating regions of lithium-dense and lithium-dilute areas during cycling. These fluctuations suggest that nanoscale lithium diffusion can proceed counter to concentration gradients. Additionally, we demonstrate that an increased presence of lithium-dilute regions near the surface enhances lithium surface insertion kinetics, emphasizing the importance of controlling surface lithium distribution to improve rate performance. Our study provides insights into nanoscale solid-state ion transport, with potential applications in batteries, solid-state fuel cells, and memristors.

Lee, Danwon [Seoul National Univ. (Korea, Republic↗

WRPS Hanford Update [Slides]

The purpose of this report is to coordinate with the staff from WRPS, the current contract holder for operations at the Hanford site to better inform design decisions for the Autonomous systems for Hanford waste tank handling project. The project goals are to support risk reduction associated with monitoring, inspection and mapping of Hanford tank underground pits and includes: 1. A pit mock-up demonstration of Idaho National Laboratory’s (INL) Autonomous Pit Exploration System (APES) technology, which has two configurations: A. The Autonomous Robotic Arm, which is a proposed collaboration with Florida International University (FIU) and has capabilities to visually inspect, monitor, map and conduct simple tool manipulation tasks in the tank pits, and B. The robotic crawler configuration, which has capabilities to deploy to the bottom of the pits and conduct closer and bottom-up visual inspections. 2. An Implementation Plan that identifies Hanford site-wide application of the INL remote robotics technologies to enhance the performance of the tank farm systems and the characterization of the waste they contain to mitigate risk and optimize the overall waste mission. 3. A first-of-a-kind environmental digital twin will be produced. Digital twins to date require permanently installed sensors in order to produce asset specific predictions. This project will use the intermittent signals during inspections from deployed sensors on robotic systems to produce the data sets used by AI/ML to enable predictions of issues on tanks.

42 - ENGINEERING↗

Pacific Northwest National Laboratory Facility Radionuclide Emission Points and Sampling Systems

Battelle–Pacific Northwest Division operates numerous research and development laboratories in Washington State. The U.S. Department of Energy (DOE) contracts to Battelle at Richland facilities on both the DOE Hanford Site and the Pacific Northwest National Laboratory (PNNL) Richland campus. These facilities have the potential for radionuclide air emissions. The PNNL contract with DOE also includes operations at the PNNL-Sequim campus in Sequim, where there is also the potential for radionuclide air emissions. This document is a periodic update that describes current PNNL facility emission units and sampling systems. The National Emission Standard for Hazardous Air Pollutants (NESHAP [40 Code of Federal Regulations 61, Subpart H]) requires an assessment of all emission units that have the potential for radionuclide air emissions. Emission units are registered with the State of Washington. Potential emissions from emission units are assessed annually by PNNL staff. Sampling, monitoring, and other regulatory compliance requirements are designated based on the potential to-emit dose criteria, a graded approach to facility-identified potential impact categories, and regulatory requirements. The purpose of this document is to describe the facility radionuclide air emission sampling program and provide current and historical facility emission unit system performance, operation, and design information. For sampled emission units, the building, exhaust unit, control technologies, and sample extraction details are provided. Additionally, applicable configuration drawings, figures, and photographs are included. For non-sampled emission units, emission estimation and radionuclide source details are provided. Site-wide permits for the lowest potential impact category are described. Deregistered/transitioned emission unit details are also provided as necessary for at least 5 years post-closure/transition. Currently, five emission units are sampled continuously for particulate radionuclides at PNNL managed facilities on the PNNL-Richland campus (3 of the 5) and on the Hanford Site (2 of the 5). Four of these units have sampling systems that comply with the American National Standards Institute/Health Physics Society (ANSI/HPS) N13.1–2011 standard for sampling from stacks and ducts of nuclear facilities, and the fifth is grandfathered and compliant with the older ANSI N13.1–1969 standard. In addition, the PNNL-managed Hanford Site 325 Building EP 325-01-S stack is sampled continuously for emissions of tritium. No emissions sampling is required for the single licensed emission unit on the PNNL-Sequim campus.

