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At least 1,351 records · Page 75

Formulation of electrically conductive thermal-control coatings

The development and formulation of electrically conductive thermal control coating was undertaken for use on the International Sun Earth Explorer spacecraft. The primary effort was to develop a coating with a bulk resistivity of less than 100,000 ohm/sqm, an optical absorptance of approximately 0.55, and a normal emittance of 0.90. The required stability in space called for a bulk resistivity of less than 100,000 ohm/sq m, an absorptance of less than 0.67, and a normal emittance of 0.90 after exposure to approximately 4 x 10 to the 16th proton/sq cm of solar-wind particles and 5300 equivalent sun-hours. These exposures represent 2 years of ISEE flight conditions. Both the unsuccessful formulation efforts and the successful use of oxide pigments fired at 1448 K are described. Problems relative to the reactivity of specific coating vehicles exposed to high humidity are discussed.

Shai, M. C.↗

Method for forming thin composite solid electrolyte film for lithium batteries

A composite solid electrolyte film is formed by dissolving a lithium salt such as lithium iodide in a mixture of a first solvent which is a co-solvent for the lithium salt and a binder polymer such as polyethylene oxide and a second solvent which is a solvent for the binder polymer and has poor solubility for the lithium salt. Reinforcing filler such as alumina particles are then added to form a suspension followed by the slow addition of binder polymer. The binder polymer does not agglomerate the alumina particles. The suspension is cast into a uniform film.

Nagasubramanian, Ganesan↗

Impact Melting of Ordinary Chondrite Regoliths and the Production of Fine-grained Fe(sup 0)

The detailed study of individual lunar soil grains provides evidence that the major optical properties of the lunar surface are primarily related to the production of fine-grained (< 20 nm, super-paramagnetic) Fe-particles in agglutinitic impact melts and to iron-rich vapor deposits on the surfaces of individual grains. These Fe-rich materials are derived from oxidized species due to high post-shock temperatures in the presence of solar-wind derived H2; part of the Fe-rich grain surfaces may also be due to sputtering processes. Identical processes were recently suggested for the optical maturation of S-type asteroid surfaces, the parent objects of ordinary chondrites (OCs). OCs, however, do not contain impact-produced soil melts, and should thus also be devoid of impact-triggered vapor condensates. The seeming disparity can only be understood if all OCs resemble relatively immature impact debris, akin to numerous lunar highland breccias. It is possible to assess this scenario by evaluating experimentally whether impact velocities of 5- 6 km/s, typical for the present day asteroid belt, suffice to produce both impact melts and fine-grained metallic iron. We used 125-250 m powders of the L6 chondrite ALH85017. These powders were aliquots from fines that were produced by collisionally disrupting a single, large (461g) chunk of this meteorite during nine impacts and by subjecting the resulting rubble to an additional 50 impacts. As a consequence, the present shock-recovery experiments employ target materials of exceptional fidelity (i.e., a real chondrite that was impact pulverized). The target powders were packed into tungsten-alloy containers to allow for the potential investigation of freshly produced, fine-grained iron and impacted by stainless-steel and tungsten flyer plates; the packing density varied between 38 and 45% porosity. Peak pressures ranged from 14.5 to 67 GPa and were attained after multiple reverberations of the shock wave at the interface of the silicate powder and metal container. Pressures in the 50 to 70 GPa range should be fairly typical for asteroid impacts at approx. 5-6 km/s, yet we note that these pressures refer to those at the projectile/target interface only and that most crater ejecta on OC parent-bodies will have experienced much lower stresses.

