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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

D and D Research on KM-IT Platform - 20494

The Knowledge Management Information Tool (KM-IT) is a web-based system developed to maintain and preserve the Department of Energy's (DoE's) knowledge base. The system was developed by Florida International University's Applied Research Center (FIU-ARC) with the support of the D and D community including the DOE Office of Environmental Management, and with the collaboration and support of the DoE's Energy Facility Contractors Group (EFCOG) and the former ALARA Centers at Hanford and Savannah. The KM-IT system is a community driven system tailored to serve the technical issues faced by the workforce across the DOE Complex. This KM-IT web-based interactive system is operational and available for use at www.dndkm.org and is currently comprised of the following modules: Web Crawler, Hotline, Technology, Hanford's ALARA Center Reports, Specialist Directory, Lessons Learned, Best Practices, Video/Picture Library, Vendors and Industry News. The Web Crawler dynamically searches through the KM-IT repository as well as the web and displays search results based on the search criteria. The Hotline allows registered users to post questions/problems related to D and D and to receive solutions from a subject-matter specialist. The Technology module serves as repository of D and D technologies and contains technology/ demonstration fact sheets and vendor information. D and D community members can add Lessons Learned, Best Practices, and Pictures/Videos to the D and D repository, after a formal approval process. The Vendor module provides a directory of commercial vendors who provide D and D related technologies, supplies, and services. KM-IT makes an excellent use of the knowledge that exists within the D and D community by allowing D and D project managers around the DOE complex to collaborate by sharing innovative ideas, past experiences, and practices and by maintaining a directory of subject matter specialists. FIU has developed the dedicated module on KM-IT platform to publish D and D research being performed at FIU. This module highlights current EM research efforts and activities in support of D and D being performed at FIU/SRNL associated with fixatives and intumescent products. FIU will expand this module to include the recent and current D and D research being performed across multiple DOE EM sites, national labs and universities. FIU will collaborate with SRNL, INL, ANL and other universities to explore and publish D and D research activities on KM-IT. As a result, the user community will have a centralized location to review new D and D related research across the DOE EM complex. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Ligand-Exchange-Induced Amorphization of Pd Nanomaterials for Highly Efficient Electrocatalytic Hydrogen Evolution Reaction

Various kinds of amorphous materials, such as transition metal dichalcogenides, metal oxides, and metal phosphates, have demonstrated superior electrocatalytic performance compared with their crystalline counterparts. Compared to other materials for electrocatalysis, noble metals exhibit intrinsically high activity and excellent durability. However, it is still very challenging to prepare amorphous noble-metal nanomaterials due to the strong interatomic metallic bonding. Herein, the discovery of a unique thiol molecule is reported, namely bismuthiol I, which can induce the transformation of Pd nanomaterials from face-centered-cubic (fcc) phase into amorphous phase without destroying their integrity. This ligand-induced amorphization is realized by post-synthetic ligand exchange under ambient conditions, and is applicable to fcc Pd nanomaterials with different capping ligands. Importantly, the obtained amorphous Pd nanoparticles exhibit remarkably enhanced activity and excellent stability toward electrocatalytic hydrogen evolution in acidic solution. This work provides a facile and effective method for preparing amorphous Pd nanomaterials, and demonstrates their promising electrocatalytic application.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Mechanistic Investigation of Co(II) Extraction by TODGA to Aid Nuclear Forensic Separations

Nuclear forensic (NF) analysis supports law enforcement inquiries by analyzing evidence tainted with radioactive substances. Separation techniques can be used to identify and quantify actinides and fission 15 products in post-detonation (PD) debris. Environmental transition metals, also present in PD residues, have been observed to impact critical isotope extractions. For example, radio stable cobalt (Co), ubiquitous in urban environments, particularly in corrosion-resistant alloys, paint-drying agents, dyes, and pigments, can impact the separation of important actinides and fission products. The presented work aims to elucidate the chemistry Q2 governing Co extraction in samples pertinent to PDNF. Chemistry between Co and N,N,N,‘N’-tetraoctyl diglyco- 20 lamide (TODGA), the ligand present in the commercial chromatographic resin diglycolamide (DGA), were studied via solvent and chromatographic extraction and spectroscopic analyses. These results indicate that a tetrahedral Co(II) species is extracted by TODGA from highly acidic (>5M HCl) solutions via a spontaneous entropy-driven reaction. Furthermore, extraction trends in varied acid concentrations are consistent between solvent extraction and chromatographic extraction methods.

