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At least 181 records · Page 10

Phytoplankton and Climate

Ocean phytoplankton supply about half of the oxygen that humans utilize to sustain life. In this lecture, we will explore how phytoplankton plays a critical role in modulating the Earth's climate. These tiny organisms are the base of the Ocean's food web. They can modulate the rate at which solar heat is absorbed by the ocean, either through direct absorption or through production of highly scattering cellular coverings. They take up and help sequester carbon dioxide, a key greenhouse gas that modulated the Earth's climate. They are the source of cloud nucleation gases that are key to cloud formation/processes. They are also able to modify the nutrient budgets of the ocean through active uptake of inert atmospheric nitrogen. Climate variations have a pronounced impact on phytoplankton dynamics. Long term variations in the climate have been studied through geological interpretations on its influence on phytoplankton populations. The presentation will focus on presenting the numerous linkages that have been observed between climate and phytoplankton and further discuss how present climate change scenarios are likely to impact phytoplankton populations as well as present findings from several studies that have tried to understand how the climate might react to the feedbacks from these numerous climate-phytop|ankton linkages.

Moisan, John R.↗

Synthesis, Characterization, Topographical Modification, and Surface Properties of Copoly(Imide Siloxane)s

Novel copoly(imide siloxane)s were synthesized from commercially available aminopropyl terminated siloxane oligomers, aromatic dianhydrides, and diamines. This synthetic approach produced copolymers with well-defined siloxane blocks linked with imide units in a random fashion. The copoly(amide acid)s were characterized by solution viscosity and subsequently used to cast thin films followed by thermal imidization in an inert atmosphere. Thin films were characterized using contact angle goniometry, attenuated total reflection Fourier transform infrared spectroscopy, confocal and optical microscopy, and tensile testing. Adhesion of micronsized particles was determined quantitatively using a sonication device. The polydimethylsiloxane (PDMS) moieties lowered the copolymer surface energy due to migration of siloxane moieties to the film s surface, resulting in a notable reduction in particle adhesion. A further reduction in particle adhesion was achieved by introducing topographical features on a scale of several to tens of microns by a laser ablation technique.

Wohl, Christopher J.↗

IR-doped ruthenium oxide catalyst for oxygen evolution

A method for preparing a metal-doped ruthenium oxide material by heating a mixture of a doping metal and a source of ruthenium under an inert atmosphere. In some embodiments, the doping metal is in the form of iridium black or lead powder, and the source of ruthenium is a powdered ruthenium oxide. An iridium-doped or lead-doped ruthenium oxide material can perform as an oxygen evolution catalyst and can be fabricated into electrodes for electrolysis cells.

Valdez, Thomas I.↗

Enhanced TiO2 Photocatalytic Processing of Organic Wastes for Green Space Exploration

The effect of transition metal co-catalysts on the photocatalytic properties of TiO2 was investigated. Ruthenium (Ru), palladium, platinum, copper, silver, and gold, were loaded onto TiO2 powders (anatase and mixed-phase P25) and screened for the decomposition of rhodamine B (RhB) under broad-band irradiation. The morphology and estimated chemical composition of photocatalysts were determined by scanning electron microscopy and energy dispersive spectroscopy, respectively. Brunhauer, Emmett and Teller (BET) analysis measured mass-specific surface area(s). X-ray diffraction analysis was performed to confirm the identity of titania phase(s) present. The BET surface area of anatase TiO2/Ru 1% (9.2 sq m/gm) was one of the highest measured of all photocatalysts prepared in our laboratory. Photolyses conducted under air-saturated and nitrogen-saturated conditions revealed photodegradation efficiencies of 85 and 2 percent, respectively, after 60 min compared to 58 percent with no catalyst. The cause of low photocatalytic activity under an inert atmosphere is discussed. TiO2/Ru 1% showed a superior photocatalytic activity relative to P25-TiO2 under broad-band irradiation. A potential deployment of photocatalytic technologies on a mission could be a reactor with modest enhancement in solar intensity brought about by a trough-style reactor, with reactants and catalyst flowing along the axis of the trough and therefore being illuminated for a controlled duration based on the flow rate.