Hoerz, Friedrich↗

Electrocomposite of Alumina in Nickel Matrix

Nickel/aluminum oxide composite was electroformed in a sulfamate bath with 50 g/L of 0.05-micron aluminum oxide powder. Different plating methods including direct current plating, periodic pulse plating, and periodic reverse pulse plating were used. With conventional direct current plating, the maximum particle inclusion in the nickel matrix remains about 2% (wt). However, much higher percentile particle inclusions were achieved when a specific pulse reversal plating technique was applied. The particle incorporation approaches theoretical maximum when the deposit thickness per cycle approaches the particle diameter size at lower duty cycle. The highest particle incorporation achieved is 23% (by weight). Conceptual models interpreting the dramatic differences in the results of these plating methods were also proposed.

Xiong-Skiba, Pei↗

Method for forming thin composite solid electrolyte film for lithium batteries

A composite solid electrolyte film is formed by dissolving a lithium salt such as lithium iodide in a mixture of a first solvent which is a cosolvent for the lithium salt and a binder polymer such as polyethylene oxide and a second solvent which is a solvent for the binder polymer and has poor solubility for the lithium salt. Reinforcing filler such as alumina particles are then added to form a suspension followed by the slow addition of binder polymer. The binder polymer does not agglomerate the alumina particles. The suspension is cast into a uniform film.

Nagasubramanian, Ganesan↗

Cold spray chromium coating for nuclear fuel rods

A method is provided for coating the substrate of a component, such as a zirconium alloy cladding tube, for use in a water cooled nuclear reactor under normal operating conditions and under high temperature oxidation conditions. The method includes heating a pressurized carrier gas to a temperature between 200° C. and 1200° C., adding chromium or chromium-based alloy particles having an average diameter of 20 microns or less to the heated carrier gas, and spraying the carrier gas and particles onto the substrate at a velocity, preferably from 800 to 4000 ft./sec. (about 243.84 to 1219.20 meters/sec.), to form a chromium and/or chromium-based alloy coating on the substrate to a desired thickness.

36 MATERIALS SCIENCE↗

Elucidating Arsenic and Selenium Speciation in Coal Fly Ashes

Coal fly ash (CFA) is produced during the coal combustion process and contains trace elements (<100 ppm) including selenium (Se) and arsenic (As), both detrimental for environmental and human health. Existing management strategies for CFAs involve disposal in landfills and ash ponds, as well as beneficial usage in other applications such as in concrete. Both the direct disposal and beneficial usage of CFA raise concerns for environmental hazards due to the potential leaching of Se and As. CFAs were classified as reusable material by the U.S. Environmental Protection Agency (EPA) with the first federal regulation (Disposal of Coal Combustion Residuals from Electric Utilities, CCR) for its disposal established six years ago. During coal combustion process, parameters such as furnace firing type, emissions controls, coal rank, use of additives, and particulate matter controls, could contribute to significant variability in As/Se concentrations and their speciation. Although there have been a handful of studies on As/Se speciation on small sets of samples, they do not fully represent the current state of coal-fired electrical generating units. Little information exists on the detailed speciation (e.g. oxidation state, complexation state) of As/Se in large set of fly ash samples. To better investigate the role of the potential contributing parameters, a large-scale survey study with representative samples of typical coal source and combustion conditions is highly desired. The overall goal of this research is to systematically characterize As and Se speciation of representative coal fly ash samples using state-of-the-art synchrotron based spectroscopic and microscopic techniques, in order to develop a correlation between coal source/type, operation condition, As/Se speciation, and As/Se mobility. A detailed survey study was conducted documenting the current state-of-knowledge on fossil power generating units as a function of coal type/source, operating conditions, environmental control systems, additive use, and fly ash handling methods. Based on this survey, a matrix of fly ash samples representing a range of conditions were chosen and collected. The collected ash samples were analyzed for bulk characteristics such as elemental composition, microstructure, chemical and mineralogical composition, surface area, and particle size distribution. State-of-the-art synchrotron X-ray microscopy and spectroscopy techniques were applied to reveal the molecular scale speciation information of As and Se, such as oxidation state, association with other elements/minerals, and complexation states.