54 ENVIRONMENTAL SCIENCES↗

Computational model for predicting the performance of fluid-powered longiudinal piston modules and motors.

A Matlab-based computational model line code has been developed for predicting the performance of fluid-powered longitudinal piston modules and motors. A system of equations has been developed based upon applying the conservation of mass to a control volume defined by a reciprocating piston. The method results in a differential equation that predicts the pressure gradient in the control volume as a function of rotor rotation angle. The model uses an integration scheme to predict the pressure state in the control volume. The orifice equation is used to predict the flowrate in and out of the control volume. From the resulting solution the torque and speed characteristics of the motor configuration can be predicted, optimized, or tailored for a specific requirement.SAND2019-13983 M Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.

Taylor, Michael↗

Electromagnetic Induction (EMI) Data, 2024, Trail Creek, Colorado

This dataset contains Electromagnetic Induction (EMI) data collected at Trail Creek, Colorado, in 2024. EMI surveys were conducted to investigate the spatial distribution of electrical conductivity in the subsurface, providing insights into soil moisture and subsurface geological features. The surveys were performed along multiple transects to capture variations in conductivity influenced by changes in soil composition, moisture content, and underlying geological structures. This dataset complements other geophysical data collected in the region, including Electrical Resistivity Tomography (ERT) and Terrestrial LiDAR Scanning (TLS), providing a detailed understanding of the subsurface and its impact on surface vegetation and hydrological processes. The data are valuable for environmental geophysics, ecological research, and hydrological modeling in mountainous ecosystems. The files include: - data.zip: the raw EMI data (.csv) - inversion.zip: the inverted resistivity model (.csv and .kml) - kriging.zip: the kriging resistivity model (.csv, .tif, .kmz) - flmd.csv: file level metadata file describing all files within this dataset - dd.csv: data dictionary file describing the column headers within CSV files This work was supported by the Watershed Function Science Focus Area at Lawrence Berkeley National Laboratory funded by the US Department of Energy, Office of Science, Biological and Environmental Research under Contract No. DE-AC02-05CH11231.

CMD Mini-Explorer↗

Passive Ultrasonic Deterrents to Reduce Bat Mortality in Wind Farms (Final Report)

The overall objective of this project was to develop active and passive ultrasonic deterrent concepts to mitigate bat mortality at wind turbines. The research was supported by the US Department of Energy under the contract DE-EE0008731. Novel ultrasonic bat deterrents are investigated in this study. The deterrents are based on the idea of aerodynamic whistles wherein flow-acoustic resonance is used to produce high-amplitude tonal sound at desired ultrasonic frequencies. The deterrents can be grouped into active and passive. The active deterrents/whistles are driven by pressurized air supplied by an external source (e.g., an air compressor). The passive deterrents/whistles are designed to be mounted on wind turbine blades and are “powered” by the energy in the air moving past the rotor blades. Multiple active and passive deterrent ideas are proposed and investigated numerically and experimentally. The computational analysis involves solving the compressible unsteady Reynolds-averaged Navier-Stokes (URANS) equations and coupling the near-field aerodynamic solution with an integral method based on the Ffowcs Williams-Hawkings acoustic analogy to predict ultrasound in the farfield. Experiments are performed in the anechoic chamber at ISU (for the active whistles) and in the Stability wind tunnel at Virginia Tech (for the passive whistles).