Udom, I.↗

Advanced Materials and Fabrication Techniques for the Orion Attitude Control Motor

Rhenium, with its high melting temperature, excellent elevated temperature properties, and lack of a ductile-to-brittle transition temperature (DBTT), is ideally suited for the hot gas components of the ACM (Attitude Control Motor), and other high-temperature applications. However, the high cost of rhenium makes fabricating these components using conventional fabrication techniques prohibitive. Therefore, near-net-shape forming techniques were investigated for producing cost-effective rhenium and rhenium alloy components for the ACM and other propulsion applications. During this investigation, electrochemical forming (EL-Form ) techniques were evaluated for producing the hot gas components. The investigation focused on demonstrating that EL-Form processing techniques could be used to produce the ACM flow distributor. Once the EL-Form processing techniques were established, a representative rhenium flow distributor was fabricated, and samples were harvested for material properties testing at both room and elevated temperatures. As a lower cost and lighter weight alternative to an all-rhenium component, rhenium- coated graphite and carbon-carbon were also evaluated. The rhenium-coated components were thermal-cycle tested to verify that they could withstand the expected thermal loads during service. High-temperature electroforming is based on electrochemical deposition of compact layers of metals onto a mandrel of the desired shape. Mandrels used for electro-deposition of near-net shaped parts are generally fabricated from high-density graphite. The graphite mandrel is easily machined and does not react with the molten electrolyte. For near-net shape components, the inner surface of the electroformed part replicates the polished graphite mandrel. During processing, the mandrel itself becomes the cathode, and scrap or refined refractory metal is the anode. Refractory metal atoms from the anode material are ionized in the molten electrolytic solution, and are deposited onto the cathodic mandrel by electrochemical reduction. Rotation of the mandrel ensures uniform distribution of refractory material. The EL-Form process allows for manufacturing in an inert atmosphere with deposition rates from 0.0004 to 0.002 in./h (10.2 to 50.8 m/h). Thicknesses typically range from microns to greater than 0.5 in. (13 mm). The refractory component produced is fabricated, dependably, to within one micron of the desired tolerances with no shrinkage or distortion as in other refractory metal manufacture techniques. The electroforming process has been used to produce solid, nonporous deposits of rhenium, iridium, niobium, tungsten, and their alloys.

Gorti, Sridhar↗

Method of Creating Micro-scale Silver Telluride Grains Covered with Bismuth Nanoparticles

Provided is a method of enhancing thermoelectric performance by surrounding crystalline semiconductors with nanoparticles by contacting a bismuth telluride material with a silver salt under a substantially inert atmosphere and a temperature approximately near the silver salt decomposition temperature; and recovering a metallic bismuth decorated material comprising silver telluride crystal grains.

Kim, Hyun-Jung↗

Synthesis, Structure, Characterization, and Decomposition of Nickel Dithiocarbamates: Effect of Precursor Structure and Processing Conditions on Solid-State Products

Single-crystal X-ray structures of four nickel dithiocarbamate complexes, the homoleptic mixed-organic bis-dithiocarbamates Ni[S2CN(isopropyl)(benzyl)]2, Ni[S2CN(ethyl)(n-butyl)]2, and Ni[S2CN(phenyl)(benzyl)]2, as well as the heteroleptic mixed-ligand complex NiCl[P(phenyl)3][(S2CN(phenyl)(benzyl)], were determined. Synthetic, spectroscopic, structural, thermal, and sulfide materials studies are discussed in light of prior literature. The spectroscopic results are routine. A slightly distorted square-planar nickel coordination environment was observed for all four complexes. The organic residues adopt conformations to minimize steric interactions. Steric effects also may determine puckering, if any, about the nickel and nitrogen atoms, both of which are planar or nearly so. A trans-influence affects the Ni-S bond distances. Nitrogen atoms interact with the CS2 carbons with a bond order of about 1.5, and the other substituents on nitrogen display transoid conformations. There are no strong intermolecular interactions, consistent with prior observations of the volatility of nickel dithiocarbamate complexes. Thermogravimetric analysis of the homoleptic species under inert atmosphere is consistent with production of 1:1 nickel sulfide phases. Thermolysis of nickel dithiocarbamates under flowing nitrogen produced hexagonal or -NiS as the major phase; thermolysis under flowing forming gas produced millerite (-NiS) at 300 C, godlevskite (Ni9S8) at 325 and 350 C, and heazlewoodite (Ni3S2) at 400 and 450 C. Failure to exclude oxygen results in production of nickel oxide. Nickel sulfide phases produced seem to be primarily influenced by processing conditions, in agreement with prior literature. Nickel dithiocarbamate complexes demonstrate significant promise to serve as single-source precursors to nickel sulfides, a quite interesting family of materials with numerous potential applications.

microscopy↗

Laser Ablation Surface Treatment of Structural Aerospace Composites and Metal Alloys for Adhesive Bonding

