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At least 289 records · Page 16

Organic Analysis of Catalytic Fischer-Tropsch Synthesis Products and Ordinary Chondrite Meteorites by Stepwise Pyrolysis-GCMS: Organics in the Early Solar Nebula

Abiotic generation of complex organic compounds, in the early solar nebula that formed our solar system, is hypothesized by some to occur via Fischer-Tropsch (FT) synthesis. In its simplest form, FT synthesis involves the low temperature (<300degC) catalytic reaction of hydrogen and carbon monoxide gases to form more complex hydrocarbon compounds, primarily n-alkanes, via reactive nano-particulate iron, nickel, or cobalt, for example. Industrially, this type of synthesis has been utilized in the gas-to-liquid process to convert syngas, produced from coal, natural gas, or biomass, into paraffin waxes that can be cracked to produce liquid diesel fuels. In general, the effect of increasing reaction temperature (>300degC) produces FT products that include lesser amounts of n-alkanes and greater alkene, alcohol, and polycyclic aromatic hydrocarbon (PAH) compounds. We have begun to experimentally investigate FT synthesis in the context of abiotic generation of organic compounds in the early solar nebula. It is generally thought that the early solar nebula included abundant hydrogen and carbon monoxide gases and nano-particulate matter such as iron and metal silicates that could have catalyzed the FT reaction. The effect of FT reaction temperature, catalyst type, and experiment duration on the resulting products is being investigated. These solid organic products are analyzed by thermal-stepwise pyrolysis-GCMS and yield the types and distribution of hydrocarbon compounds released as a function of temperature. We show how the FT products vary by reaction temperature, catalyst type, and experimental duration and compare these products to organic compounds found to be indigenous to ordinary chondrite meteorites. We hypothesize that the origin of organics in some chondritic meteorites, that represent an aggregation of materials from the early solar system, may at least in part be from FT synthesis that occurred in the early solar nebula.

Locke, Darren R.↗

Project Development of an Electrochemical Denitration and Caustic Generation System for HLW Pretreatment at Hanford - 26350

An engineering-scale electrochemical processing skid is proposed to perform the denitration of Hanford tank waste, which would help to mitigate a key process concern with the direct feed processing of the Hanford Tank Waste Treatment and Immobilization Plant (WTP). The reduction of nitrates and organic compounds in the waste feed will directly reduce hazardous NOx and ammonia gases generated during the vitrification process, which in turn will aid in addressing potential regulatory and safety challenges associated with processing large volumes of tank waste. This paper highlights the past legacy work, project layout, accomplishments from Phase 1 and research and development envisioned for Phase 2. An innovative electrochemical denitration and caustic generation (EDCGe) process was demonstrated for the pretreatment of tank waste at the Savannah River Site (SRS) in the early 2000s. The denitration electrolyzer, off-gas abatement system, and caustic generator electrolyzer are being developed with the intent that the denitration electrolyzer will convert nitrate and nitrite anions to nitrogen gas while also yielding other gaseous byproducts, which may include N2O, NH3, VOCs, and H2. The gaseous byproducts will be managed via a tandem off-gas catalyst-bed treatment system. The caustic generation electrolyzer will recycle NaOH from the feed to produce a clean caustic stream for use within the batching tanks at Hanford, aiding in the preparation of waste for WTP. The reduction in hazardous emissions and improved waste treatment processes provides a robust solution for nuclear waste management, contributing to environmental safety and regulatory compliance. The EDCGe technology is being adapted, modified, and updated for the preparation of the Direct Feed-High Level Waste (DF-HLW) flowsheet at Hanford. Phase 1 demonstrated a bench-scale proof-of-concept for reactions involving the denitration electrolyzer and gas phase abatement of ammonia. The electrochemical technology is drawing on the scientific outcomes that were reported in the legacy work. The results from Phase 1 demonstrated the viability of the EDCGe system in reducing the nitrogen species of simple non-radioactive waste simulants. Commercially available alloys used as electrode materials and membranes are being studied for the denitration and caustic generation electrolyzers. The continuation of this project holds promise for broader applications, such as energy-efficient ammonia production, and contributes significant advancements in nuclear waste management. Additional material discovery has been investigated into ceramic Na super ion conductive (NaSICON) materials and off-gas abatement catalyst discovery. NaSICON is of interest for selective transport of Na within the electrolyzers to make a clean caustic stream. Future integration and optimization efforts, informed by Phase 1 results and ongoing research, will continue to drive advancements in nuclear waste management technology. The technology developed for the EDCGe treatment of tank waste will also have broader potential to inform other fields, such as energy-efficient ammonia production, as well as ammonia abatement catalysis through the lessons learned in electrochemical nitrate reduction. The applications and benefits of this research extend beyond Hanford and the Savannah River Site, supported by a collaborative team of scientists and engineers from national labs, academia, and industry, ensuring a comprehensive approach to solving complex waste treatment challenges. The team is leveraging advanced electrochemical technologies, machine learning, novel catalysts tailored for gaseous nitrogen species, and cutting-edge reactor systems to enhance the process efficiency and effectiveness of the denitration process.