17 WIND ENERGY↗

Utility-Scale Solar, 2023 Edition: Empirical Trends in Deployment, Technology, Cost, Performance, PPA Pricing, and Value in the United States [Slides]

Berkeley Lab’s “Utility-Scale Solar, 2023 Edition” presents analysis of empirical plant-level data from the U.S. fleet of ground-mounted photovoltaic (PV), PV+battery, and concentrating solar-thermal power (CSP) plants with capacities exceeding 5 MWAC (PV plants of 5 MWAC or less, including residential rooftop systems, are covered separately in Berkeley Lab’s companion annual report, Tracking the Sun). Highlights of this year’s update include: -10.4 GWAC of new utility-scale PV capacity came online in 2022, bringing cumulative installed capacity to more than 61.7 GWAC across 46 states. -94% of all new utility-scale PV capacity added in 2022 uses single-axis tracking. -Median installed project costs declined to $\$1.32$/WAC (or $\$1.07$/WDC) in 2022. -Plant-level capacity factors vary widely, from 9% to 35% (on an AC basis), with a sample median of 24%. The report explores drivers of this variation. -Utility-scale PV’s LCOE fell to $\$39$/MWh in 2022 ($\$29$/MWh if factoring in the federal investment tax credit, or ITC). -PPA prices have largely followed the decline in solar’s LCOE over time, but have recently stagnated and even moved slightly higher. Prices from a sample of recent contracts average around $\$20-30$/MWh (levelized) in the West and $\$30-40$/MWh elsewhere in the continental US. -In 2022, solar’s average market value (defined in the report to include only energy and capacity value) rose by 40% to $\$71$/MWh and exceeded average wholesale prices in 4 of the 7 ISOs/RTOs and 11 of 18 other balancing authorities analyzed. -Adding battery storage is one way to increase the value of solar. Our public data file tracks metadata and PPA prices from ~100 PV+battery hybrid projects that are already online or that have secured offtake arrangements. -the end of 2022, there were at least 947 GW of utility-scale solar power capacity within the interconnection queues across the nation, 456 GW of which include batteries. For more information, and to explore related interactive data visualizations, go to utilityscalesolar.lbl.gov.

14 SOLAR ENERGY↗

Qthreads Support for MPICH

SAND2024-00944O Qthread Support for MPICH is software that provides additions needed to enable the use of the Qthreads library. The high-performance message passing interface (MPICH) is an open-source implementation of MPI mainly developed and distributed by Argonne National Laboratory. Qthreads is a lightweight, user-level threading library developed and distributed by Sandia National Laboratories. MPICH currently supports Posix threads, Windows threads, and Argobots. This software enables parallel programs built with the MPICH implementation of MPI to use Qthreads user-level threads rather than Posix system-level threads. The software uses existing infrastructure in MPICH to interface to the Qthreads library. The existing interfaces in MPICH allow for creating, destroying, and managing the execution of multiple threads within a process and this software translates these calls to the equivalent Qthreads library functions. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.

Ciesko, Jan↗

Wide Bandgap Generation (WBGen): Developing the Future Wide Bandgap Power Electronics Engineering Workforce

