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Selective CO 2 Reduction by Bis(bipyridine)cobalt(II) Catalysts: The Role of Pendant Pyridine as a Proton Acceptor

Electrochemical CO 2 reduction reaction (CO 2 RR) catalyzed by molecular earth-abundant metal catalysts is a promising strategy to convert CO 2 into value-added products. One recent trend in this field has been focusing on the rational design of catalysts by incorporating redox-active ligands and modifying the secondary coordination sphere (SCS) to achieve efficient and selective CO 2 RR. Herein, we report a series of Co bis­(bipyridine) catalysts featuring various dangling groups, such as pyridine, tertiary amine, or butyl, in the secondary coordination sphere (Co-PyMe, Co-Py, Co-PrN, and Co-Bu). Efficient, selective electrocatalytic CO 2 RR was achieved by the complexes after the generation of triply reduced intermediate consisting of a Co I center and a dianionic ligand, producing CO as the major product and trace amount of H 2 . Strong correlations with the identity of dangling groups and turnover frequency (TOF) have been observed, in which Co-PyMe displayed the highest TOF (1086 s –1 in MeCN/H 2 O). Mechanistic studies indicated that the acceleration of CO 2 RR with pyridine-functionalized catalysts were derived from the protonation of pyridine dangling groups which participated as weak acids in the H-bonding network with exogenous proton sources, stabilizing CO 2 -bound intermediates and facilitating proton transfer. In addition, precatalytic CO 2 binding and activation at the third reduction (−2.1 V) was revealed by CV and SEC-IR studies. The resultant doubly reduced CO-bound species acted as a trapping state which inhibited CO 2 RR electrocatalysis. Regeneration of active species was accessed via reductive dissociation of CO at a more negative potential. In conclusion, this study highlights the combined effects of redox-active ligands and pyridine/pyridinium as SCS groups on CO 2 RR catalysis and provides design principles for future development of CO 2 RR catalysts utilizing pyridine/pyridiniums as SCS functional groups to fine-tune the catalytic activity.

CO2 reduction↗

Precision Kinematic Sunyaev--Zel'dovich Measurements Across Halo Mass and Redshift with DESI DR2 and ACT DR6: Part I. Luminous Red Galaxies

We present the most precise measurements of the kinetic Sunyaev-Zel'dovich (kSZ) effect around luminous red galaxies to date, detecting the signal at $18σ$ significance in both harmonic and configuration space. Our analysis cross-correlates 2.4 million spectroscopic LRGs from the Dark Energy Spectroscopic Instrument (DESI) DR2 sample with Data Release 6 (DR6) of the Atacama Cosmology Telescope (ACT). We develop a novel harmonic-space cross-correlation approach using momentum-weighted kSZ templates, yielding nearly uncorrelated bandpowers within a framework consistent with other large-scale structure analyses. By incorporating the LRG halo occupation distribution (HOD) and its uncertainty, we convert measured galaxy gas profiles into halo gas profiles and provide generalized Navarro-Frenk-White (GNFW) fitting profiles, providing empirical targets for tuning feedback efficiency in hydrodynamical simulations and for baryonic modeling in large-scale structure analyses. We find strong evidence that gas profiles do not trace dark matter, providing direct evidence for gas redistribution beyond gravitational collapse. Comparing to hydrodynamical simulations, our measurements favor feedback efficiencies exceeding those in the Battaglia profile, suggesting more efficient gas ejection in group-scale halos than previously predicted. Splitting by redshift, we detect the kSZ signal at SNR $\approx 5$--$10$ in each of four bins and find amplitude evolution consistent with the expected decline in mean halo mass at fixed comoving number density. Splitting by stellar mass, we study the scaling of kSZ amplitude with galaxy properties. Together with BGS and ELG measurements in Paper II, these results span $0.1 \lesssim z \lesssim 1.6$ across three galaxy populations, demonstrating the potential of spectroscopic kSZ to map circumgalactic gas and constrain baryonic feedback.