activation product↗
DOE OSTI2023

Cyber-Physical Power Systems Protection: The Byzantine Cybersecurity Framework

Cybersecurity of smart grids have been topic of much interest in recent years. As this critical infrastructure operation increases dependency on automated processes and controls, exposure to cyber-physical threats become inevitable. Considering cyber-physical security of the grid, much focus of attention has been made towards smart grids real-time monitoring solutions, including the state estimation process. Analyzing the relevant literature, one can note though that seldom research has been done on cyber-physical security of smart grids protection systems. Protection systems have intangible value towards grid reliability. This paper presents a cybersecurity framework for smart grids protection systems. A physics-based inspired machine learning solution is at the core process of the framework. Processed relay inputs and outputs are used by a deep predictive coding network. Formal models, a quasi-static state estimator, provides an oracle when low confidence decision is reached. Evolving knowledge is derived through reinforcement learning. Implementation aspects considering the Pacific Northwest National Laboratory Electricity Infrastructure Operations Center are presented. Built as an extra control layer to protection systems, without hard-to-derive parameters, highlights potential aspects towards real-life applications.

Bretas, Arturo Suman↗
DOE OSTI2022

Recommendations for Secure Transport: Material Conveyance Physical Protection Technology

Nuclear material is at higher risk of theft and sabotage during transport than during any other phase of the nuclear fuel lifecycle. Nuclear materials are transported in the public domain where adversaries have an upper hand by taking advantage of the time and location of the theft or sabotage attempt. As such, even modest threat profiles for transport of nuclear and radioactive material can require substantial detection and delay measures to support timely response. Conveyance tracking augmented with technology that improves on-the-scene situational awareness at a remote monitoring center has been adopted as a de-facto standard approach for transportation security. At present, the extended tracking and situational awareness capabilities needed for a nuclear material shipment, as is provided by the purpose designed, Transportation – Security, Tracking and Reporting (T-STAR) System, do not exist in a single commercial off-the-shelf (COTS) solution. Typically, the COTS systems that excel in one area are deficient in other areas, presenting challenges to designing well-rounded, robust systems. Still, COTS solutions can offer the basic set of tracking and situational awareness capabilities by indicating last update time, current location, and route taken. By incorporating vehicle and driver performance measures via the vehicle’s controller area network (CAN bus) and video alongside other data streams allows telemetry and other shipment information to be assessed in novel ways.This paper describes the operation, capabilities and features of various conveyance protection systems and approaches, assesses emerging technologies and how they could be used through a unified interface, and enumerates additional ways to provide early detection using vehicle, onboard technologies, effective delay technologies and approaches and simple equipment to improve protection during transport.

Shannon, Michael↗
DOE OSTI2020

Artificial Iron Proteins: Modeling the Active Sites in Non-Heme Dioxygenases

An important class of non-heme dioxygenases contains a conserved Fe binding site that consists of a 2-His-1-carboxylate facial triad. Results from structural biology show that, in the resting state, these proteins are six-coordinate with aqua ligands occupying the remaining three coordination sites. Here, we have utilized biotin–streptavidin (Sav) technology to design new artificial Fe proteins (ArMs) that have many of the same structural features found within active sites of these non-heme dioxygenases. An Sav variant was isolated that contains the S 112 E mutation, which installed a carboxylate side chain in the appropriate position to bind to a synthetic Fe II complex confined within Sav. Structural studies using X-ray diffraction (XRD) methods revealed a facial triad binding site that is composed of two N donors from the biotinylated ligand and the monodentate coordination of the carboxylate from S 112 E. Two aqua ligands complete the primary coordination sphere of the Fe II center with both involved in hydrogen bond networks within Sav. The corresponding Fe III protein was also prepared and structurally characterized to show a six-coordinate complex with two exogenous acetato ligands. The Fe III protein was further shown to bind an exogenous azido ligand through replacement of one acetato ligand. Spectroscopic studies of the ArMs in solution support the results found by XRD.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Performance-based earthquake early warning for tall buildings