Rodene, Dylan [Savannah River National Laboratory ↗

Numerical simulations of liquid jetting with solid inclusions

The dynamics of finite-sized particles in fluids, and their influence on the overall flow, are of great interest across several industrial, environmental, and medical fields. In the context of inkjet printing, the presence of solid inclusions can be either intentional, as in additive manufacturing, or unintentional, as in standard printing processes. These inclusions can strongly impact the jetting process, causing effects such as jet asymmetry, bubble entrapment, and the formation of satellite droplets. Understanding and controlling particle behavior is therefore essential, particularly to predict how and when particles are ejected over multiple jetting cycles. It is therefore critical to develop reliable models that allow for a deeper understanding of the complex interplay between particle and fluid during the whole printing process. To address this, we present a tailored implementation of the Color-Gradient multicomponent Lattice Boltzmann Method for fully resolved three-dimensional (3D) simulations of multicycle liquid jetting with particles. Our method supports realistic parameter settings aligned with industrial inkjet systems, and we provide both qualitative and quantitative validation against experimental data. Additionally, we introduce a simplified model based on the Stokes drag law, in which solid particles are represented as point particles and do not influence the fluid flow. Despite this limitation, the model offers a computationally efficient means to explore the vast parameter space typically encountered in industrial applications, allowing, e.g., identifying critical ejection regions and estimating the number of cycles required for particle release. These qualitative insights are valuable for guiding and complement fully two-way coupled simulations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Solid Oxide Electrochemical Systems: Material Degradation Processes and Novel Mitigation Approaches

Solid oxide electrochemical systems, such as solid oxide fuel cells (SOFC), solid oxide electrolysis cells (SOEC), and oxygen transport membranes (OTM) enable clean and reliable production of energy or fuel for a range of applications, including, but not limited to, residential, commercial, industrial, and grid-support. These systems utilize solid-state ceramic oxides which offer enhanced stability, fuel flexibility, and high energy conversion efficiency throughout operation. However, the nature of system conditions, such as high temperatures, complex redox atmosphere, and presence of volatile reactive species become taxing on solid oxide materials and limit their viability during long-term operation. Ongoing research efforts to identify the material corrosion and degradation phenomena, as well as discover possible mitigation techniques to extend material efficiency and longevity, is the current focus of the research and industrial community. In this review, degradation processes in select solid oxide electrochemical systems, system components, and comprising materials will be discussed. Overall degradation phenomena are presented and certain degradation mechanisms are discussed. State-of-the-art technologies to mitigate or minimize the above-mentioned degradation processes are presented.