Qu, F. J. [KIPAC, Menlo Park; Stanford U., HEPL; S↗

West Valley Demonstration Project Annual Site Environmental Report (CY2019)

The report, prepared for the U.S. Department of Energy West Valley Demonstration Project office (DOE-WVDP), summarizes the environmental protection program at the WVDP for calendar year (CY) 2019. Monitoring and surveillance of the facilities used by the DOE are conducted to verify protection of public health and safety and the environment. The report is a key component of DOE’s effort to keep the public informed of environmental conditions at the WVDP. The quality assurance protocols applied to the environmental monitoring program ensure the validity and accuracy of the monitoring data. In addition to demonstrating compliance with environmental laws, regulations, and directives, evaluation of data collected in 2019 continued to indicate that WVDP activities pose no threat to public health or safety, or to the environment.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

13 C ENDOR Characterization of the Central Carbon within the Nitrogenase Catalytic Cofactor Indicates That the CFe 6 Core Is a Stabilizing “Heart of Steel”

Substrates and inhibitors of Mo-dependent nitrogenase bind and react at Fe ions of the active-site FeMo-cofactor [7Fe–9S–C–Mo–homocitrate] contained within the MoFe protein α-subunit. The cofactor contains a CFe 6 core, a carbon centered within a trigonal prism of six Fe, whose role in catalysis is unknown. Targeted 13 C labeling of the carbon enables electron-nuclear double resonance (ENDOR) spectroscopy to sensitively monitor the electronic properties of the Fe–C bonds and the spin-coupling scheme adopted by the FeMo-cofactor metal ions. Here this report compares 13 CFe 6 ENDOR measurements for (i) the wild-type protein resting state (E 0 ; α-Val 70 ) to those of (ii) α-Ile 70 , (iii) α-Ala 70 -substituted proteins; (iv) crystallographically characterized CO-inhibited “hi-CO” state; (v) E 4 (4H) Janus intermediate, activated for N 2 binding/reduction by accumulation of 4[ e– /H + ]; (vi) E 4 (2H)* state containing a doubly reduced FeMo-cofactor without Fe-bound substrates; and (vii) propargyl alcohol reduction intermediate having allyl alcohol bound as a ferracycle to FeMo-cofactor Fe6. All states examined, both S = 1/2 and 3/2 exhibited near-zero 13 C isotropic hyperfine coupling constants, $^Ca$ = [-1.3 ↔ +2.7] MHz. Density functional theory computations and natural bond orbital analysis of the Fe-C bonds show that this occurs because a (3 spin-up/3 spin-down) spin-exchange configuration of CFe 6 Fe-ion spins produces cancellation of large spin-transfers to carbon in each Fe–C bond. Previous X-ray diffraction and DFT both indicate that trigonal-prismatic geometry around carbon is maintained with high precision in all these states. The persistent structure and Fe–C bonding of the CFe 6 core indicate that it does not provide a functionally dynamic (hemilabile) “beating heart”-instead it acts as “a heart of steel”, stabilizing the structure of the FeMo-cofactor-active site during nitrogenase catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Treatment of Problematic Reactive Metal Wastes Using GeoMelt ICV - WM2020 Conference Paper