The ShakeAlert Earthquake Early Warning (EEW) system aims to issue an advance warning to residents on the West Coast of the United States seconds before the ground shaking arrives, if the expected ground shaking exceeds a certain threshold. However, residents in tall buildings may experience much greater motion due to the dynamic response of the buildings. Therefore, there is an ongoing effort to extend ShakeAlert to include the contribution of building response to provide a more accurate estimation of the expected shaking intensity for tall buildings. Currently, the supposedly ideal solution of analyzing detailed finite element models of buildings under predicted ground-motion time histories is not theoretically or practically feasible. The authors have recently investigated existing simple methods to estimate peak floor acceleration (PFA) and determined these simple formulas are not practically suitable. Instead, this article explores another approach by extending the Pacific Earthquake Engineering Research Center (PEER) performance-based earthquake engineering (PBEE) to EEW, considering that every component involved in building response prediction is uncertain in the EEW scenario. Additionally, while this idea is not new and has been proposed by other researchers, it has two shortcomings: (1) the simple beam model used for response prediction is prone to modeling uncertainty, which has not been quantified, and (2) the ground motions used for probabilistic demand models are not suitable for EEW applications. In this article, we address these two issues by incorporating modeling errors into the parameters of the beam model and using a new set of ground motions, respectively. We demonstrate how this approach could practically work using data from a 52-story building in downtown Los Angeles. Using the criteria and thresholds employed by previous researchers, we show that if peak ground acceleration (PGA) is accurately estimated, this approach can predict the expected level of human comfort in tall buildings.

58 GEOSCIENCES↗
DOE OSTI2025

Advanced Fuels Campaign Time-at-Temperature Irradiation Campaign and Post-Irradiation Examination Plan

With increasing per capita energy consumption and rapidly growing energy consumption predicted for data centers, the US faces challenges in meeting projected energy demands. The current administration is attempting to accelerate the deployment of new nuclear construction by providing significant investments in advanced nuclear and by modernizing regulatory approaches for the licensing new reactors. However, enabling extended power uprates (EPUs) for the current nuclear reactor fleet would provide a shorter-term solution to better calibrate near-term energy generation capacity to the ever-growing energy demands of the modern era. One pathway to achieve power uprates is to increase the operational window by reassessing fuel safety limits around anticipated transients. Existing light-water reactors (LWRs) utilize a targeted operational window with well-defined operational efficiencies, yet this window is also often bound by conservative safety limits that result in suboptimal operational performance. For example, the operation of the existing fleet is highly constrained by safeguards to operation related to anticipated operational occurrences (AOOs), which are moderate-frequency transients expected with a frequency greater than 0.01 per reactor-year. These AOOs include temperature excursions where the critical heat flux for the system is exceeded, resulting in a departure from nucleate boiling (DNB) at the cladding surface. This DNB event is a thermohydraulic condition that, with current conservative fuel safety limits, results in the fuel rods being classified as “failed,” meaning that the cladding may not be returned to service.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Solution‐Processed Spin‐Polarized Light‐Emitting Diodes of Colloidal Quantum Wells and Magnetic Nanoparticles