36 MATERIALS SCIENCE↗

On the hitchhiker Robot Operated Materials Processing System: Experiment data system

The Space Shuttle Discovery STS-64 mission carried the first American autonomous robot into space, the Robot Operated Materials Processing System (ROMPS). On this mission ROMPS was the only Hitchhiker experiment and had a unique opportunity to utilize all Hitchhiker space carrier capabilities. ROMPS conducted rapid thermal processing of the one hundred semiconductor material samples to study how micro gravity affects the resulting material properties. The experiment was designed, built and operated by a small GSFC team in cooperation with industry and university based principal investigators who provided the material samples and data interpretation. ROMPS' success presents some valuable lessons in such cooperation, as well as in the utilization of the Hitchhiker carrier for complex applications. The motivation of this paper is to share these lessons with the scientific community interested in attached payload experiments. ROMPS has a versatile and intelligent material processing control data system. This paper uses the ROMPS data system as the guiding thread to present the ROMPS mission experience. It presents an overview of the ROMPS experiment followed by considerations of the flight and ground data subsystems and their architecture, data products generation during mission operations, and post mission data utilization. It then presents the lessons learned from the development and operation of the ROMPS data system as well as those learned during post-flight data processing.

Kizhner, Semion↗

Structural Dynamics in UV Curable Resins Resolved by In Situ 3D Printing X-ray Photon Correlation Spectroscopy

Additive manufacturing (AM) is a promising technique to rapidly produce polymeric materials into complex 3-dimensional (3D) geometries. While AM is widespread and relevant for a range of applications, implementation in industry has outpaced our fundamental understanding of polymer dynamics and structure development during the printing process. Characterization and quantification of such dynamics is necessary to optimize final material properties and design future materials and processes for 3D printing. Here, we utilize X-ray photon correlation spectroscopy (XPCS) to measure spatial and time-resolved, out-of-equilibrium dynamics during direct ink write (DIW) 3D printing. Specifically, we investigate the progression of structural dynamics in a dual cure (UV/thermal) nanocomposite during and directly after printing. As the filament is printed and cured in situ, the relaxation processes of the cross-linking network are measured through the dynamics of inorganic filler particles. The characteristic relaxation time of the dynamics is calculated through the intensity–intensity autocorrelation function g 2 and directly correlated to the printing process parameters, such as printhead velocity and UV light intensity. The time-resolved evolution of nanoscale dynamics follows a power-law dependence as the filament is cured. Additionally, bulk rheological characterizations reveal the macroscopic solidification of the resin, providing correlation of material properties across a wide range of length and time scales. Overall, the measurement of multiscale, out-of-equilibrium dynamics provides insight into the development of structure in polymer nanocomposite filaments during 3D printing and is used to further understand the influence of such parameters on the AM process.

36 MATERIALS SCIENCE↗

A Conceptual Architecture for a Quantum-HPC Middleware

Abstract-Quantum computing promises potential for science and industry by solving certain computationally complex problems faster than classical computers. Quantum computing systems evolved from coupled to classical computing nodes (HPC). With the increasing monolithic systems towards modular architectures comprising multiple quantum processing units (QPUs) scale, middleware systems that facilitate the efficient coupling of quantum-classical computing are becoming critical. Through an in-depth analysis of quantum applications, integration patterns and systems, we identified a gap in understanding Quantum HPC middleware systems. We present a conceptual middleware to facilitate reasoning about quantum-classical integration and serve as the basis for a future middleware system. An essential contribution of this paper lies in leveraging well-established high performance computing abstractions for managing workloads, tasks, and resources to integrate quantum computing into HPC systems seamlessly

97 MATHEMATICS AND COMPUTING↗

Los Alamos National Security, LLC Request for Information on how industry may partner with the Laboratory on KIVA software.

KIVA is a family of Fortran-based computational fluid dynamics software developed by LANL. The software predicts complex fuel and air flows as well as ignition, combustion, and pollutant-formation processes in engines. The KIVA models have been used to understand combustion chemistry processes, such as auto-ignition of fuels, and to optimize diesel engines for high efficiency and low emissions. Fuel economy is heavily dependent upon engine efficiency, which in turn depends to a large degree on how fuel is burned within the cylinders of the engine. Higher in-cylinder pressures and temperatures lead to increased fuel economy, but they also create more difficulty in controlling the combustion process. Poorly controlled and incomplete combustion can cause higher levels of emissions and lower engine efficiencies.