Decommissioning of sodium-cooled reactors and fast reactor technologies has generated a number of reactive metal waste configurations that are problematic to treat and typically lack cost effective treatment methods and disposition options. As a result, Veolia Nuclear Solutions, under contract with Idaho National Laboratory (owned by the U.S. Department of Energy and managed and operated by Battelle Energy Alliance, LLC) demonstrated its GeoMelt® In-Container Vitrification (ICV)™ technology to safely convert sodium metal to a non-reactive vitrified oxide form. The demonstration project, supported by glass formulation and crucible testing, consisted of a series of ICV™ melts that processed elemental sodium into stable non-reactive glass. INL is currently implementing GeoMelt® technology as a means to safely and reliably convert radioactive reactive metal residues that contaminate sodium cooled reactor components into waste forms that comply with existing disposition pathways. Reactive metal wastes require treatment in order to remove the Resource Conservation and Recovery Act (RCRA) reactivity and ignitability characteristics to comply with land disposal restrictions. GeoMelt®, which is an alternative to other potential treatment approaches, provides a robust approach that chemically converts the reactive metals to an inert oxide while also immobilizing radionuclides in a vitrified waste form with durability equal to or better than vitrified nuclear fuel reprocessing wastes (very robust and inert waste forms). Most other treatment approaches generate hydrogen gas which is problematic. In 2016, Veolia Nuclear Solutions first demonstrated the effectiveness of the GeoMelt® ICV™ process in deactivating reactive sodium metal. Crucible, bench-scale, and engineering-scale demonstrations were conducted on several surrogate waste configurations with various ratios of sodium metal and glass-formers. Each ratio and configuration demonstrated complete deactivation of the surrogate sodium metal. Follow-on work in 2017 demonstrated the deactivation of reactive sodium by GeoMelt® ICV™ at a higher waste loading relative to previously demonstrated work performed in 2016; the higher waste loading optimized glass chemistry while enhancing the economical full-scale treatment of reactive metals. Additionally, follow-on demonstration testing in 2018 and 2019 focused on more complex shapes and other reactive-metals (mocked up Experimental Breeder Reactor II [EBR-II] subassembly, sodium filled heat exchanger, and a can containing sodium potassium alloy) which were all performed at engineering-scale. Since 2018, a 10-metric ton full-scale GeoMelt unit (GeoMelt® Richland) was designed, installed, and commissioned at Perma-Fix Northwest in Richland, Washington for the treatment of reactive metal wastes. As of September 2019, over 900 55-gallon drums containing a total of around 3,500 lb of sodium with low levels of radioactivity have been treated at GeoMelt ® Richland, with resulting glass monoliths disposed at the Nevada National Security Site (NNSS). A full-scale radiological demonstration melt on an actual EBR-II subassembly has also been performed using the full-scale melter in 2019. The GeoMelt® technology is a proven radioactive waste treatment technology capable of immobilizing radioactive wastes, including bulk rubble such as drums and other steel vessels usually without pretreatment. Utilizing the GeoMelt® technology to treat reactive metals eliminates pretreatment steps resulting from having to separate the reactive metal from steel containers or jackets as GeoMelt® can easily operate at temperatures sufficient to melt the steel and expose the reactive metal for treatment. Eliminating handling steps of reactive metals is a significant safety advantage since reactive metals are pyrophoric. The results generated as a part of the 2018-2019 demonstration program are presented in the paper.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Planar Defect Layers Template a High-Pressure InBi Polymorph

The short- and long-range order of III–V materials under high pressure has long been the subject of debate, with advancements in structural characterization leading to significant revisions to the accepted structural models. Despite these revisions, previous high-pressure structural assignments in the In–Bi system include the site-disordered β-Sn structure type, a structure type demonstrated to be nonexistent in analogous III–V systems. While X-ray diffraction is consistent with site disordering in InBi at high pressure, cluster expansion calculations indicate that disordering requires temperatures above 3000 K. Here, we propose InBi as a model material for studying unique high-pressure planar defects due to its highly anisotropic stress-dependent properties and structure. Specifically, we identify two sets of planar defects that mimic the diffraction pattern of a site disordered β-Sn structure type and are compatible with the calculated disorder barrier. We derive these defects by symmetry relations over crystallographic transitions. Density functional theory calculations of the proposed defects suggest that these defects are stabilized by diminishing interlayer separations with pressure. Further, we find that one of the proposed defects closely resembles a bulk high-pressure phase of InBi, InBi-ϵ, and we assert that the proposed defects order upon heating, acting as a template for InBi-ϵ growth. The proposed defects and their electronic structure provide a basis for the trend of superconducting critical temperature with increasing pressure. These methods for identifying defects are generalizable to other materials with reports of site disorder at high pressure, prompting a broader search for related high-pressure defects.

36 MATERIALS SCIENCE↗

Treatment of Problematic Reactive Metal Wastes Using the GeoMelt{sup R} In-Container Vitrification (ICV{sup TM}) Process - 20326