Electrical injection of spin-polarized carriers into semiconductors enables circularly-polarized emission from spin-polarized light-emitting diodes (spin-LEDs). The incredible level of tunability of magnetic and electronic properties in colloidal nanocrystals offers unprecedented opportunities for the modulation of polarization of light in solution-processed spin-LEDs based on magnetic nanoparticles unlike epitaxially grown spin-LEDs restricted by a very limited range of materials for their exploitation, and solution-processed spin-LEDs based on chiral molecules, which do not allow the modulation of polarization in general. Here, it is shown that electrical injection of spin-polarized electrons from magnetic Fe 3 O 4 nanoparticles into CdSe/CdZnS core/shell colloidal quantum wells (CQWs) in solution-processed LEDs that allows for polarization modulation of electroluminescence. In this structure, a monolayer of face-down oriented CQWs is deposited as an active layer to avoid polarization losses due to the hopping of the electrons between the CQWs before the radiative recombination process. In this solution-processed spin-LED, the circular polarization reaches 4.5% at 3 K and survives up to 100 K. A net circular polarization is observed at zero magnetic field up to 100 K because of the remnant magnetization of the Fe 3 O 4 nanoparticles. This new colloidal spin-LED architecture presents significant prospects for future solution-processed advanced opto-spintronic devices.

circularly polarized electroluminescence↗
DOE OSTI2024

Automated Lane Centering: An Off-the-Shelf Computer Vision Product vs. Infrastructure-Based Chip-Enabled Raised Pavement Markers

Safe autonomous vehicle (AV) operations depend on an accurate perception of the driving environment, which necessitates the use of a variety of sensors. Computational algorithms must then process all of this sensor data, which typically results in a high on-vehicle computational load. For example, existing lane markings are designed for human drivers, can fade over time, and can be contradictory in construction zones, which require specialized sensing and computational processing in an AV. But, this standard process can be avoided if the lane information is simply transmitted directly to the AV. High definition maps and road side units (RSUs) can be used for direct data transmission to the AV, but can be prohibitively expensive to establish and maintain. Additionally, to ensure robust and safe AV operations, more redundancy is beneficial. A cost-effective and passive solution is essential to address this need effectively. In this research, we propose a new infrastructure information source (IIS), chip-enabled raised pavement markers (CERPMs), which provide environmental data to the AV while also decreasing the AV compute load and the associated increase in vehicle energy use. CERPMs are installed in place of traditional ubiquitous raised pavement markers along road lane lines to transmit geospatial information along with the speed limit using long range wide area network (LoRaWAN) protocol directly to nearby vehicles. This information is then compared to the Mobileye commercial off-the-shelf traditional system that uses computer vision processing of lane markings. Our perception subsystem processes the raw data from both CEPRMs and Mobileye to generate a viable path required for a lane centering (LC) application. To evaluate the detection performance of both systems, we consider three test routes with varying conditions. Our results show that the Mobileye system failed to detect lane markings when the road curvature exceeded ±0.016 m -1 . For the steep curvature test scenario, it could only detect lane markings on both sides of the road for just 6.7% of the given test route. On the other hand, the CERPMs transmit the programmed geospatial information to the perception subsystem on the vehicle to generate a reference trajectory required for vehicle control. The CERPMs successfully generated the reference trajectory for vehicle control in all test scenarios. Moreover, the CERPMs can be detected up to 340 m from the vehicle’s position. Our overall conclusion is that CERPM technology is viable and that it has the potential to address the operational robustness and energy efficiency concerns plaguing the current generation of AVs.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2023

Exploring Future Storage Options for ATLAS at the BNL/SDCC facility

The ATLAS experiment is expected to deliver an unprecedented amount of scientific data in the High Luminosity(HL-LHC) era. As the demand for disk storage capacity in ATLAS continues to rise steadily, the BNL Scientific Data and Computing Center (SDCC) faces challenges in terms of cost implications for maintaining multiple disk copies and adapting to the coming ATLAS storage requirements. To address these challenges, the SDCC Storage team has undertaken a thorough analysis of the ATLAS experiment's requirements, matching them to suitable storage options and strategies, and has explored alternatives to enhance or replace the current storage solution. This paper aims to present the main challenges encountered while supporting big data experiments such as ATLAS. We describe the experiment's specific requirements and priorities, particularly focusing on the critical storage system characteristics of the high-luminosity run and how the key storage components provided by the Storage team work together: the dCache disk storage system; its archival back-end, HPSS; and its OS-level backend Storage. Specifically, we investigate a novel approach to integrate Lustre and XRootD. In this setup, Lustre serves as backend storage and XRootD acts as an access layer frontend, supporting various grid access protocols. Additionally, we also describe the validation and commissioning tests, including the performance comparison between dCache and XRootd. Furthermore, we provide a performance and cost analysis comparing OpenZFS and LINUX MD RAID, evaluate different storage software stacks, and showcase stress tests conducted to validate Third Party Copy (TPC) functionality.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2022