01 COAL, LIGNITE, AND PEAT↗

Effect of Zr Microalloying on Austenite Grain Size of Low-Carbon Steels

The effect of microalloying addition of Zr on the characteristics of inclusions and prior austenite grain sizes following a quench heat treatment has been investigated for two custom-made steels. The average size of particles in the Zr-containing steel is found to be the same as the Zr-free steel (0.49 μm). However, the number of smaller particles in the Zr-containing steel is much higher than the Zr-free steel. The inclusions in the Zr-containing steel are composed of ZrO{sub 2}-TiN-MnS, and inclusions in the Zr-free steel are consisted of TiOx-Ti(C,N). The average prior austenite grain size of the Zr-containing steel is consistently smaller than that of the Zr-free steel, due to a large number of fine oxide inclusions and Ti(C,N) precipitates, working to pin the austenite grain boundaries at temperatures up to 1673 K (1400 °C). The grain refinement mechanisms by inclusions through the addition of Zr are discussed via thermodynamic and kinetic calculations.

36 MATERIALS SCIENCE↗

The response of thermally and optically stimulated luminescence from Al2O3:C to high-energy heavy charged particles

The thermoluminescence (TL) and optically stimulated luminescence (OSL) response of Al2O3 dosimeters to high-energy heavy charged particles (HCP) has been studied using the heavy ion medical accelerator at Chiba, Japan. The samples were Al2O3 single-crystal chips, of the type usually known as TLD-500, and Luxel(TM) dosimeters (Al2O3:C powder in plastic) from Landauer Inc. The samples were exposed to 4He (150 MeV/u), 12C (400 MeV/u), 28Si (490 MeV/us) and 56Fe (500 MeV/u) ions, with linear energy transfer values covering the range from 2.26 to 189 keV/micrometers in water and doses from 1 to 100 mGy (to water). A 90Sr/90Y beta source, calibrated against a 60Co secondary standard, was used for calibration purposes. For OSL, we used both continuous-wave OSL measurements (CW-OSL, using green light stimulation at 525 nm) and pulsed OSL measurements (POSL, using 532 nm stimulation from a Nd:YAG Q-switched laser). The efficiencies (eta HCP, gamma) of the different HCPs at producing OSL or TL were observed to depend not only upon the linear energy transfer (LET) of the HCP, but also upon the sample type (single crystal chip or Luxel(TM)) and the luminescence method used to define the signal--i.e. TL, CW-OSL initial intensity, CW-OSL total area, or POSL. Observed changes in shape of the decay curve lead to potential methods for extracting LET information of unknown radiation fields. A discussion of the results is given, including the potential use of OSL from Al2O3 in the areas of space radiation dosimetry and radiation oncology. c2004 Elsevier Ltd. All rights reserved.

Heavy Ions↗

Global and Regional Impacts of HONO on the Chemical Composition of Clouds and Aerosols

Recently, realistic simulation of nitrous acid (HONO) based on the HONO/NO(sub x) ratio of 0.02 was found to have a significant impact on the global budgets of HO(sub x) (OH + HO2) and gas phase oxidation products in polluted regions, especially in winter when other photolytic sources are of minor importance. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that simulating realistic HONO levels can significantly enhance aerosol sulphate (S(VI)) due to the increased formation of H2SO4. Even though in-cloud aqueous phase oxidation of dissolved SO2 (S(IV)) is the main source of S(VI), it appears that HONO related enhancement of H2O2 does not significantly affect sulphate because of the predominantly S(IV) limited conditions, except over eastern Asia. Nitrate is also increased via enhanced gaseous HNO3 formation and N2O5 hydrolysis on aerosol particles. Ammonium nitrate is enhanced in ammonia-rich regions but not under ammonia-limited conditions. Furthermore, particle number concentrations are also higher, accompanied by the transfer from hydrophobic to hydrophilic aerosol modes. This implies a significant impact on the particle lifetime and cloud nucleating properties. The HONO induced enhancements of all species studied are relatively strong in winter though negligible in summer. Simulating realistic HONO levels is found to improve the model measurement agreement of sulphate aerosols, most apparent over the US. Our results underscore the importance of HONO for the atmospheric oxidizing capacity and corroborate the central role of cloud chemical processing in S(IV) formation.

