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At least 721 records · Page 40

Identification of Second Shell Coordination in Transition Metal Species Using Theoretical XANES: Example of Ti–O–(C, Si, Ge) Complexes

X-ray absorption near-edge structure (XANES) is a common technique for elucidating oxidation state and first shell coordination geometry in transition metal complexes, among many other materials. However, the structural information obtained from XANES is often limited to the first coordination sphere. In this study, we show how XANES can be used to differentiate between C, Si, and Ge in the second coordination shell of Ti–O–(C, Si, Ge) molecular complexes based on differences in their Ti K-edge XANES spectra. Experimental spectra were compared with theoretical spectra calculated using density functional theory structural optimization and ab initio XANES calculations. The unique features for second shell C, Si, and Ge present in the Ti K pre-edge XANES are attributed to the interaction between the Ti center and the O–X (X = C, Si, or Ge) antibonding orbitals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Substituent and Heteroatom Effects on π–π Interactions: Evidence That Parallel-Displaced π-Stacking is Not Driven by Quadrupolar Electrostatics

Stacking interactions are a recurring motif in supramolecular chemistry and biochemistry, where a persistent theme is a preference for parallel-displaced aromatic rings rather than face-to-face π-stacking. This is usually explained in terms of quadrupole–quadrupole interactions between the arene moieties but that interpretation is inconsistent with accurate calculations, which reveal that the quadrupolar picture is qualitatively wrong. At typical π-stacking distances, quadrupolar electrostatics may differ in sign from an exact calculation based on charge densities of the interacting arenes. We apply symmetry-adapted perturbation theory to dimers composed of substituted benzene and various aromatic heterocycles, which display a wide range of electrostatic interactions, and we investigate the interplay of Pauli repulsion, dispersion, and electrostatics as it pertains to parallel-displaced π-stacking. Profiles of energy components along cofacial slip-stacking coordinates support a prominent role for the “van der Waals model” (dispersion in competition with Pauli repulsion), even for polar monomers where electrostatic interactions are significant. While electrostatic interactions are necessary to explain the optimal face-to-face π-stacking distance and to account for the relative orientation of one polar arene with respect to another, we find no evidence to support continued invocation of quadrupolar electrostatics as a basis for π-stacking. Our results suggest that a driving force for offset-stacking exists even in the absence of electrostatic interactions. Consequently, tuning electrostatics via functionalization does not guarantee that slip-stacking can be avoided. This has implications for rational design of soft materials and other supramolecular architectures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interrogation of bimetallic particle oxidation in three dimensions at the nanoscale

An understanding of bimetallic alloy oxidation is key to the design of hollow-structured binary oxides and the optimization of their catalytic performance. However, one roadblock encountered in studying these binary oxide systems is the difficulty in describing the heterogeneities that occur in both structure and chemistry as a function of reaction coordinate. This is due to the complexity of the three-dimensional mosaic patterns that occur in these heterogeneous binary systems. By combining real-time imaging and chemical-sensitive electron tomography, we show that it is possible to characterize these systems with simultaneous nanoscale and chemical detail. We find that there is oxidation-induced chemical segregation occurring on both external and internal surfaces. Additionally, there is another layer of complexity that occurs during the oxidation, namely that the morphology of the initial oxide surface can change the oxidation modality. As a result, this work characterizes the pathways that can control the morphology in binary oxide materials.

36 MATERIALS SCIENCE↗

Tuning the thermal activation atmosphere breaks the activity–stability trade-off of Fe–N–C oxygen reduction fuel cell catalysts

Fe–N–C catalysts are the most promising platinum group metal-free oxygen-reduction catalysts, but they suffer from a low density of active metal sites and the so-called activity–stability trade-off. Here we report an Fe–N–C catalyst prepared by adding an optimal amount of H 2 to the traditional inert atmosphere during the thermal activation. The presence of H 2 significantly increases the total density of FeN 4 sites, suppressing the unstable pyrrolic-N-coordinated S1 sites and favouring the stable pyridinic-N-coordinated S2 sites with shortened Fe–N bond lengths. Here, we propose that the intrinsically stable S2 sites are probably arranged in well-graphitized carbon layers, and the S1 sites exist in less-graphitized carbon. H 2 could remove unstable S1 sites and retain stable S2 sites during the pyrolysis to break the challenging activity–stability trade-off. The Fe–N–C catalyst in membrane electrode assemblies maintains a current density of 67 mA cm -2 at 0.8 V (H 2 –air) after 30,000 voltage cycles (0.60 to 0.95 V under H 2 –air), achieving encouraging durability and performance simultaneously.