33 ADVANCED PROPULSION SYSTEMS↗

Hydrothermal Liquid Recovery of Rare Earth Elements and Critical Materials

This project demonstrated the technical viability of using tunable hydrothermal liquid (HTL) solutions to recover valuable minerals from a range of source materials. The effort focused upon rare earth elements (REE) and other minerals critical to the industrial security of the United States. This effort demonstrated, for the first time, that s, supercritical water (SCW) in particular, can: Extract critical and valuable minerals from a range of matrices ranging from rock ore to biomass; The process can be used to recover a wide range of minerals; This novel extraction chemistry can be cheap, simple, and nontoxic/”green”: The chemical extraction uses water, the cheapest industrial acid (sulfuric), and simple salts (i.e. sodium sulfate). However, other acids, salts, and additives could be used as appropriate. This Laboratory Directed Research and Development (LDRD) project identified that the process is complex with many interacting factors, but the benefits are significant if the complexities can be resolved. Challenges remain in the development of this technology and are described in this report. However, the results are positive, and commercial partners have already expressed interest. In summary, a novel, green, inexpensive mineral extraction process has been developed and demonstrated in a small batch reactor system. The effort provided information for an invention disclosure, proposal to DOE, and will support future business development efforts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Numerical Flow Visualization in Basic- and Hyper-Cluster Spheres

Packed spherical particle beds have wide applications throughout the process industry and are usually analyzed using an appropriate combination of laminar and turbulent flows with empirically derived coefficients of which the Ergun (1952) relation is probably the best known. The 3-D complexity of the void distribution within the beds has precluded detailed studies of sphere clusters. Numerical modeling and flow vector visualization for the basic tetra- and hexa-sphere clusters and two hyper-sphere clusters are presented at two Reynolds numbers, 400 and 1200. Cutting planes are used to enable visualization of the complex flows generated within the sphere clusters and are discussed herein. The boundary conditions and flow fields for the simple clusters are also compared to the hyper-clusters with larger variations found for hexa-clusters.

Hendricks, R. C.↗

Computational Modeling in Structural Materials Processing

High temperature materials such as silicon carbide, a variety of nitrides, and ceramic matrix composites find use in aerospace, automotive, machine tool industries and in high speed civil transport applications. Chemical vapor deposition (CVD) is widely used in processing such structural materials. Variations of CVD include deposition on substrates, coating of fibers, inside cavities and on complex objects, and infiltration within preforms called chemical vapor infiltration (CVI). Our current knowledge of the process mechanisms, ability to optimize processes, and scale-up for large scale manufacturing is limited. In this regard, computational modeling of the processes is valuable since a validated model can be used as a design tool. The effort is similar to traditional chemically reacting flow modeling with emphasis on multicomponent diffusion, thermal diffusion, large sets of homogeneous reactions, and surface chemistry. In the case of CVI, models for pore infiltration are needed. In the present talk, examples of SiC nitride, and Boron deposition from the author's past work will be used to illustrate the utility of computational process modeling.

Meyyappan, Meyya↗

Demand response event simulator and risk-aware bidding tool for industrial customers

Incentive Based Demand Response (IBDR) program participation delivers financial benefits to the consumers and resiliency benefits to the electricity grid. Effectively participating in these programs as an industrial consumer requires bidding strategies that balance financial risk with operational constraints. Existing bidding tools tend not to fully incorporate stochastic IBDR event modeling, program specific baseline and payment/penalty calculations, or demand reduction process control schemes that account for the cascading impacts of shutdown in complex facilities. Here, this work presents an IBDR event simulator and risk-aware bidding framework tool integrating three key components: a flexible, parameterized demand response event generator that rigorously accounts for program structures and stochasticity, a demand response operational simulation model that generates explicit control strategies for load reduction, and a Monte Carlo simulator to evaluate financial risk for varied capacity bids. A case study at a wastewater treatment plant participating in PG&E's Capacity Bidding Program demonstrates the framework's utility. In the peak capacity price month of August, optimal bidding by the wastewater treatment plant nets a mean IBDR benefit of $101,000 (67% of the August electricity bill) with 0.4% probability of a financial loss. This framework enables industrial operators to make informed bidding decisions, negotiate better program terms with demand response load aggregators, and analyze energy flexibility investments at their facilities. Ultimately, this work reduces participation barriers in IBDR programs and supports the broader goal of enhancing grid reliability and renewable energy integration.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Integrating Efficiency of Industry Processes and Practices Alongside Technology Effectiveness in Space Transportation Cost Modeling and Analysis