HONO↗

Global and Regional Impacts of HONO on the Chemical Composition of Clouds and Aerosols

Recently, realistic simulation of nitrous acid (HONO) based on the HONO / NOx ratio of 0.02 was found to have a significant impact on the global budgets of HOx (OH + HO2) and gas phase oxidation products in polluted regions, especially in winter when other photolytic sources are of minor importance. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that simulating realistic HONO levels can significantly enhance aerosol sulphate (S(VI)) due to the increased formation of H2SO4. Even though in-cloud aqueous phase oxidation of dissolved SO2 (S(IV)) is the main source of S(VI), it appears that HONO related enhancement of H2O2 does not significantly affect sulphate because of the predominantly S(IV) limited conditions, except over eastern Asia. Nitrate is also increased via enhanced gaseous HNO3 formation and N2O5 hydrolysis on aerosol particles. Ammonium nitrate is enhanced in ammonia-rich regions but not under ammonia-limited conditions. Furthermore, particle number concentrations are also higher, accompanied by the transfer from hydrophobic to hydrophilic aerosol modes. This implies a significant impact on the particle lifetime and cloud nucleating properties. The HONO induced enhancements of all species studied are relatively strong in winter though negligible in summer. Simulating realistic HONO levels is found to improve the model measurement agreement of sulphate aerosols, most apparent over the US. Our results underscore the importance of HONO for the atmospheric oxidizing capacity and corroborate the central role of cloud chemical processing in S(IV) formation

Global and regional impacts↗

Enhanced Methanol Synthesis from CO 2 Hydrogenation Achieved by Tuning the Cu–ZnO Interaction in ZnO/Cu 2 O Nanocube Catalysts Supported on ZrO 2 and SiO 2

The nature of the Cu–Zn interaction and especially the role of Zn in Cu/ZnO catalysts used for methanol synthesis from CO 2 hydrogenation are still debated. Migration of Zn onto the Cu surface during reaction results in a Cu–ZnO interface, which is crucial for the catalytic activity. However, whether a Cu–Zn alloy or a Cu–ZnO structure is formed and the transformation of this interface under working conditions demand further investigation. Here, ZnO/Cu 2 O core–shell cubic nanoparticles with various ZnO shell thicknesses, supported on SiO 2 or ZrO 2 were prepared to create an intimate contact between Cu and ZnO. The evolution of the catalyst’s structure and composition during and after the CO 2 hydrogenation reaction were investigated by means of operando spectroscopy, diffraction, and ex situ microscopy methods. The Zn loading has a direct effect on the oxidation state of Zn, which, in turn, affects the catalytic performance. High Zn loadings, resulting in a stable ZnO catalyst shell, lead to increased methanol production when compared to Zn-free particles. Low Zn loadings, in contrast, leading to the presence of metallic Zn species during reaction, showed no significant improvement over the bare Cu particles. Therefore, our work highlights that there is a minimum content of Zn (or optimum ZnO shell thickness) needed to activate the Cu catalyst. Furthermore, in order to minimize catalyst deactivation, the Zn species must be present as ZnO x and not metallic Zn or Cu–Zn alloy, which is undesirably formed during the reaction when the precatalyst ZnO overlayer is too thin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Efficient Control of Atom Arrangement in Ternary Metal Chalcogenide Nanoparticles Using Precursor Oxidation State