25 ENERGY STORAGE↗

Fabrication, Assembly, and Metrology of the Neutron Imaging Pinhole

The neutron imaging pinhole is a complex aperture that is designed to have its image plane at the center of a laser fusion capsule implosion. The aperture’s high-Z materials of tungsten and gold block the neutrons so that only the neutrons passing through the machined apertures make it to the image plane and detector. The pinhole assembly consists of 11 layers of gold in between two layers of tungsten and gold. These 64 triangular pinholes and six penumbra apertures provide a matrix image that can be reconstructed to image complex deuterium-tritium neutron burn details in laser fusion capsules. The gold layers were diamond turned flat before the profiles were cut into their faces. Four of the layers were profiled with penumbral profile arrays that tapered from a radius of 250 to 150 µm. Three gold layers were just diamond turned to wedges to set the tilt of the whole aperture. Three gold layers were profiled on both sides with triangle groove arrays that consist of eight equilateral triangles with the depth of 200 to 15 µm over the 200-mm length, with a tolerance of 2 µm. Custom software programming routines were written using Labview to move the diamond-turning profiler through the required X-Y-Z movements to cut the penumbral and grooved profiles of the pinhole into the varying tilted arrays of features. The software is optimized to push the profile of the whole part into the face while eliminating any unneeded passes that do not cut any material. Each layer was thoroughly inspected on both sides using an optical coordinate measuring machine and white-light interferometer to validate each of the profiles. The pinhole assembly was inspected on a rotary stage so that both ends of the assembly can be inspected and presented in a single point cloud. The process of machining, programming, assembly, and inspection of the neutron imaging pinhole is covered.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Maximization of ICRF power by SOL density tailoring with local gas injection

We report that experiments have been performed under the coordination of the International Tokamak Physics Activity (ITPA) on several tokamaks, including ASDEX Upgrade (AUG), JET and DIII-D, to characterize the increased Ion cyclotron range of frequency (ICRF) antenna loading achieved by optimizing the position of gas injection relative to the RF antennas. On DIII-D, AUG and JET (with the ITER-Like Wall) a 50% increase in the antenna loading was observed when injecting deuterium in ELMy H-mode plasmas using mid-plane inlets close to the powered antennas instead of divertor injection and, with smaller improvement when using gas inlets located at the top of the machine. The gas injection rate required for such improvements (similar to 0.7 x 10(22) el s(-1) in AUG, similar to 1.0 x 10(22) el s(-1) in JET) is compatible with the use of this technique to optimize ICRF heating during the development of plasma scenarios and no degradation of confinement was observed when using the mid-plane or top inlets compared with divertor valves. An increase in the scrape-off layer (SOL) density was measured when switching gas injection from divertor to outer mid-plane or top. On JET and DIII-D, the measured SOL density increase when using main chamber puffing is consistent with the antenna coupling resistance increase provided that the distance between the measurement lines of sight and the injection location is taken into account. Optimized gas injection was also found to be beneficial for reducing tungsten (W) sputtering at the AUG antenna limiters, and also to reduce slightly the W and nickel (Ni) content in JET plasmas. Modeling the specific effects of divertor/top/mid-plane injection on the outer mid-plane density was carried out using both the EDGE2D-EIRENE and EMC3-EIRENE plasma boundary code packages; simulations indeed indicate that outer mid-plane gas injection maximizes the density in the mid-plane close to the injection point with qualitative agreement with the AUG SOL density measurements for EMC3-EIRENE. Field line tracing for ITER in the 15 MA Q(DT) = 10 reference scenario indicates that the planned gas injection system could be used to tailor the density in front the antennas. Lastly, benchmarking of EMC3-EIRENE against AUG and JET data is planned as a first step towards the ITER SOL modelling required to quantify the effect of gas injection on the SOL density in front of the antennas.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