NASA Langley Research Center (LaRC) has been involved over the past decade in the development of laser ablation as a method to surface treat aerospace structural fiber reinforced composites (CFRPs) and metal alloys. [1- 18] Laser surface treatment has been shown to be a rapid, high precision, and reproducible method for surface treatment of these materials, and is amenable to automation. The laser ablation process removes surface contamination such as silicones, creates surface roughness, and chemically activates a surface for bonding. The degree of ablation is controllable by adjusting laser parameters. In the case of CFRPs, ablation can be performed without damage to any underlying carbon fibers. In the case of metal alloys, ablation is possible without surface embrittlement, heat damage or creation of undesirable grain structures or morphologies. The optimum laser treatment conditions are substrate dependent and generally are influenced by laser wavelength and pulse duration (typically fixed for a laser system), and laser power. In the case of metal alloys such as Ti-6Al-4V, the laser ablation process eliminates the need for several steps of the conventional processes, including hydrofluoric (HF) acid and caustic treatment. These steps are often conducted in dip tanks and require costly facilities and environmentally unfriendly liquids. In addition, the laser can create nano-porosity on the Ti-6Al-4V alloy surface allowing for sol-gel penetration and thereby creating a gradient interface with improved temperature and mechanical performance. NASA LaRC has also been involved with the development of in-line characterization methods compatible with the laser treatment process to rapidly determine the presence of key contaminates such as silicones that, even at very low concentrations, are a threat to adhesive bonding. A spectroscopic technique called micro-laser induced breakdown spectroscopy (u-LIBS) has been developed to rapidly detect silicones at concentrations below those known to cause bonding problems. This technique requires no sample preparation, vacuum or inert atmosphere, has no practical size limitations, and provides nearly instantaneous feedback to the operator. This presentation will give an overview and update of these developments with specific examples highlighted.

Connell, John W.↗

Enhanced Thermal Stability of High Yttria Concentration YSZ Aerogels

Aerogels demonstrate extraordinarily low thermal conductivity and low density, presenting a promising form of lightweight insulation for aerospace applications. The primary challenge is stabilization of the highly porous structure at temperatures to 1200 °C. Upon collapse of the pore structure, the favorable thermal properties and low density are diminished. Yttria-stabilized zirconia (YSZ) aerogels are synthesized to investigate the effect of composition on morphology, phase behavior, and thermal stability (specific surface area, pore size distribution). This work demonstrates the improvement in thermal stability of zirconia aerogels with increased yttria content. Furthermore, changes in structure and surface chemistry of YSZ aerogels are studied in both oxidizing and inert atmospheres. With an improved understanding of aerogel structure and performance, metal oxide aerogels can be developed to withstand the extreme environments of space exploration.

Nathaniel Olson↗

Additive Manufacturing and Working Fluid Characterization of Ceramic Heat Pipes

In this work, additively manufactured (AM) aluminum nitride (AlN) ceramic heat pipes were developed to improve spacecraft heat rejection capabilities beyond the current state-of-the-art metal systems. A low sintering temperature aluminum nitride slurry is developed for digital light processing printing (DLP) and the optimal debinding curves are examined. Printed AlN parts are characterized via SEM and optical profilometry. AlN 3D-printed parts are also tested for compatibility with aluminum bromide, aluminum chloride, and iodine, among other proposed working fluids at 350-600 K in an inert atmosphere, with reactivity measured via SEM and Fourier transform infrared spectroscopy (FTIR).

Thermal Management↗

High energy, long cycle life electrode for lithium-ion batteries

Anodes for electrochemical cells and batteries are described herein. In particular, and anode comprises silicon oxide particles on a transition metal current collector (e.g., copper, nickel, copper alloy, and the like), wherein the particles comprise nanocrystalline domains of silicon dispersed within a silicon oxide matrix. The particles do not include a metal oxide coating, and are produced by heating a silicon monoxide powder at a temperature in the range of about 400 to about 1100° C. under an inert atmosphere for about 2 to about 20 hours. In some embodiments, the particles are free from a metal oxide coating and have an average diameter of about 20 to 10000 nm; the nanocrystalline domains of silicon comprise about 10 to about 90 mole percent of the particles; and the nanocrystalline domains have dimensions of about 0.2 to about 50 nm in average diameter.

25 ENERGY STORAGE↗

Characterizing Dynamic Structure in Battery Electrodes by Time-Resolved Cryo-TEM

In recent years, cryogenic transmission electron microscopy (cryo-TEM) has enabled high-resolution characterization of sensitive battery materials by minimizing electron beam-induced artifacts and damage. Success of this technique relies on the preparation of thin, rapidly frozen samples, generally by disassembling batteries under inert atmosphere, transferring materials of interest to a TEM grid, and finally plunge freezing into a cryogen. In material degradation studies, this extensive time between electrochemical cycling and cryo-TEM characterization leaves room for structural relaxation, diffusion, and other dynamic processes that make it difficult to precisely correlate the imaged structure with the native structure that evolves during battery cycling or aging. Here, we present a method to integrate battery cycling with fast preparation of electrode samples for cryo-TEM. This enables higher fidelity between the structures characterized and the electrochemical state of interest, which we use to study deformation in silicon nanoparticle anodes for lithium-ion batteries.