User-Focused Tools to Enhance IT/OT Cyber Resilience within the Power Grid

The power grid is undergoing several changes that are increasing its complexity as nexuses between electric-gas, transmission-distribution, and energy-communications continue to become increasingly critical. This system is heavily dependent on communication infrastructure and controls, and it relies on humans in operational technology (OT) and information technology (IT) roles to manage the increasing breadth, depth, and speed of data. Many technical challenges have presented themselves and will need to be addressed to provide reliable grid operations. With increased reliance on distributed controls and communication infrastructure, cybersecurity becomes an inherent requirement. When considering current cyber-physical security solutions for the power grid, one can notice a clear divide between information technology and operation technology networks. However, in real-life applications, these networks are interdependent. This work presents results of interviews with key utility cybersecurity personnel, analyzes the results, and makes recommendations towards solution of existing technical and operational challenges realized. Existing workflows are presented, wireframe interviews are discussed, and tool requirements are described. The existence of easy-to-implement solutions, based on existing energy management systems, highlight the potential for real-life applications.

cybersecurity, resilience, user-centered design, p↗
DOE OSTI2022

ORNL_AISD_NiNb

This dataset describes the nickel-niobium solid solution binary alloy, where the two constituent elements nickel (Ni) and niobium (Nb) are randomly placed on an underlying crystal lattice. This dataset for nickel-niobium (Ni-Nb) alloys available includes the formation energy and bulk modulus for each crystal structure. Each atomic sample has a disordered phase which is obtained starting from an initial regular crystal structure of type body-centered cubic (BCC), face-centered cubic (FCC), or hexagonal compact packed (HCP). The geometry optimization ensures that all the alloy samples reached the equilibrium with negative formation energy. We perform geometry optimizations using the LAMMPS simulation package [1], a flexible simulation tool for particle-based materials modeling at the atomic, meso, and continuum scales. We utilized the embedded atom model (EAM) potential for Ni and Nb developed in a previous study [2]. The potential could describe behaviors of the liquid and solid phases of Ni-Nb alloy. The structural factors and angular distributions of three atoms are well-matched with X-ray and ab initio-based molecular dynamics data. We prepared the three different crystals with different initial lattice parameters (3.52 Ã… for FCC, 3.32 Ã… for BCC, and 3.5 Ã… for HCP). We performed energy minimization in two steps. Firstly, we minimized the structures with an isotropic unit cell to minimize the side effects from our arbitrary lattice parameters for all other compositions. Then, we applied geometry optimization with a triclinic (non-orthogonal) unit cell to fully minimize the stress components to calculate the elastic constants. In this procedure, we chose 10,000 as the maximum number of allowable steps aimed at obtaining fully relaxed atomic geometries. The dataset consists of three sets of crystal structures. The first set contains 46,086 irregular crystal structures, each of them with 54 atoms, obtained through optimization starting from a regular BCC crystal structure. The second set contains 24,543 irregular crystal structures, each of them with 32 atoms, obtained through optimization starting from a regular FCC crystal structure. The third set contains 39,303 irregular crystal structures, each of them with 48 atoms, obtained through optimization starting from a regular HCP crystal structure. The atomic configurations within each set span the possible compositional range. The three sets have been unified in a global dataset, which is extremely heterogeneous in terms of crystal structures, lattice volumes, and atomic configurations. Organization of files inside the dataset: the dataset contains three subdirectories called • BCC_opt • FCC_opt • HCP_opt based on the type of initial regular structure used to start the geometry optimization. Inside each of these folders, every atomic structure is identified by a string “A_B_Câ€, where A denotes the number of Nb in the system, B denotes index of structure with a given Nb number, and C denotes the total number of structures generated with a given Nb number. For each optimized crystal structure identified by the unique string of characters “A_B_Câ€, three files are provided: • A_B_C_opt.xyz: The optimized geometries in xyz format • A_B_C_opt.cfg: The optimized geometries in cfg format. It includes cell information and atomic energy, and forces calculated from LAMMPS. • A_B_C.elastic: Raw data of 21 elastic constants from LAMMPS output. • A_B_C.bulk: Calculated upper and lower bounds of bulk modulus and averaged one based on Voigt-Reuss-Hill approach from *.elastic. References: [1] A. P. Thompson, H. M. Aktulga, R. Berger, D. S. Bolintineanu, W. M. Brown, P. S. Crozier, P. J. in 't Veld, A. Kohlmeyer, S. G. Moore, T. D. Nguyen, R. Shan, M. J. Stevens, J. Tranchida, C. Trott, and S. J. Plimpton. LAMMPS - a flexible simulation tool for particle-based materials modeling at the atomic, meso, and continuum scales. Comp. Phys. Comm., 271:108171, 2022. [2] Y Zhang, R Ashcraft, MI Mendelev, CZ Wang, and KF Kelton. Experimental and molecular dynamics simulation study of structure of liquid and amorphous ni62nb38 alloy. The Journal of chemical physics, 145(20):204505, 2016.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Investigation of Theoretical Solutions to a Bottom-Raised Oscillating Surge Wave Energy Converter (OSWEC) Through Experimental and Parametric Studies