MASK3 for Advanced WEC Dynamics and Controls

This report outlines the "MASK3" wave tank test within the Advanced WEC Dynamics and Controls (AWDC) project. This test represents the final test in the AWDC project. The focus of the MASK3 test was to consider coordinated 3-degree-of-freedom (3DOF) control of a WEC in a realistic ocean environment. A key aspect of this test was the inclusion of a "self-tuning" mechanism which uses an optimization algorithm to update controller gains based on a changing sea state. The successful implementation of the self-tuning mechanism is the last crucial step required for such a controller to be implemented in real ocean environments.

16 TIDAL AND WAVE POWER↗

STOCHASTIC OPTIMAL POWER FLOW FOR REAL-TIME MANAGEMENT OF DISTRIBUTED RENEWABLE GENERATION AND DEMAND RESPONSE (Final Report)

To meet the grand challenge of a sustainable energy future, there has been a surge of interest in renewable energy. Today, the uncertainty associated with renewable resources is handled by using operating reserves. The high penetration of renewable resources, however, introduces difficult-to-control dynamics and challenges for power system operation. Decision support tools are necessary at the bulk system operational level to recognize and efficiently utilize renewable resources and distributed demand response products in concert with traditional grid resources. It is envisaged that responsive load can potentially have very significant cost advantages over either spinning or non-spinning ramping reserve. Critical decisions are made during hour(s)-ahead and real-time power system operation regarding the commitment and dispatch of generators to ensure power delivery is both reliable and economic. These decisions are typically made by a security constrained optimal flow, which determines future generator commitments, dispatches, and ensures adequate reserves are available in the event of a contingency (unexpected outage) or if future system conditions deviate from forecasts. However, security has been always based on a pre-specified subset of contingency constraints whose enforcement does not guarantee security under all possible future possibilities while also giving little or no weight to the likelihood of each contingent event or the severity of its consequences. Existing tools, which are based exclusively on deterministic optimization models, do not yield optimal operational decisions to address these new challenges, in terms of both reliability and cost-effectiveness. This project has focused on developing a stochastic optimal power flow (SOPF) framework, which integrates renewable resource uncertainty, load uncertainty, distributed storage (DS), demand response (DR) products, in a holistic manner to address the uncertainty associated with ever-increasing renewable resources, along with the inclusion of distributed demand response products in future power systems. A proof-of-concept problem was created using the Pennsylvania-Jersey-Maryland (PJM) power system network. Synthetic wind generation was added to the system to simulate 50% wind penetration. A 1-hour test of SOPF operation indicated more than 6% operational cost savings. The project continued by adding the Midwestern Independent System Operator (MISO) as a partner, with focus shifting from SOPF to Stochastic Look-Ahead Unit Commitment (SLAC). Unlike PJM, MISO is faced with significant renewable energy resources within its footprint and is challenged with substantial uncertainty in its operations. The SLAC distinguishes itself from existing tools that operators use. At best, today’s tools solve two to three cases independently, where one or two system parameters, such as forecasted load level (e.g., a low, base, and high forecast), are varied and the resulting scenarios are analyzed independently. The stochastic-based optimization of SLAC leverages statistical information from an ensemble of potential operational scenarios and their respective likelihood. The SLAC output can be translated into valuable information to the operator such as suggested commitments, optimal scheduling and dispatch of resources, reserve requirements at both locational and zonal resolutions, ramping availability and requirements, availability of demand response including operational guidance concerning the near-term and real-time coordination between distributed energy resources, and utilization of distributed storage resources. The developed SOPF/SLAC tool, a stand-alone tool compatible with existing EMSs, will provide system operators with unprecedented visibility, flexibility and predictability to these resources and operational guidance concerning the real-time coordination between DERs and DR/DS products. The game changing and practical impact of this disruptive technology will be dramatic and will usher in a new era in the electric power industry, wherein green energy concepts are fully embraced, and electric power costs are lowered throughout the nation.