This paper presents past and current work in dealing with indirect industry and NASA costs when providing cost estimation or analysis for NASA projects and programs. Indirect costs, when defined as those costs in a project removed from the actual hardware or software hands-on labor; makes up most of the costs of today's complex large scale NASA space/industry projects. This appears to be the case across phases from research into development into production and into the operation of the system. Space transportation is the case of interest here. Modeling and cost estimation as a process rather than a product will be emphasized. Analysis as a series of belief systems in play among decision makers and decision factors will also be emphasized to provide context.

Zapata, Edgar↗

A Molecular Compound for Highly Selective Purification of Ethylene

Purification of C 2 H 4 from an C 2 H 4 /C 2 H 6 mixture is one of the most challenging separation processes, which is achieved mainly through energy-intensive, cryogenic distillation in industry. Sustainable, non-distillation methods are highly desired as alternatives. We discovered that the fluorinated bis(pyrazolyl)borate ligand supported copper(I) complex {[(CF 3 ) 2 Bp]Cu} 3 has features very desirable in an olefin–paraffin separation material. It binds ethylene exclusively over ethane generating [(CF 3 ) 2 Bp]Cu(C 2 H 4 ). This molecular compound exhibits extremely high and record ideal adsorbed solution theory (IAST) C 2 H 4 /C 2 H 6 gas separation selectivity, affording high purity (>99.5 %) ethylene that can be readily desorbed from separation columns. In-situ PXRD provides a “live” picture of the reversible conversion between [(CF 3 ) 2 Bp]Cu(C 2 H 4 ) and the ethylene-free sorbent in the solid-state, driven by the presence or removal of C 2 H 4 . As a result, molecular structures of trinuclear {[(CF 3 ) 2 Bp]Cu} 3 and mononuclear [(CF 3 ) 2 Bp]Cu(C 2 H 4 ) are also presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Central Appalachian Basin CarbonSAFE Integrated Pre-Feasibility Project (Final Technical Report)

The Central Appalachian Basin-Carbon Storage Assurance Facility Enterprise (CarbonSAFE) (CAB-CS) Integrated Prefeasibility Project identified several “Selected Areas” in eastern Ohio where the Cambrian-Ordovician age sandstones and carbonates show the most promising reservoir potential for carbon capture and storage (CCS). These selected areas are located near depleted oil and gas fields where oil recovery could be improved with enhanced oil recovery. This region has many large carbon dioxide (CO 2 ) point sources that represent a diverse array of industries, including coal-fired power plants, natural gas processing, refineries, chemical plants, and natural gas power. In a carbon-constrained future, one of the most promising ways to make coal a viable fuel option for power generation or industrial processes is to capture and store CO 2 emissions. The project is a pre-feasibility study to mitigate the emissions from 1.67 million metric tons CO 2 per year by developing a storage complex capable of storing 50 million metric tons. The pre-feasibility study identified two candidate locations for a carbon storage hub in the Appalachian Basin, analyzed six source-sink scenarios in the CAB-CS study area with analysis of capture and transport, defined infrastructure needs for a CCS project in the area, conducted an economic, liability, and social assessment, and built a team to evaluate CCS options in the CAB-CS study area. The project was an important step in implementing CCS in the CAB-CS study area. Major accomplishments include experience in investigating CCS projects in the area (learning by doing), adding to National Energy Technology Laboratory (NETL) best practices tools and tool sets, and building the elements of the CCS road map for the region.