Decommissioning of sodium-cooled reactors and fast reactor technologies has generated a number of reactive metal waste configurations that are problematic to treat and typically lack cost effective treatment methods and disposition options. As a result, Veolia Nuclear Solutions, under contract with Idaho National Laboratory (owned by the U.S. Department of Energy and managed and operated by Battelle Energy Alliance, LLC) demonstrated its GeoMelt{sup R} In-Container Vitrification (ICV){sup TM} technology to safely convert sodium metal to a non-reactive vitrified oxide form. The demonstration project, supported by glass formulation and crucible testing, consisted of a series of ICV{sup TM} melts that processed elemental sodium into stable non-reactive glass. INL is currently implementing GeoMelt{sup R} technology as a means to safely and reliably convert radioactive reactive metal residues that contaminate sodium cooled reactor components into waste forms that comply with existing disposition pathways. Reactive metal wastes require treatment in order to remove the Resource Conservation and Recovery Act (RCRA) reactivity and ignitability characteristics to comply with land disposal restrictions. GeoMelt{sup R}, which is an alternative to other potential treatment approaches, provides a robust approach that chemically converts the reactive metals to an inert oxide while also immobilizing radionuclides in a vitrified waste form with durability equal to or better than vitrified nuclear fuel reprocessing wastes (very robust and inert waste forms). Most other treatment approaches generate hydrogen gas which is problematic. In 2016, Veolia Nuclear Solutions first demonstrated the effectiveness of the GeoMelt{sup R} ICV{sup TM} process in deactivating reactive sodium metal. Crucible, bench-scale, and engineering-scale demonstrations were conducted on several surrogate waste configurations with various ratios of sodium metal and glass formers. Each ratio and configuration demonstrated complete deactivation of the surrogate sodium metal. Follow-on work in 2017 demonstrated the deactivation of reactive sodium by GeoMelt{sup R} ICV{sup TM} at a higher waste loading relative to previously demonstrated work performed in 2016; the higher waste loading optimized glass chemistry while enhancing the economical full-scale treatment of reactive metals. Additionally, follow-on demonstration testing in 2018 and 2019 focused on more complex shapes and other reactive-metals (mocked up Experimental Breeder Reactor II [EBR-II] subassembly, sodium filled heat exchanger, and a can containing sodium potassium alloy) which were all performed at engineering scale. Veolia Nuclear Solutions designed, installed, and commissioned in September 2018, at Perma-Fix Northwest in Richland Washington, a 10-metric ton full-scale GeoMelt unit (GeoMelt{sup R} Richland) for the treatment of reactive metal wastes. As of September 2019, over 900 55-gallon drums containing a total of around 3,500 lb of sodium with low levels of radioactivity have been treated at GeoMelt{sup R} Richland, with resulting glass monoliths disposed at the Nevada National Security Site (NNSS). A full-scale radiological demonstration melt on an actual EBR-II subassembly has also been performed using the full-scale melter in 2019. The GeoMelt{sup R} technology is a proven radioactive waste treatment technology capable of immobilizing radioactive wastes, including bulk rubble such as drums and other steel vessels usually without pretreatment. Utilizing the GeoMelt{sup R} technology to treat reactive metals eliminates pretreatment steps resulting from having to separate the reactive metal from steel containers or jackets as GeoMelt{sup R} can easily operate at temperatures sufficient to melt the steel and expose the reactive metal for treatment. Eliminating handling steps of reactive metals is a significant safety advantage since reactive metals are pyrophoric. The results generated as a part of the 2018-2019 demonstration program are presented in the paper. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Tonal Emergence: An agent-based model of tonal coordination

Humans have a remarkable capacity for coordination. Our ability to interact and act jointly in groups is crucial to our success as a species. Joint Action (JA) research has often concerned itself with simplistic behaviors in highly constrained laboratory tasks. But there has been a growing interest in understanding complex coordination in more open-ended contexts. In this regard, collective music improvisation has emerged as a fascinating model domain for studying basic JA mechanisms in an unconstrained and highly sophisticated setting. A number of empirical studies have begun to elucidate coordination mechanisms underlying joint musical improvisation, but these empirical findings have yet to be cached out in a working computational model. The present work fills this gap by presenting TonalEmergence, an idealized agent-based model of improvised musical coordination. TonalEmergence models the coordination of notes played by improvisers to generate harmony (i.e., tonality), by simulating agents that stochastically generate notes biased towards maximizing harmonic consonance given their partner’s previous notes. Here, the model replicates an interesting empirical result from a previous study of professional jazz pianists: feedback loops of mutual adaptation between interacting agents support the production of consonant harmony. The model is further explored to show how complex tonal dynamics, such as the production and dissolution of stable tonal centers, are supported by agents that are characterized by (i) a tendency to strive toward consonance, (ii) stochasticity, and (iii) a limited memory for previously played notes. TonalEmergence thus provides a grounded computational model to simulate and probe the coordination mechanisms underpinning one of the more remarkable feats of human cognition: collective music improvisation.