Experiments were conducted on a wave tank model of a bottom raised oscillating surge wave energy converter (OSWEC) model in regular waves. The OSWEC model shape was a thin rectangular flap, which was allowed to pitch in response to incident waves about a hinge located at the intersection of the flap and the top of the supporting foundation. Torsion springs were added to the hinge in order to position the pitch natural frequency at the center of the wave frequency range of the wave maker. The flap motion as well as the loads at the base of the foundation were measured. The OSWEC was modeled analytically using elliptic functions in order to obtain closed form expressions for added mass and radiation damping coefficients, along with the excitation force and torque. These formulations were derived and reported in a previous publication by the authors. While analytical predictions of the foundation loads agree very well with experiments, large discrepancies are seen in the pitch response close to resonance. These differences are analyzed by conducting a sensitivity study, in which system parameters, including damping and added mass values, are varied. The likely contributors to the differences between predictions and experiments are attributed to tank reflections, standing waves that can occur in long, narrow wave tanks, as well as the thin plate assumption employed in the analytical approach.

analytical↗
DOE OSTI2023

Polymer Compositions in Critical Experiments: Possibly Not What You Think

The Chlorine Worth Study (CWS) Experiment was performed at the National Criticality Experiments Research Center (NCERC) in December 2021. Its goal was to provide a validation benchmark experiment with chlorine and plutonium in the thermal neutron spectrum. This purpose is necessary to reduce the margin of subcriticality in aqueous chloride operations at the Los Alamos National Laboratory Plutonium Facility (PF-4). Reducing the margin of subcriticality will enable higher throughput, required to meet NNSA mission needs. The experiment used layers of plutonium plates, polyethylene (HDPE), aluminum, and polyvinyl chloride (PVC) or chlorinated polyvinyl chloride (CPVC). They were optimized to match plutonium-chloride solutions of 30 g/L, 300 g/L, and 600 g/L. Upon completion of the experiment, a International Criticality Safety Benchmark Evaluation Program (ICSBEP) report was immediately started. The compositions of all materials were assumed pure unless additional information was known (such as for the plutonium plates). During the benchmark analysis, the assumed CPVC composition was questioned. The follow-on work led to lessons learned on compositions in benchmarks. Materials, and specifically polymers, are often much more complex than a basic chemical formula. The CWS experiment is used as an example in this paper to document the lessons learned.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Divalent Titanium via Reductive N−C Coupling of a Ti IV Nitrido with π ‐Acids