42 ENGINEERING↗

Hierarchical Management of Distributed Energy Resources Using Chance-Constrained OPF and Extremum Seeking Control

Distributed energy resources (DERs) are becoming an important part of distribution systems, because of their economic and environmental benefits. Although their inherent intermittency and volatility introduce uncertainties into the electric power system, they have the potential to provide controllability to the system under proper coordination. In this paper, we propose a hierarchical control algorithm for distribution systems with DERs so that they have controllability similar to a generator bus. The upper level scheduler solves a chance-constrained optimal power flow (OPF) problem to plan the operation of the DERs based on forecasts, and the lower level distributed DER controllers leverage the extremum seeking approach to deliver the planned power at the feeder head. The proposed algorithm is tested on a modified IEEE 13-node feeder, demonstrating its effectiveness.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Coordination Sphere of Lanthanide Aqua Ions Resolved with Ab Initio Molecular Dynamics and X-ray Absorption Spectroscopy

To resolve the fleeting structures of lanthanide Ln 3+ aqua ions in solution, we (i) performed the first ab initio molecular dynamics (AIMD) simulations of the entire series of Ln 3+ aqua ions in explicit water solvent using pseudopotentials and basis sets recently optimized for lanthanides and (ii) measured the symmetry of the hydrating waters about Ln 3+ ions (Nd 3+ , Dy 3+ , Er 3+ , Lu 3+ ) for the first time with extended X-ray absorption fine structure (EXAFS). EXAFS spectra were measured experimentally and generated from AIMD trajectories to directly compare simulation, which concurrently considers the electronic structure and the atomic dynamics in solution, with experiment. In this study, we performed a comprehensive evaluation of EXAFS multiple-scattering analysis (up to 6.5 Å) to measure Ln–O distances and angular correlations (i.e., symmetry) and elucidate the molecular geometry of the first hydration shell. This evaluation, in combination with symmetry-dependent L 3 - and L 1 -edge spectral analysis, shows that the AIMD simulations remarkably reproduces the experimental EXAFS data. The error in the predicted Ln–O distances is less than 0.07 Å for the later lanthanides, while we observed excellent agreement with predicted distances within experimental uncertainty for the early lanthanides. Our analysis revealed a dynamic, symmetrically disordered first coordination shell, which does not conform to a single molecular geometry for most lanthanides. This work sheds critical light on the highly elusive coordination geometry of the Ln 3+ aqua ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Challenges of Modeling Distributed Energy Resources (DERs) as Blackstart Resources and for Volt-VAR Optimality

Modeling, testing and instituting Distributed Energy Resources (DERs) as Blackstart Resoucrces presents several challenges due to the fundamental differences between traditional black start resources (e.g., large generators) versus DERs like solar PV systems with battery storage. This paper addresses some of these key challenges. These include intermittency of coordinating DERs to provide continuous power during a black start event, especially during extended periods of cloud cover or when battery energy storage is depleted. This paper additionally addresses the collapsing voltage and stability control challenges specific to maintaining bulk power system stability during black start synchronization These physical and engineering limitations require careful engineering design, modeling and engineering to ensure that DERs can support critical loads and substations during black start events. A variety of additional challenges also exist. Additionally, there are challenges associated with feeder location and low voltage secondary system impacts on DER functions and settings. We compare typical functions and settings for DERs for power factor control and correction. We also demonstrate how voltag control via Volta-VAR power factor correction can be done

Mukherjee, Srijib↗

Maturation of biomass‐to‐biofuels conversion technology pathways for rapid expansion of biofuels production: a system dynamics perspective