60 APPLIED LIFE SCIENCES↗

West Valley Demonstration Project (WVDP) Annual Site Environmental Report (ASER) for Calendar Year 2021

The report, prepared for the U.S. Department of Energy West Valley Demonstration Project office (DOE-WVDP), summarizes the environmental protection program at the WVDP for calendar year (CY) 2021. Monitoring and surveillance of the facilities used by the DOE are conducted to verify protection of public health and safety and the environment. The report is a key component of DOE’s effort to keep the public informed of environmental conditions at the WVDP. The quality assurance protocols applied to the environmental monitoring program ensure the validity and accuracy of the monitoring data. In addition to demonstrating compliance with environmental laws, regulations, and directives, evaluation of data collected in 2021 continued to indicate that WVDP activities pose no threat to public health or safety, or to the environment.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Polarization‐Engineered Near‐Field Generation Using a Hybrid Tip–Antenna System

Precise control of light polarization at the nanoscale is critical for accessing chiral optical responses and manipulating spin–photon interactions in advanced materials. Yet, conventional scattering-type near-field probes predominantly generate out-of-plane linear polarization and offer little control over phase or polarization state. Here, in this study, we introduce a polarization-engineered near-field methodology based on a combined metallic tip and planar dipole nanoantenna system. Using full-wave electromagnetic simulations, we show that the tip acts as a vertically oriented plasmonic resonator, while the antenna supports an in-plane dipolar mode. By tuning the tip–antenna geometry and tip height, the two orthogonal field components attain comparable amplitudes and a controllable ∼90° phase offset, producing circularly polarized nano-light in the antenna gap. The proposed system effectively functions as a nanoscale quarter-wave plate, converting linearly polarized illumination into circularly polarized hotspots without external polarization optics. This method establishes an experimentally accessible route toward polarization-programmable near-field nanoscopy, enabling chiral spectroscopy, selective excitation of spin/valley degrees of freedom, and quantum optical investigations at the nanoscale.

36 MATERIALS SCIENCE↗

In Situ Surface Reconstruction via Lithium Residue Regulation for Direct Recycling of Ni-Rich Cathodes

Surface stability is crucial for the long cycling performance of Ni-rich cathodes, as it dictates and governs side reactions, preserves crystal integrity, and mitigates capacity degradation during cycling. For spent Ni-rich cathodes targeted for one-step direct recycling, constructing a robust and stable surface is particularly challenging because prior cycling induces severe structural and morphological degradation. Here, in this study, we introduce an in situ surface reconstruction strategy that converts surface lithium residues into a protective layer via a direct liquid-phase coating with ammonium dihydrogen phosphate (ADP). During the process, residual lithium remaining after the hydrothermal relithiation is removed, while a conformal lithium phosphate (Li 3 PO 4 , LPO) layer is formed to act as both a chemical barrier and a structural stabilizer. This dual function enhances cycling stability and rate capability in regenerated cathodes, and the approach is applicable to various Ni-rich compositions including spent LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) and scrap LiNi 0.866 Mn 0.066 Co 0.05 Al 0.018 O 2 (NCMA). Its scalability and compositional versatility make it a promising route for sustainable regeneration of high-performance cathode materials.

36 MATERIALS SCIENCE↗

Southwest Regional Partnership on Carbon Sequestration: Phase III (Final Scientific/Technical Report)