This Final Technical Report (FTR) summarizes the work conducted at the Center for Power Electronics Systems (CPES) under the Wide-Bandgap Generation (WBGen) fellowship and traineeship program established by the Advanced Manufacturing and Technologies Office (AMMTO) of the U.S. Department of Energy Office of Energy Efficiency and Renewable Energy (EERE) at Virginia Tech, which had as main objective to train the next generation of U.S. citizen power engineers with wide-bandgap (WBG) power semiconductor expertise, with the intent to aid in fulfilling the future workforce needs in this field. The latter was deemed of strategic importance given the fast-paced growth observed—and predicted—in the demand of this technical expertise, whose practitioners have become the enablers and executioners of the electrification transformation process that not just the U.S., but the whole world, is currently undergoing as it seeks for more effective and efficient ways to use energy. As such, the WBGen program set forth to achieve its educational goals, which in addition sought to broaden the range of WBG-based power electronics by conducting research and development on high-efficiency grid apparatus and high-efficiency electrical power systems, and to also enhance the power engineering curriculum by formalizing WBG-oriented design procedures replacing existent yet now obsolete design procedures developed for Silicon (Si) based power electronics. This effort led CPES to spearhead the development of a new major within The Bradley Electrical and Computer Engineering (ECE) Department at Virginia Tech, namely Electronic Power and Energy Systems (EPES), which coalesced power electronics and power systems courses to provide undergraduate students with a strong formation in the power engineering field, while creating a pipeline of graduate students that could pursue the WBG-based curriculum and conduct research at CPES. In all, in what is considered a true success, eight of the twenty WBGen fellows that graduated program were recruited from the ECE department undergraduate cohort. The traineeship emphasized as well, from its beginning, the partnership with industry and national laboratories, which took advantage of the successful industry consortium at CPES that has historically been formed by 80–90 power and energy companies working in close collaboration with the center. This gave WBGen fellows the accessibility and possibility to conduct internships at partner facilities during the summer months, focused solely on the evaluation, testing, and adoption of WBG devices, which were many times tightly related to their respective research work and plans. In addition, WBGen fellows conducted their main research work within the confines of research programs at CPES conducted with these industry partners, providing them with a unique opportunity to develop not just their technical expertise—while advancing their knowledge, but to also learn and practice a slew of skills needed for their professional growth. As such, the fellows tackled a variety of WBG-related research topics, from device reliability and capability aspects as well as packaging and integration, encompassing the use of advanced materials and new structures, current sharing challenges, and insulation systems, to advanced gate-drivers with integrated sensors and protection mechanisms and active current- and voltage-based control, to optimized layouts seeking to maximize the switching and power processing performance of these devices, to power processing solutions adopting Gallium-Nitride (GaN) and Silicon-Carbide (SiC) power semiconductors for a variety of applications; including radiation-hardened converters for space dc distribution systems, direct three-phase ac-to-ac power converters for aerospace systems, dc-ac inverters for automotive traction drives, high-frequency isolated dc-dc battery chargers also for heavy transportation systems, and medium-voltage dc-dc and dc-ac converters for distribution systems and future power grids. The WBGen program ultimately graduated a total of 20 power engineers, all experts on WBG-based power electronics, awarding 18 M.S. and 2 PhD degrees in the process. These fellows, all U.S. citizens, allowed CPES to increase the number of citizens students to 33 % at the peak of the program, as the traineeship made possible the recruitment of talent with more attractive graduate research assistantship (GRA) contracts. Unfortunately, the present U.S. citizen enrollment at CPES has declined back to historic levels—approximately 10 %, as the regular GRA rates are not competitive enough when compared with entry-level industry jobs. In all, WBGen fellows published a total of 7 peer-reviewed journal articles, 44 papers at international technical conferences, made 42 presentations at international technical conferences, and filed 4 invention disclosures and patent applications, which have since then been granted by the U.S. Patent and Trademark Office (USPTO). Their contribution to CPES, Virginia Tech, the United States, and the world, has been significant, and continues to yield results thanks to the exemplary career that the fellows have initiated at many of the partners of the program, which include Wolfspeed, Raytheon Technologies, Infineon, Lockheed Martin, Dominion Energy, Northrop Grumman, Rivian, Aerospace Corporation, Sandia National Laboratory, National Renewable Energy Laboratory, John Hopkins University, and Virginia Tech.

14 SOLAR ENERGY↗

Turning Normal to Abnormal: Reversing CO 2 /C2–Hydrocarbon Selectivity in HKUST–1

Metal–organic frameworks (MOFs) can efficiently purify hydrocarbons from CO 2 , but their rapid saturation, driven by preferential hydrocarbon adsorption, requires energy-intensive adsorption–desorption processes. To address these challenges, an innovative approach is developed, enabling control over MOF flexibility through densification and defect engineering, resulting in an intriguing inverse CO 2 /C2 hydrocarbon selectivity. Here, in this study, the densification process induces the shearing of the crystal lattice and contraction of pores in a defective CuBTC MOF. These changes have led to a remarkable transformation in selectivity, where the originally hydrocarbon-selective CuBTC MOF becomes CO 2 -selective. The selectivity values for densified CuBTC are significantly reversed when compared to its powder form, with notable improvements observed in CO 2 /C 2 H 6 (4416 vs 0.61), CO 2 /C 2 H 4 (15 vs 0.28), and CO 2 /C 2 H 2 (4 vs 0.2). The densified material shows impressive separation, regeneration, and recyclability during dynamic breakthrough experiments with complex quinary gas mixtures. Simulation studies indicate faster CO 2 passage through the tetragonal structure of densified CuBTC compared to C 2 H 2 . Experimental kinetic diffusion studies confirm accelerated CO 2 diffusion over hydrocarbons in the densified MOF, attributed to its small pore window and minimal interparticle voids. This research introduces a promising strategy for refining existing and future MOF materials, enhancing their separation performance.