The nitrido-ate complex [(PN) 2 Ti(N){μ 2 -K(OEt 2 )}] 2 (1) (PN − =(N-(2-P i Pr 2 -4-methylphenyl)-2,4,6-Me 3 C 6 H 2 ) reductively couples CO and isocyanides in the presence of DME or cryptand (Kryptofix222), to form rare, five-coordinate Ti II complexes having a linear cumulene motif, [K(L)][(PN) 2 Ti(NCE)] (E=O, L=Kryptofix222, (2); E=NAd, L=3 DME, (3); E=N t Bu, L=3 DME, (4); E=NAd, L=Kryptofix222, (5)). Oxidation of 2–5 with [Fc][OTf] afforded an isostructural Ti III center containing a neutral cumulene, [(PN) 2 Ti(NCE)] (E=O, (6); E=NAd (7), N t Bu (8)) and characterization by CW X-band EPR spectroscopy, revealed unpaired electron to be metal centric. Moreover, 1e − reduction of 6 and 7 in the presence of Kryptofix222cleanly reformed corresponding discrete Ti II complexes 2 and 5, which were further characterized by solution magnetization measurements and high-frequency and -field EPR (HFEPR) spectroscopy. Furthermore, oxidation of 7 with [Fc*][B(C 6 F 5 ) 4 ] resulted in a ligand disproportionated Ti IV complex having transoid carbodiimides, [(PN) 2 Ti(NCNAd) 2 ] (9). Comparison of spectroscopic, structural, and computational data for the divalent, trivalent, and tetravalent systems, including their 15 N enriched isotopomers demonstrate these cumulenes to decrease in order of backbonding as Ti II →Ti III →Ti IV and increasing order of π-donation as Ti II →Ti III →Ti IV , thus displaying more covalency in Ti III species. Lastly, we show a synthetic cycle whereby complex 1 can deliver an N-atom to CO and CNAd.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Exploring structural transitions at grain boundaries in Nb using a generalized embedded atom interatomic potential

The advancement in experimental techniques, like the atom probe tomography and high resolution electron microscopy, is fueling interest in studying structural transformations of grain boundaries in metal and alloys to uncover correlations between mechanical properties and solute or impurity segregation to grain boundaries. Atomistic modeling is an important tool that can pinpoint the intricate dynamics of grain boundary phase transitions, but the lack of accurate interatomic potentials needed to simulate the complex dynamics of grain boundary structural transitions and identify different metastable phases has been the bottleneck. To this end, we use niobium as a model body centered cubic (BCC) metal and develop an interatomic potential to study grain boundary phase transitions. The potential for Nb is based on a generalization of the embedded atomic method potential and has sufficient flexibility to learn complex energy landscapes using a small set of training structures. We systematically test and validate the using data from ab initio density functional theory calculations and experiments. Using this potential, we calculate energies of multiple symmetric-tilt grain boundaries spanning a wide range of misorientation angles. Additionally, we explore different metastable structures of the Σ 27(552) [$1\overline{1}0$] grain boundary and use molecular dynamic simulations to study the coexistence of metastable phases and grain boundary transitions at finite temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Condensation and growth of amorphous aluminosilicate nanoparticles via an aggregation process

The precipitation of zeolite nanoparticles involves the initial formation of metastable precursors, such as amorphous entities, that crystallize through non-classical pathways. Here, using reactive force field-based simulations, we reveal how aluminosilicate oligomers grow concomitantly to the decondensation of silicate entities during the initial step of the reaction. Aluminate clusters first form in the solution, thus violating the Loewenstein rule in the first instant of the reaction, which is then followed by their connection with silicate oligomers at the terminal silanol groups before reorganization to finally diffuse within the silicate oligomers to form stable amorphous aluminosilicate nanoparticles that do obey the Loewenstein rule. Our results clearly indicate that aluminate does not serve as the nucleation center for the growth of aluminosilicates in a nucleation-like process but rather proceeds via an aggregation process. Furthermore, the coexistence of aluminosilicate oligomers and small silicate entities induces a phase separation that promotes the precipitation of zeolites with aging.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