The Southwest Regional Partnership on Carbon Sequestration (SWP) is one of 7 regional partnerships formed in 2003 under the U.S. Department of Energy’s (DOE) Regional Carbon Sequestration Partnerships (RCSPs) initiative. The overall purpose of the initiative was to help determine and implement the technology, infrastructure, and regulations most appropriate to promote carbon storage in different regions of the country. Covering Arizona, Colorado, New Mexico, Oklahoma, Utah, and parts of Texas, Wyoming, and Kansas, the SWP evaluated regional carbon storage and utilization potential and focused on technologies and sites that could complement the region’s strong position in energy production. The project progressed through three phases: • Phase I (2003–2005): Characterized regional geologic formations and CO 2 sources, assessed sequestration potential, and identified pilot test sites. • Phase II (2005–2013): Conducted small-scale field tests to validate sequestration methods, including geologic and terrestrial projects. • Phase III (2008–2022): Demonstrated large-scale CO 2 injection at a commercial oil field to test monitoring, verification, and long-term storage strategies. This report covers Phase III. The final project site, the Farnsworth Unit (FWU) in Texas, provided real-world testing of reservoir characterization, monitoring, and risk evaluation tools and processes that could be used in any commercial scale carbon capture, utilization, and storage (CCUS) project. Extensive data collection and analysis helped refine best practices for reservoir characterization, injection monitoring, and storage verification. The SWP contributed to national databases, DOE best practice manuals, and regional geological assessments to support future sequestration efforts. Key lessons learned include the importance of robust data management, strategic site selection, regulatory navigation, and effective industry collaboration. The project’s findings will inform ongoing and future carbon storage initiatives. Task 1 (Regional Characterization) • The SWP continued to participate in national outreach efforts and NATCARB. • The SWP evaluated multiple potential sites before selecting the FWU as the primary field test location. Task 2 (Public Outreach and Education) • The SWP contributed to national databases, DOE best practice manuals, and regional geological assessments to support future sequestration efforts. Task 3 (Permitting and Regulatory Compliance) • The SWP ensured compliance with federal and state regulations, including National Environmental Policy Act (NEPA) requirements. • The SWP obtained all necessary permits for drilling, injection, and monitoring activities. Task 4 (Site Characterization and Planning) • The SWP developed work plans for four key activities: characterization, simulation, monitoring and verification, and risk evaluation. • The SWP collected and synthesized legacy data from multiple sources to build initial static geological models and dynamic reservoir models demonstrating project feasibility. • The SWP conducted an initial risk evaluation and developed mitigation plans. Task 5 (Field Operations and Data Collection) • The SWP drilled, logged, and cored three characterization wells to gather critical subsurface data. • The SWP conducted multiple geophysical surveys, including 3D seismic, crosswell seismic, and vertical seismic profiling, to improve reservoir characterization. Task 6 (Monitoring and Verification) • The SWP performed extensive geological characterization using data from characterization wells and seismic surveys. • The SWP established a surface monitoring network to track CO 2 flux in soil gas, groundwater chemistry, and near-surface atmospheric CO 2 levels. • The SWP built and refined reservoir models to study the effects of relative permeability on simulation behavior and improve calibration with experimental data. Task 7 (Risk Assessment and Model Refinement) • The SWP conducted multiple studies to evaluate reservoir integrity, predict CO 2 plume behavior and improve predictive modeling capabilities. • The SWP refined geological models and used them to enhance the accuracy of simulation models. • The SWP continued quantitative risk assessment of top-ranked risks and strengthened the link between qualitative and quantitative risk methodologies.

02 PETROLEUM↗

Cathode-Confined Polysulfide Retention-Release Reprograms Li 2 S Deposition in High-Loading Li–S Batteries

High-loading lithium-sulfur (Li-S) cells operated with lean electrolyte are limited by polysulfide crossover to Li metal and by transport-limited liquid-solid conversion that forms passivating Li 2 S films. Here, we show that a cathode-facing separator coating of carboxylated multiwalled carbon nanotubes acts as a cathode-confined polysulfide reservoir with intermediate binding. Early in discharge it captures newly generated polysulfides at the separator interface, suppressing shuttle reactions. As polysulfides are consumed, the reservoir buffers concentration gradients and feeds reactants back to the cathode, shifting Li 2 S deposition from burst-like film growth to progressive, three-dimensional, porous formation. Synchrotron XRD and S K-edge XANES, together with Scharifker–Hills nucleation analysis and depth-of-discharge EIS/DRT, substantiate this coupled transport–reaction control. With 4.3 mg S cm -2 and E/S = 5, cells reach 4.2 mAh cm -2 and retain 90% capacity over 100 cycles at 20 °C.

25 ENERGY STORAGE↗

Development of an immersion fiber optic Raman probe for real-time analysis of molten materials

This study presents an advancement in high-temperature Raman spectroscopy, specifically for analyzing molten materials. It introduces an approach by integrating a fiber-optic Raman probe with a copper block protection system designed to endure extreme thermal conditions. The copper block features an open port designed to accommodate an external telescope with a 3 cm focal length, enabling Raman spectra collection in challenging high-temperature environments. A built-in gas channel ensures a continuous flow of argon gas to prevent flux intrusion. The robust copper block acts as a reliable shield, safeguarding the fiber-optic Raman probe within molten materials. This enhancement maintains the probe's integrity and significantly improves its resilience, making it ideal for rigorous investigations of molten substances. This advancement is particularly relevant in metallurgy, where flux materials impact production quality and efficiency. The ability to acquire Raman signals under elevated thermal conditions offers opportunities for studying molecular dynamics, compositional changes, and chemical interactions within molten substances. This introduced direct immersion probing technique has implications, benefiting both scientific and industrial fields. It holds promise for advancing research and exploration in various contexts, from fundamental scientific inquiries to practical applications in metallurgical processes, where flux materials are critical for optimizing production quality and efficiency. Furthermore, this approach enhances the capabilities of high-temperature Raman spectroscopy, making it a valuable tool for investigating molten materials and their properties in diverse settings.