36 MATERIALS SCIENCE↗

Life-Cycle Baseline Customization for the Formerly Utilized Sites Remedial Action Program - 20304

One of the responsibilities of the federal government is to estimate sound and defensible life-cycle baseline costs for use in federal budget estimates and to meet federal financial reporting requirements. To accomplish this, the US Department of Energy (DOE) Office of Legacy Management (LM) and the US Army Corps of Engineers (USACE) have partnered together to ensure that the liabilities documented in each Formerly Utilized Sites Remedial Action Program (FUSRAP) site's life-cycle baseline are specifically tailored. FUSRAP was created in the mid-1970's to clean up radiological contamination resulting from the early development of nuclear weapons. DOE was responsible for FUSRAP until October 1997, when Congress transferred the administration and execution of FUSRAP site cleanups to USACE. By 1997, DOE had completed the cleanup of 25 of the 46 sites that were active within the program and had begun cleanup at 13 additional sites. USACE was assigned responsibility for the cleanup of the 21 remaining FUSRAP sites, and at 8 additional sites that had since been referred for cleanup. The LM mission for the FUSRAP sites is to perform long-term surveillance and maintenance (LTS and M). Currently, LM provides long-term stewardship for 34 completed FUSRAP sites. Another 20 sites are under active remediation by USACE. Within the last 5 years, USACE has completed the cleanup at five FUSRAP sites and the LTS and M responsibility has been transferred to LM. By 2029, USACE will compete remediation at eight additional sites and LTS and M for those sites will transfer to LM. Because responsibilities for the FUSRAP sites transfer between USACE and LM upon completion of remedial actions, both agencies maintain life-cycle baselines for different stages of the project and both must have a strong understanding of the needs and requirements for each site. This understanding ensures that the life-cycle baselines form a complete and accurate picture of what is required for the site and for the FUSRAP program. LM focuses on several things when customizing the life-cycle baseline estimates for the FUSRAP sites, including (1) Understanding the unique requirements for each site. By reviewing site-specific documents prepared by USACE, such as Feasibility Studies and Records of Decision, and partnering with USACE to gain additional insight about site conditions and requirements for stewardship, as well as potential risks, LM can better develop the life-cycle baselines. (2) Developing site-specific labor breakdowns. This ensures the required labor mix is baselined for specific activities by comparing the labor mix required to perform activities at (a) other LM-managed FUSRAP sites and (b) non-FUSRAP LM sites and (c) by USACE at active FUSRAP sites. (3) Taking a tiered approach to life-cycle baseline planning. Estimates for sites transferring to LM in the near term (5 years) are more definitive than for sites transferring in the out-year period. Remedial actions at the near-term sites are at or near completion, providing LM a strong understanding of the LTS and M requirements and remaining liabilities. This in turn allows for site-specific customization of the baseline. (4) Using a robust risk management approach to ensure that liabilities specific to each site are identified, evaluated by probability and severity, and documented in relation to the impact to cost or schedule. To ensure the most accuracy within all the baselines, the FUSRAP life-cycle baselines are updated as needed to support program, project, and contract management needs. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Probing C–I bond fission in the UV photochemistry of 2-iodothiophene with core-to-valence transient absorption spectroscopy