Abstract The Biomass Scenario Model ( BSM ) is a system‐dynamics simulation model intended to explore the potential for rapid expansion of the biofuels industry. The model is not predictive — it uses scenario assumptions based on various types of data to simulate industry development, emphasizing how incentives and technological learning‐by‐doing might accelerate industry growth. The BSM simulates major sectors of the biofuels industry, including feedstock production and logistics, conversion, distribution, and end uses, as well as interactions among sectors. The model represents conversion of biomass to biofuels as a set of technology pathways, each of which has allowable feedstocks, capital and operating costs, allowable products, and other defined characteristics. This study and the BSM address bioenergy modeling analytic needs that were identified in recent literature reviews. Simulations indicate that investments are most effective at expanding biofuels production through learning‐by‐doing when they are coordinated with respect to timing, pathway, and target sector within the biofuels industry. Effectiveness metrics include timing and magnitude of increased production, incentive cost and cost effectiveness, and avoidance of windfall profits. Investment costs and optimal investment targets have inherent risks and uncertainties, such as the relative value of investment in more‐mature versus less mature pathways. These can be explored through scenarios, but cannot be precisely predicted. Dynamic competition, including competition for cellulosic feedstocks and ethanol market shares, intensifies during times of rapid growth. Ethanol production increases rapidly, even up to Renewable Fuel Standards‐targeted volumes of biofuel, in simulations that allow higher blending proportions of ethanol in gasoline‐fueled vehicles. Published 2014. This article is a U.S. Government work and is in the public domain in the USA. Biofuels, Bioproducts, Biorefining published by John Wiley & Sons, Ltd on behalf of Society of Chemical Industry.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Advanced WEC Dynamics and Controls MASK3 Test

Sandia National Laboratories and the Department of Energy (DOE) have completed on a multi-year program to examine the effects of control theory on increasing power produced by resonant wave energy conversion (WEC) devices. The tank tests have been conducted at the Naval Surface Warfare Center Carderock Division (NSWCCD) Maneuvering and Sea Keeping Basin (MASK) in West Bethesda, MD. This report outlines the "MASK 3 " wave tank test within the Advanced WEC Dynamics and Controls (AWDC) project. This test represents the final test in the AWDC project. The focus of the MASK 3 test was to consider coordinated 3 -degree-of-freedom ( 3 DOF) control of a WEC in a realistic ocean environment. A key aspect of this test was the inclusion of a "self-tunine mechanism which uses an optimization algorithm to update controller gains based on a changing sea state. The successful implementation of the self-tuning mechanism is the last crucial step required for such a controller to be implemented in real ocean environments.

16 TIDAL AND WAVE POWER↗

Control system for multi-system coordination via a single reference governor

This report describes the improvements to the Feasible Actuator Range Modifier (FARM) component of the RAVEN-based HYBRID framework for analysis of Integrated Energy Systems (IES). FARM supports the HERON plug-in that solves the power dispatch problem. The solution involves economically optimal dispatches that satisfy the limits on production variables and corresponding rates of variation (explicit constraints) as well as the limits on the process variables tied to the service life of equipment (implicit constraints). The problem can be addressed as a two-stage process, i.e., HERON power dispatcher estimates a solution that meets explicit constraints (low-resolution physics), whereas FARM uses the simulation outcomes of HYBRID high-fidelity model to capture the system dynamic response and enforce implicit constraints (high-resolution physics). The initial version of the code (FARM-Alpha) was released by Argonne National Laboratory in January 2021 followed by FARM-Beta (January 2022) and FARM-Gamma (April 2022).

42 ENGINEERING↗

Review of In Situ Sensing for Directed Energy Deposition for Industrial Part Quality Assessment

As the use additive manufacturing (AM) processes continues to grow in critical industries, improved quality assurance methods are becoming increasingly sought after for qualification and certification of AM components. Traditional nondestructive evaluation of printed components is often unable to supply the required confidence in print quality to justify qualification and certification, but the layer-by-layer nature of AM provides unprecedented opportunities for in situ quality inspection. This document summarizes recent developments in process monitoring research specifically related to Directed Energy Deposition (DED). Particular attention is given to three aspects of the highlighted manuscripts: (1) the type of sensors used, (2) features extracted from each sensor modality, and (3) analysis of extracted features for AM quality assessment. Based on the review of the state-of-the-art, several observations have been made. First, none of the reviewed works have applied their trained models to real part geometries, with many of the works relying on single track experiments, thin-walled structures, and cubes. Similarly, there have not been any works demonstrating model generalizability, i.e., a model trained on data from one build allows for fruitful analysis of data from another build. Many works used machine learning techniques to distinguish different process regimes (i.e., normal, keyholing, lack-of-fusion), but very few papers have investigated stochastic variation in an already “optimized” process. Sensor fusion approaches are also limited in the DED sensing literature, but the few works that have employed such techniques have demonstrated the benefits. Finally, registration of in situ data to the build coordinate system is of paramount importance to producing industrially relevant in situ monitoring systems. Data registration allows direct correlations between process anomalies detected in the process monitoring data to localized departures in part quality, but such techniques are generally lacking in the current literature.