Argon↗

Slow Wake Recovery and Low Turbulence Behind Wind Farms Parameterized in Mesoscale Simulations

Numerical weather prediction (NWP) and climate models equipped with wind-farm parameterizations (WFPs) can simulate cluster wake effects affecting downstream wind farms in both onshore and offshore environments. This study evaluates wake recovery behind a wind farm represented by the NWP-WFP approach in the Weather Research and Forecasting (WRF) model using either the Fitch et al. (2012) or Ma et al. (2022a, b) WFPs. Results are benchmarked against large-eddy simulations (LES) of an idealized offshore wind farm with aligned and staggered layouts under neutral atmospheric stability. Near-farm wake recovery is underestimated in NWP-WFP simulations due to its representation on a coarse mesoscale grid. This limitation leads to slow wake recovery through two interconnected mechanisms: (i) spatial gradients in the wind velocity field are weaker compared to LES and (ii) turbulence kinetic energy (TKE) remains low not because of excessive dissipation but due to insufficient shear production caused by these weakened gradients. For the scenario considered here, a wind-speed bias develops in the near-farm wake and persists into the far wake. Differences between the NWP-WFP simulations and LES emerge within a short distance downstream of the farm exit, where the mesoscale simulations recover too slowly. This reduced recovery contributes approximately 0.15-0.50 m s-1 to the near-farm wind-speed bias. The bias established in this region is not subsequently compensated for downstream but instead propagates into the far wake, where wind-speed differences of approximately 0.4-0.6 m s-1 remain up to 50 km downstream. Higher-resolution mesoscale simulations partially reduce this bias. Increasing turbine-added TKE or including subgrid wake effects provides additional improvement, but neither fully addresses the underlying cause. The slow wake recovery is not caused by limitations of the WFPs themselves, as it also occurs outside their region of influence, and adding subgrid wake effects does not significantly impact recovery. Rather, the slow wake recovery is a consequence of mesoscale flow representation. This behavior is not limited to regions downstream of the wind farm but is less visible within the farm, where wake recovery occurs simultaneously with turbine-induced momentum extraction. These results highlight the need for improved representations of wake recovery both within and downstream of wind farms. While enhanced subgrid modeling, shear-driven TKE production, and refined WFP formulations may improve intra-farm dynamics, accurately capturing near-farm wake recovery downstream remains challenging, as WFPs do not act in this region.

17 WIND ENERGY↗

Vortex guidance and transport in channeled pinning arrays

Here, we numerically examine vortices interacting with pinning arrays where a portion of the pinning sites have been removed in order to create coexisting regions of strong and weak pinning. The region without pinning sites acts as an easy-flow channel. For driving in different directions with respect to the channel, we observe distinct types of vortex flow. When the drive is parallel to the channel, the flow first occurs in the pin free region followed by a secondary depinning transition in the pinned region. At high vortex densities there is also an intermediate plastic flow phase due to the coupling between the weak and strong pinning regions. For driving applied perpendicular to the channel, we observe a jammed phase in which vortices accumulate on the boundary of the pinned region due to the vortex-vortex repulsion, while at higher drives the vortices begin to flow through the pinning array. For driving at an angle to the channel, depending on the filling we observe a drive-induced reentrant pinning effect as well as negative differential mobility which occurs when vortices move from the unpinned to the pinned portion of the sample.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Coupled Aerodynamic and Hydrodynamic Hybrid Simulation of Floating Offshore Wind Turbines