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS↗

Removal of Bond Sodium from Full-Length Unirradiated Fermi-1 Blanket Elements and Assembly via Melt-Drain-Evaporate Process

Equipment was designed, fabricated, tested, and operated in an inert atmosphere radiological glovebox at Idaho National Laboratory to demonstrate the removal of bond sodium from full-length unirradiated Fermi-1 radial blanket elements and an entire radial blanket assembly using a Melt-Drain-Evaporate process. A series of three runs was performed with individual and multiple radial Fermi-1 blanket elements, and a fourth run was conducted with an entire Fermi-1 radial blanket assembly. After each run, the depleted uranium alloy slugs in every element slid out of its cladding, mechanically exhibiting the effectual absence of bond sodium. Quantitative and further qualitative analyses of the treated Fermi-1 material revealed the substantive, if not complete, absence of sodium metal in blanket element components. Indeed, entire columns of depleted uranium alloy slugs and associated cladding from select treated elements were separately contacted with water to react with residual sodium metal on the element surfaces, forming hydrogen gas. Samples of the resultant gas were analyzed to quantify the hydrogen concentration, which correlated to a residual sodium metal content for the treated element. Accordingly, no detectable sodium metal (<7 µg) was found on the surfaces of multiple depleted uranium alloy slugs after removal from its cladding. Detectable sodium metal, ranging from 14 to 30 µg, was found on the surfaces of one separated column of slugs and two separated full-length cladding segments. Each element originally contained ~25 g of bond sodium, resulting in quantitative sodium metal removal efficiencies of =99.9998%. The remaining separated uranium alloy slugs and cladding segments from the four runs were piece-wise immersed in alcohol while videorecording possible gas bubble formation as an additional qualitative analysis for residual sodium metal on treated surfaces, which identified the predominant absence of sodium reactivity on the balance of treated Fermi-1 blanket material. The results of this demonstration substantiate a path forward for treatment and disposal of 34 metric tons heavy metal of irradiated sodium-bonded Fermi-1 blanket material currently stored at Idaho National Laboratory.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Elucidating the corrosion mechanism of commercial Ni-based Superalloys in UCl3 containing-chloride Molten Salt Systems

Molten salt reactors (MSRs) have gained renewed interest, providing several advantages over their predecessors, including the capability to consume spent fuels, enhancing the environmental sustainability of the uranium fuel cycle. For example, molten chloride fast reactors (MCFRs) can reach criticality with molten chloride spent fuel containing high concentrations of impurities, such as actinide products like uranium chloride (UCl3). However, the redox potential of chloride molten salt fuels may change in the presence of these impurities, dictating their corrosivity and in turn the corrosion performance of structural components, such as those constructed from nickel (Ni)-based alloys. The purpose of this investigation is to assess the extent of corrosion of Ni-based alloy, Inconel 617, when exposed to UCl3-LiCl-KCl eutectic salt. Inconel 617 one of only six structural materials that are fully qualified by the American Society for Mechanical Engineers (ASME) Boiler and Pressure Vessel Code for high-temperature nuclear reactor components, making it a technologically mature material to consider for constructing MCFRs. Inconel 617 specimens were submerged in a static LiCl-KCl-UCl3 eutectic salt mixture heated at 700 C for 1000 h under an inert atmosphere. Upon completion, the extent of corrosion was analyzed through a multi-modal characterization approach spanning the engineering to nanoscale, employing computed tomography, focused-ion beam, and transmission electron microscopy techniques. Results from this investigation will enhance our understanding of property-to-performance relationships of candidate structural materials for MSRs with respect to corrosion resistance and interactions between the salt and alloy interface.