36 MATERIALS SCIENCE↗

Challenges Conducting a Radiological Site Assessment at a Remote Uranium Mine - 16259

A radiological site assessment was performed as part of an environmental site assessment at a former uranium mine located in the Northwest Territories of Canada. The only access to the site was by helicopter, so the field program was a limited to only a few days. Radiological surveys were conducted to assess conditions for safety of the field crew as well as to provide overland survey of uranium at the site. Limited radiological data existed for this site and the objective was to collect as much data as possible during the short field program. ScanPlot{sup SM} gamma spectroscopy land survey system was utilized for the overland survey utilizing a backpack system. ScanPlotSM platform utilized spectroscopy grade sodium iodide detectors configured for optimal spatial coverage and radiation detection. Survey locations were recorded using an on-board global positioning system (GPS). The radiological spectral data from the radiation detectors is automatically logged and linked with the GPS coordinates to an on-board computer to create iso-contour figures using a color scale to represent radioactivity levels (ground concentration by radionuclide). The advantage of utilizing the ScanPlotSM system for this assessment is that the nature and extent of uranium is provided without having to collect and assay a large number of samples during a short period of time. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Does practice make perfect? Lessons learned from full-scale power system incident response exercise

While threats to the energy sector occur daily, few utilities get the opportunity to fully test out their detection and response mechanisms to advanced threats in the real world. With the high demand for reliability, few grid operators would allow execution of simulated cyber-attacks on their live systems. The DOE-funded Liberty Eclipse project offers a unique opportunity for small and large utilities and coops to practice their combined IT/OT responses to a live red team executing attacks against an isolated power system on an island in New York. Both cyber teams and power operations teams must work together to detect and respond to attacks, even restoring the power system against extreme impacts. Lessons learned from these exercises reveal key takeaways for understanding what a real attack against the electric sector will look like, gaps in execution of the best-laid plans when the pressure of a real event is bearing down, and how organizations can better prepare for advanced attacks by optimizing participation in exercises. This presentation will discuss successes and opportunities for improvement both in how utilities can prepare for and respond to events, as well as how full-scale IT/OT exercises can be coordinated.

24 POWER TRANSMISSION AND DISTRIBUTION↗

SU-F-T-336: A Quick Auto-Planning (QAP) Method for Patient Intensity Modulated Radiotherapy (IMRT)

Purpose: The aim of this study is to develop a quick auto-planning system that permits fast patient IMRT planning with conformal dose to the target without manual field alignment and time-consuming dose distribution optimization. Methods: The planning target volume (PTV) of the source and the target patient were projected to the iso-center plane in certain beameye- view directions to derive the 2D projected shapes. Assuming the target interior was isotropic for each beam direction boundary analysis under polar coordinate was performed to map the source shape boundary to the target shape boundary to derive the source-to-target shape mapping function. The derived shape mapping function was used to morph the source beam aperture to the target beam aperture over all segments in each beam direction. The target beam weights were re-calculated to deliver the same dose to the reference point (iso-center) as the source beam did in the source plan. The approach was tested on two rectum patients (one source patient and one target patient). Results: The IMRT planning time by QAP was 5 seconds on a laptop computer. The dose volume histograms and the dose distribution showed the target patient had the similar PTV dose coverage and OAR dose sparing with the source patient. Conclusion: The QAP system can instantly and automatically finish the IMRT planning without dose optimization.

60 APPLIED LIFE SCIENCES↗