The development and innovation of floating offshore wind energy in the U.S. requires detailed high-fidelity observations and measurements of turbine and platform loading due to wind, waves, and currents. However, full-scale and quasi-full-scale experiments require significant financial and temporal investments for construction, experimental testing, and long-term field campaigns. To support the commercial advancement of the offshore wind energy industry, specialized wind tunnel and wave basin experimental facilities are critical to be able to test FOWT designs at small scale under controlled conditions prior to full-scale deployment. Oregon State University (OSU) is internationally known as a leader in water and energy research, development, and testing. The O.H. Hinsdale Wave Research Laboratory (HWRL) and the Wallace Energy Systems and Renewables Facility (WESRF) at OSU have extensive experience building, modeling, monitoring, controlling, and actuating scaled systems. Experiments on wave-structure interaction have been performed at the HWRL since its establishment in 1972. Studies have included the interaction of waves with coastal structures (breakwaters, seawalls, buildings, cylinders, bridges, fixed foundations of offshore wind turbines, etc.) and with floating structures (e.g., wave energy converters, maneuvering of vessels, etc.). Hinsdale is actively used by marine energy technology developers, both for private testing and OSU-collaborative research projects. However, despite the availability of several large-scale facilities for hydrodynamic testing (at OSU and elsewhere in the U.S.), existing experimental laboratories are generally limited in their ability to accurately generate combined wind and wave conditions. The simulation of both wind and waves in experimental testing is complicated due to a number of constraints, including: [i] incompatible similitude laws governing the wind and waves for scaled experiments, [ii] producing accurate wind over a large enough control volume via fans, and [iii] generating wind that reasonably represents the atmospheric boundary layer in existing wave basins/flumes. Hence, physical test data providing insight into the simultaneous wave- and wind-structure response of floating offshore wind components can be difficult to generate. Given the aforementioned challenges in classic hydrodynamic experiments, the motivation of this project is to establish a real-time hybrid simulation (RTHS) approach that can apply aero- and hydro-dynamic loading by augmenting wave-only experimental facilities with virtual aerodynamic forces through numerical models representing the remaining dynamic forces. RTHS is a physical-numerical approach that partitions a prototype system into physical and numerical sub-assemblies that interact with each other through actuators and sensors in real time. In coupling physical and numerical models, the hybrid simulation approach applied herein is ideal for problems with: (1) structures subjected to different scaling laws, such as floating offshore wind turbines subjected to combined aero/hydro-dynamic loading, (2) structures that are too large or complex to be tested entirely in a laboratory setting, such as deep-water mooring applications, and (3) component testing, where the behavior of a portion of the assembly is uncertain but still interacts with other portions of the structure, such as testing the fatigue life of turbine blades. Few U.S. experimental facilities are able to test simultaneous aero- and hydro-dynamic loading and none can accurately produce aero/hydro-dynamic response on scaled FOWT models due to conflicting similitude laws between the wind (commonly Reynolds) and the waves (commonly Froude). To aid in accelerating the development of the U.S. floating offshore industry, there is a significant need to develop a flexible, modular framework that can expand the capacities of existing wave-only laboratories. The project goal is to demonstrate a hydrodynamic real-time hybrid simulation (hydro-RTHS) framework that couples numerical wind and physical waves acting on a FOWT, thus representing simultaneous aero/hydro-dynamic loading. The FOWT is partitioned into a full-scale numerical sub-assembly associated with the aerodynamics and a model-scale physical sub-assembly associated with the hydrodynamics. The numerical-physical partition associated with hydro-RTHS mitigates scaling constraints by supplying different scaling laws to the physical and numerical sub-assemblies. Herein, length, force, and time are scaled and exchanged between the sub-assemblies using Froude scaling to represent the open-channel flow in the physical sub-assembly. Other similitude laws could also be utilized depending on the problem definition. It is envisioned that the ability to model FOWTs under waves and wind, with mitigation of similitude distortions, would result in reduced development costs (currently, FOWT concept development is performed with full-size pro- totypes at enormous expense and risk) and increase the reliability of the FOWT industry (since extreme wave and wind conditions and contingency events can be tested safely in a controlled environment).

16 TIDAL AND WAVE POWER↗

A comparative study on cubic and tetragonal Ce-ZrO 2 supported Rh catalysts for N 2 O decomposition

Zirconium oxide (ZrO 2 ) exhibits strong synergy with cerium oxide (CeO 2 ), acting as a structural and electronic promoter during catalytic redox reactions. As a result, Ce-ZrO 2 composite oxides are widely used as supports in various catalytic systems. In our previous work, we demonstrated that the incorporation of Zr 4+ into the CeO 2 lattice significantly enhanced Rh dispersion, improved redox ability, and stabilized surface Rh species, which collectively boosted the de-N 2 O activity of Rh/Ce-ZrO 2 catalysts. Building on these findings, the present study emphasizes that the crystallographic phase of Ce-ZrO 2 , governed by the Ce/Zr ratio, plays a decisive role in tuning the physicochemical environment of Rh active sites and thereby optimizing catalytic performance. In conclusion, tailoring the Ce/Zr ratio to favor the cubic fluorite structure emerges as a promising strategy for the rational design of highly active and stable catalysts for N 2 O decomposition and potentially other redox-sensitive environmental applications.

36 MATERIALS SCIENCE↗