Controlling both the concentration and the distribution of elements in a given material is often crucial to extracting and optimizing synergistic properties of the various constituents. An interesting class of such multielement materials is metal chalcogenide nanoparticles, which exhibit a wide range of composition-dependent optoelectronic properties including both bandgap-mediated processes and localized surface plasmon resonance properties, each of which is useful in applications ranging from energy conversion to sensing. Because metal chalcogenide nanoparticles can support several different metal elements in a variety of chalcogen lattices, this material class has particularly benefited from the ability to control both atom concentration and atom arrangement to tailor final particle properties. The primary method to access complex, multimetallic chalcogenide particles is via a postsynthetic cation exchange strategy. One-pot syntheses have been less explored to access these complex particles, although this route is desirable for economy and scalability. In this work, we compare the composition and morphology outcomes from cation exchange and one-pot preparation approaches using a Cu/Ag/Se system, which is already known to exhibit both binary and ternary metal chalcogenide phases. We show that at similar concentrations of the two metal cations, initial reaction conditions for the one-pot method yield multicomponent nanoparticles, whereas cation exchange yields homogeneous ternary metal chalcogenide structures. We then show that by tuning the precursor oxidation state for the one-pot method, this approach can be used to access homogeneous ternary metal chalcogenide particles that are similar in atom arrangement to the particles obtained using cation exchange. Taken together, our results demonstrate reliable synthetic methods that yield a variety of controlled compositions and composition morphologies in the Cu/Ag/Se system. Importantly, we demonstrate that this entire collection of architectures can all be accessed via a one-pot method simply by modifying metal precursor chemistry. The mechanistic insights gained and the resulting streamlined syntheses outlined indicate pathways to easily scaled, highly tailorable syntheses for rapid translation into downstream technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct high-altitude observations of 2-methyltetrols in the gas- and particle phase in air masses from Amazonia

We present direct observations of 2-methyltetrol (C 5 H 12 O 4 ) in the gas- and particle phase from the deployment of a Filter Inlet for Gases and Aerosols coupled to a Time-of-Flight Chemical Ionization Mass Spectrometer (FIGAERO-CIMS) during the Southern Hemisphere High Altitude Experiment on Particle Nucleation and Growth (SALTENA), which took place between December 2017 and June 2018 at the high-altitude Global Atmosphere Watch station Chacaltaya (CHC) located at 5240 m a s l in the Bolivian Andes. 2-Methyltetrol signals were dominant in a factor resulting from Positive Matrix Factorization (PMF) identified as influenced by Amazon emissions. We combine these observations with investigations of isoprene oxidation chemistry and uptake in an isolated deep convective cloud in the Amazon using a photochemical box model with coupled cloud microphysics and show that, likely, 2-methyltetrol is taken up by hydrometeors or formed in situ in the convective cloud, and then transported in the particle phase in the cold environment of the Amazon outflow and to the station, where it partially evaporates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polymersomes Decorated with the SARS-CoV-2 Spike Protein Receptor-Binding Domain Elicit Robust Humoral and Cellular Immunity

The COVID-19 pandemic underscores the need for rapid, safe, and effective vaccines. In contrast to some traditional vaccines, nanoparticle-based subunit vaccines are particularly efficient in trafficking antigens to lymph nodes, where they induce potent immune cell activation. Here, we developed a strategy to decorate the surface of oxidation-sensitive polymersomes with multiple copies of the SARS-CoV-2 spike protein receptor-binding domain (RBD) to mimic the physical form of a virus particle. We evaluated the vaccination efficacy of these surface-decorated polymersomes (RBD surf ) in mice compared to RBD-encapsulated polymersomes (RBD encap ) and unformulated RBD (RBD free ), using monophosphoryl-lipid-A-encapsulated polymersomes (MPLA PS) as an adjuvant. While all three groups produced high titers of RBD-specific IgG, only RBD surf elicited a neutralizing antibody response to SARS-CoV-2 comparable to that of human convalescent plasma. Moreover, RBD surf was the only group to significantly increase the proportion of RBD-specific germinal center B cells in the vaccination-site draining lymph nodes. Both RBD surf and RBD encap drove similarly robust CD4 + and CD8 + T cell responses that produced multiple Th1-type cytokines. We conclude that a multivalent surface display of spike RBD on polymersomes promotes a potent neutralizing antibody response to SARS-CoV-2, while both antigen formulations promote robust T cell immunity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Gel composite electrolyte – an effective way to utilize ceramic fillers in lithium batteries