20 FOSSIL-FUELED POWER PLANTS↗

Elaboration of Metallic Materials by SPS: Processing, Microstructures, Properties, and Shaping

After a few decades of increasing interest, spark plasma sintering (SPS) has now become a mature powder metallurgy technique, which allows assessing its performances toward fabricating enhanced materials. Here, the case of metals and alloys will be presented. The main advantage of SPS lies in its rapid heating capability enabled by the application of high intensity electric currents to a metallic powder. This presents numerous advantages balanced by some limitations that will be addressed in this review. The first section will be devoted to sintering issues, with an emphasis on the effect of the electric current on the densification mechanisms. Then, typical as-SPS microstructures and properties will be presented. In some cases, they will be compared with that of materials processed by conventional techniques. As such, examples of nanostructured materials, intermetallics, metallic glasses, and high entropy alloys, will be presented. Finally, the implementation of SPS as a technique to manufacture complex, near-net shape industrial parts will be discussed.

36 MATERIALS SCIENCE↗

Basic Research Needs for Catalysis Science

Catalysis is the core of modern chemical conversions—the production processes for the vast majority of our fuels and chemicals use catalysts. Solid and molecular catalysts increase chemical transformation rates (reactivity) by lowering energy barriers for chemical reactions and can increase the yield of desired products (selectivity) by controlling the relative rates of competing reactions. High catalytic reactivity and selectivity reduce the required energy input, the number of process steps, and unwanted byproducts in the overall catalytic conversion. New catalysts will enable more efficient chemical transformations of raw materials and interconversion of the energy stored in chemical bonds with thermal and electrical energy. Advancing our understanding of and ability to control catalyzed reactions is essential to ensure the long-term economic viability of the energy and chemical industries. Over the past decade, advances in the characterization of working catalysts, theory and computation, and high-precision chemical and materials synthesis have enabled impressive progress in catalysis science. This progress has provided detailed insight into how reactions occur and has led to increased appreciation of the intrinsic complexity of catalytic processes. Understanding this complexity has further enabled advances in areas as diverse as high-temperature transformation of hydrocarbons, low-temperature conversion of highly functionalized bio-derived compounds, highly selective synthesis of complex molecules, and improved electrochemical processes. By integrating the knowledge gained from studies of homogeneous, heterogeneous, and biological catalysts, we are beginning to understand and take advantage of the remarkably diverse capabilities of catalysts based on multifunctional molecular complexes, functionalized porous materials, and stabilized nanostructures and single atoms. A Basic Research Needs workshop held in May 2017 identified five Priority Research Directions that address complexity in catalysis science. This emerging and transformative approach will lead to catalysts with unprecedented reactivity and selectivity for use in critical energy and chemical technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Graph theory approach to determine configurations of multidentate and high coverage adsorbates for heterogeneous catalysis

Abstract Heterogeneous catalysts constitute a crucial component of many industrial processes, and to gain an understanding of the atomic-scale features of such catalysts, ab initio density functional theory is widely employed. Recently, growing computational power has permitted the extension of such studies to complex reaction networks involving either high adsorbate coverages or multidentate adsorbates, which bind to the surface through multiple atoms. Describing all possible adsorbate configurations for such systems, however, is often not possible based on chemical intuition alone. To systematically treat such complexities, we present a generalized Python-based graph theory approach to convert atomic scale models into undirected graph representations. These representations, when combined with workflows such as evolutionary algorithms, can systematically generate high coverage adsorbate models and classify unique minimum energy multidentate adsorbate configurations for surfaces of low symmetry, including multi-elemental alloy surfaces, steps, and kinks. Two case studies are presented which demonstrate these capabilities; first, an analysis of a coverage-dependent phase diagram of absorbate NO on the Pt 3 Sn(111) terrace surface, and second, an investigation of adsorption energies, together with identifying unique minimum energy configurations, for the reaction intermediate propyne (CHCCH 3 *) adsorbed on a PdIn(021) step surface. The evolutionary algorithm approach reproduces high coverage configurations of NO on Pt 3 Sn(111) using only 15% of the number of simulations required for a brute force approach. Furthermore, the screening of potentially hundreds of multidentate adsorbates is shown to be possible without human intervention. The strategy presented is quite general and can be applied to a spectrum of complex atomic systems.

36 MATERIALS SCIENCE↗