The UV photochemistry of small heteroaromatic molecules serves as a testbed for understanding fundamental photo-induced chemical transformations in moderately complex compounds, including isomerization, ring-opening, and molecular dissociation. Here, a combined experimental-theoretical study of 268 nm UV light-induced dynamics in 2-iodothiophene (C 4 H 3 IS) is performed. The dynamics are experimentally monitored with a femtosecond extreme ultraviolet (XUV) probe that measures iodine N-edge 4d core-to-valence transitions. Experiments are complemented by density functional theory calculations of both the pump-pulse induced valence excitations and the XUV probe-induced core-to-valence transitions. Possible intramolecular relaxation dynamics are investigated by ab initio molecular dynamics simulations. Furthermore, gradual absorption changes up to ~0.5 to 1 ps after excitation are observed for both the parent molecular species and emerging iodine fragments, with the latter appearing with a characteristic rise time of 160 ± 30 fs. Comparison of spectral intensities and energies with the calculations identifies an iodine dissociation pathway initiated by a predominant π → π* excitation. In contrast, initial excitation to a nearby n ⟂ → σ* state appears unlikely based on a significantly smaller oscillator strength and the absence of any corresponding XUV absorption signatures. Excitation to the π → π* state is followed by contraction of the C–I bond, enabling a nonadiabatic transition to a dissociative π→σ C-I * state. For the subsequent fragmentation, a relatively narrow bond-length region along the C–I stretch coordinate between 230 and 280 pm is identified, where the transition between the parent molecule and the thienyl radical + iodine atom products becomes prominent in the XUV spectrum due to rapid localization of two singly occupied molecular orbitals on the two fragments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural Changes during the Conversion Reaction of Tungsten Oxide Electrodes with Tailored, Mesoscale Porosity

In-plane tungsten oxide nanostructures, including hexagonally patterned cylinders and holes in a matrix, were fabricated via sequential infiltration synthesis (SIS) on self-assembled block copolymer templates. Using the tailored morphology and porosity of these model electrodes with in situ grazing incidence small angle X-ray scattering, the intrinsic structural change of nanoscale active materials during the conversion reaction of WO 3 + 6Li ↔ W + 3 Li 2 O was investigated at controlled electrochemical conditions. Reversible electrode volume expansion and contraction was observed during lithiation and delithiation cycles, respectively. The potential where electrode’s thickness expansion started was ~1.6 V, which is close to thermodynamically expected one for conversion reaction of WO 3 with lithium (1.65 V). The temporal evolution of the electrode volume at constant electrode potentials revealed high overpotential for bulk lithiation and slow conversion reaction kinetics, despite the tailored porosity of the SIS electrodes. Oxide cylinders showed smaller overall electrode thickness change, likely due to unconstrained lateral volume change, as compared to a matrix with holes. On the other hand, better connectivity and guided volume change of the latter electrode morphology provided improved cycling stability. Additionally, heterogeneity in an electrode, from internal pores and density gradients, was found to aggravate the fragmentation of the electrode during conversion reaction. Insights into oxide conversion reaction kinetics and the relationship between electrode mesostructure and cycling behavior obtained from this study can help guide the more rational design of conversion electrode for high performing batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Co-Registered In-Situ and Ex-Situ Dataset of Electrical, Acoustic, and CT Characteristics from Wire Arc Additive Manufacturing Process