Achieving synergy between ion-conducting polymers and ceramics in a composite electrolyte has been proven to be difficult as the complicated ceramic/polymer interface presents challenges to understand and control. In this work, we report a strategy to utilize discrete ceramic fillers to form a gel composite electrolyte with enhanced transport properties for lithium metal batteries. The matrix of the composite membrane is crosslinked poly(ethylene oxide) with bis(trifluoromethane)sulfonimide lithium salt (LiTFSI). The membrane is plasticized with tetraethylene glycol dimethyl ether (TEGDME). The incorporation of doped-lithium aluminum titanium phosphate particles (LICGC™) into the membrane greatly improves the membrane's cycling characteristics against the lithium electrode, exhibiting lower interfacial impedance, lower overpotential and higher rate capability. The underpinnings of the superior performance of the gel composite electrolyte are discussed in depth. LICGC™ can immobilize the TFSI - anions in the polymer matrix and simultaneously promote Li+ transport by increasing the plasticizer to Li + ratio. Further, the transport enhancement is achieved without sacrificing mechanical properties. The composite membrane shows significantly improved handleability and processability. This work sheds light on the design strategy for a safe electrolyte towards stable Li metal batteries.

25 ENERGY STORAGE↗

Surface Tagging of Al 6061-T6 using Photoluminescent Oxides

The goal of tagging nuclear fuels (or related materials, such as fuel cladding) is to provide a persistent marker, traceable to the fuel manufacturer, that can be detected after some length of time, likely after the fuel has been lost, rerouted, or partially destroyed. Ideally, the tag is complicated enough to encode data pertaining to the provenance (manufacturer, date or time, constituents, etc.) and robust enough to survive in-pile exposure and/or further destruction. The taggant should not change the behavior or performance of the fuel in any meaningful way. Photoluminescent tagging was an attractive solution to many of these challenges, as it is undetectable under normal lighting conditions, visible to the naked eye under specific lighting conditions, does not require a significant quantity of material to be photoluminescent, observable with simple commercial detection tools, and is versatile and robust in application. In FY23, the team focused on embedding photoluminescent taggants onto the replicate fuel cladding surface using welding. From a welding standpoint, photoluminescent taggants, in the form of oxides, are a viable option for tagging because the taggants have high melting points, and thus likely to survive welding temperatures (i.e., remain as a secondary phase particle and maintain luminescent properties). Additionally, these taggants have the potential to act as a metal matrix composite which may increase the strength-to-weight ratio, stiffness, and ductility of the base material, all beneficial to cladding and fuel performance.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

A sputtering derived atomic oxygen source for studying fast atom reactions

A technique for the generation of fast atomic oxygen was developed. These atoms are created by ion beam sputtering from metal oxide surfaces. Mass resolved ion beams at energies up to 60 KeV are produced for this purpose using a 150 cm isotope separator. Studies have shown that particles sputtered with 40 KeV Ar(+) on Ta2O5 were dominantly neutral and exclusively atomic. The atomic oxygen also resided exclusively in its 3P ground state. The translational energy distribution for these atoms peaked at ca 7 eV (the metal-oxygen bond energy). Additional measurements on V2O5 yielded a bimodal distribution with the lower energy peak at ca 5 eV coinciding reasonably well with the metal-oxygen bond energy. The 7 eV source was used to investigate fast oxygen atom reactions with the 2-butene stereoisomers. Relative excitation functions for H-abstraction and pi-bond reaction were measured with trans-2-butene. The abstraction channel, although of minor relative importance at thermal energy, becomes comparable to the addition channel at 0.9 eV and dominates the high-energy regime. Structural effects on the specific channels were also found to be important at high energy.

Ferrieri, Richard A.↗