36 MATERIALS SCIENCE↗

Removal and Deactivation of Bond Sodium from Fast Reactor Blanket Materials

The disposition of sodium-bonded spent nuclear fuel and blanket materials in a repository is complicated by the presence of sodium metal that is used as a thermal bond between the uranium metal fuel and blanket slugs and their cladding. The concern is that the metallic sodium could react with water, producing explosive hydrogen gas, or could exhibit a pyrophoric character. Thus, experimental studies were performed to investigate and demonstrate the removal and deactivation of bond sodium from blanket material in a dry environment. Specifically, bond sodium was removed from unirradiated Fermi-1 blanket elements and an assembly via a melt-drain-evaporate process using elevated temperature and reduced pressure. The effectiveness of sodium metal removal from the blanket materials and their associated cladding was =99.9998%, based on post-test quantitative analyses. The separated sodium metal was collected and subsequently deactivated by reacting it in a molten state with a controlled addition of ammonium chloride particles atop a molten salt medium. In this process sodium chloride is formed and assimilates into the salt pool. The subsequent deactivation of the bond sodium produced a solid ingot of sodium chloride, potassium chloride, lithium chloride, and cesium chloride that was devoid of sodium metal based on post-test analyses of the salt product. Both the sodium removal and deactivation operations were conducted within a dry inert atmosphere enclosure. The results of this study substantiate a path forward for the disposition of sodium-bonded blanket materials, including 34 metric tons heavy metal in irradiated Fermi-1 blanket material currently stored at Idaho National Laboratory.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Post-irradiation 1600°C Heating Test of AGR-1 UCO Fuel Kernels

Five bare kernels were selected from the U.S. Advanced Gas Reactor (AGR) 1 irradiation experiment Compact 5-3-1 to perform post-irradiation safety tests. The safety test involved heating the kernels in the Fuel Accident Condition Simulator (FACS) furnace in the inert atmosphere to a peak temperature of 1600°C and isothermally holding at this temperature for about 47 hours while collecting fission products released. This test was to assess the retention of fission products in bare kernels without the effects of the other TRISO layers (buffer, IPyC, SiC, and OPyC) or the graphitic matrix material. The bare kernels released nearly 100% of cesium and antimony, while they were able to maintain about 30% of europium, 50% of strontium, and the majority of cerium and ruthenium. In addition, about 48% of the calculated inventory of Kr-85 released during the test, indicating that kernels were capable of retaining a considerable fraction of fission gas K-85 during irradiation.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

2025 Intern Poster

The Hot Fuel Examination Facility (HFEF) at the Materials and Fuels Complex (MFC) houses the largest U.S. inert atmosphere hot cell for nuclear material research. Key features include the precision gamma scanning (PGS), Fuel Accident Condition Simulator (FACS), Neutron Radiography Reactor (NRAD), and the focus of this project, the Metallograph Loading Cell (MET Cell). The MET Cell performs tests on spent nuclear fuel, such as microhardness testing, microscopy, and neutron radiography. However, the MET Cell’s existing pressure and lighting control systems are outdated and inefficient, with inadequate documentation for system changes over time. This project aims to design a new automated control system for the MET Cell, ensuring longevity (minimum ten years), ease of troubleshooting/repair, and integration into the building monitoring system. The design process addressed challenges such as space restrictions, varied voltages within enclosures, sourcing new components, and security limitations. Compliance with NFPA 70, UL508A, MFC Physical Security, and INL Engineering standards was essential. The project involves repurposing an existing PLC to manage lighting and pressure control using digital and analog signals, simplifying wiring, and ensuring thorough documentation for future reference.

42 - ENGINEERING↗

Product specific thermal degradation kinetics of bisphenol F epoxy in inert and oxidative atmospheres using evolved gas analysis–mass spectrometry

Knowledge of the degradation kinetics for polymer materials is important for understanding thermal stability. In this study, evolved gas analysis–mass spectrometry and pyrolysis gas-chromatography-mass spectrometry were evaluated for the potential to deliver additional insight into thermal degradation kinetics of diglycidal ether of bisphenol F (DGEBF) epoxy thermoset under inert and oxidative atmospheres. Degradation products of selected precursor ions were evaluated for their uniqueness to the specific precursor using extracted ion thermographs. Unique mass peaks, solely attributed to a single reaction pathway of a specific product, were determined from extracted ion thermographs and used to determine both activation energy (E a ) and pre-exponential factors for the specific primary reaction pathways. These primary reaction pathways for DGEBF epoxy degradation were then evaluated in the context of transition state theory (TST) and related transition state enthalpies (ΔH ‡ ) and entropies (ΔS ‡ ) of activation to further elucidate the degradation process. It was determined under pyrolysis conditions, as suggested by the E a , the formation of bisphenol F monomer was the rate-limiting step toward the formation of xanthene and phenol. In contrast, under thermo-oxidative conditions, reactions involving oxygen containing species were identified as the rate-limiting step for all observed products based on the large negative ΔS ‡ calculated from TST. This work demonstrates a powerful combination of technique and theory that can provide new insight into the degradation of polymer materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