Recent progress in sensing techniques and data analytics tools have significantly accelerated the development of Wire Arc Additive Manufacturing (WAAM) systems. This data centric approach emphasizes leveraging available data throughout the production process to optimize performance. Integration of extensive data analysis provides the opportunity to improve precision, reduce waste, and enhance the quality of produced parts. This method relies on AI/ML models and optimization techniques, which are developed using the data collected from various sources, including in-situ sensors, ex-situ imaging, and manufacturing process parameters. The quality and diversity of this data, along with the alignment between different data streams (achieved through spatiotemporal registration) are critical for the successful development of AI/ML and optimization models. In this work, we present a spatiotemporally registered dataset generated during the WAAM process of deposition of a rectangular block. The dataset includes the comprehensive description of deposition process, process parameters, in-situ collected welding characteristics, acoustic data, and X-Ray Computed Tomography analysis data for the build. Dataset A Co-Registered In-Situ and Ex-Situ Dataset of Electrical, Acoustic, and CT Characteristics from Wire Arc Additive Manufacturing Process has arisen under UT-Battelle, LLC’s Prime Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy (DOE) to manage and operate the Oak Ridge National Laboratory. UT-Battelle, LLC will not assert any rights under United States law or under the Prime Contract it has in the dataset against any user of the dataset, including any copyrights or patent rights. UT-Battelle, LLC requests that attribution to the dataset is provided as academically appropriate.

42 ENGINEERING↗

Analysis of Exposure during Transportation of Waste to the Nevada National Security Site (NNSS) - 20445

Safety is a priority for the U.S. Department of Energy (DOE) Environmental Management (EM) Nevada Program. This commitment to safety is integrated into requirements and work procedures at DOE sites across the U.S. that generate low-level radioactive waste, mixed low-level radioactive waste, and classified waste that is transported to the Nevada National Security Site (NNSS) for permanent disposal. Generators of this waste are responsible for ensuring it is packaged and transported in a safe and compliant manner. These generators and their contracted commercial carriers must comply with U.S. Department of Transportation (DOT) regulations; the Nevada National Security Site Waste Acceptance Criteria (NNSSWAC); and other applicable federal, state, and local regulations and requirements. This includes packaging and shipping the waste to meet DOT regulatory radiation dose limits to ensure public safety during transportation. NNSS waste generators have a solid safety record for complying with these stringent regulations as demonstrated by the fact that no shipments exceeding DOT dose rate limits were received at the NNSS Area 5 Radioactive Waste Management Complex (RWMC) during FY 2014 through FY 2018. A 2005 study conducted by the Desert Research Institute validated shipments to the NNSS comply with DOT radiation dose limits. In response to recent Nevada stakeholder requests for an updated study, an analysis was conducted to verify and provide evidence that the public continues to be safe from exposure to radioactive waste shipment to the NNSS. Radiation exposure from radioactive waste shipments in transit to the NNSS was evaluated. Three studies were performed: 1. Confirm compliance of waste shipments to the DOT radiation limits using dose rate surveys taken at the generator site and at the disposal site. 2. Estimate the dose to the public from waste shipments using the dosimetry results for disposal site personnel by comparing time of exposure for various individuals/scenarios. 3. Estimate the truck driver dose using the receipt dose rate surveys and time of exposure, and from dosimetry results. Study 1 confirmed compliance with the DOT dose rate limits for a sample of waste shipments (123 of 1,038) received during fiscal year (FY) 2017. Study 2 showed that the average annual radiation equivalent dose for disposal site personnel during FY 2017 was approximately 6.7% [0.415 mSv (41.5 millirem)] of the annual average dose that a person living in the U.S. receives from all sources [6.2 mSv (620 mrem)]. Maximum dose to a member of the public, a person resting/sleeping in an adjacent truck at a rest area to a waste shipment, was 0.0166 mSv (1.66 mrem), which is less than the dose received from a person taking a round trip from the east coast to the west coast of the continental U.S. on an airplane [0.07 mSv (7 mrem) per round trip]. Study 3 showed that the truck driver who made the most shipments of radioactive waste to the NNSS, who drove the most hours (estimated time of exposure 2,520 hours), during FY 2017 had a total dose of 0.15 mSv (15 mrem), which was obtained from their personal dosimeter. The annual dose recorded for disposal site personnel, the dose estimates for the public, and the truck driver dose were all a small percentage of the average radiation dose a person receives from all sources (e.g., background and medical radiation). At these levels, risk should only be described qualitatively. Radiation exposure from radioactive waste shipments to the NNSS were shown to be compliant with the DOT dose rate limits, safe, and very low (i.e., within background levels). (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