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Control of Permanent Porosity in Type 3 Porous Liquids via Solvent Clustering

Porous liquids (PLs) are an exciting new class of materials for carbon capture due to their high gas adsorption capacity and ease of industrial implementation. They are composed of sorbent particles suspended in a nonadsorbed solvent, forming a liquid with permanent porosity. While PLs have a vast number of potential compositions based on the number of solvents and sorbent materials available, most of the research has been focused on the selection of the sorbent rather than the solvent. Therefore, PL design criteria on the supramolecular structures of the solvent are explored to create a fundamental understanding of how the solvent enables PL formation for rapid discovery of new PL compositions. Atomistic molecular dynamics simulation of eight solvents with a range of molecular sizes, shapes, and intramolecular bonding was performed, identifying that the shape and size of molecular clusters formed in the solvent are the driving predictor of PL formation rather than the size of the individual solvent molecule. The results demonstrate a significant departure from common approaches to PL formation based on the steric exclusion of solvent molecules from the sorbent via the size of the pore aperture. A modeling and experimental validation study further supports these findings. In conclusion, through this computational material design study, a previously unexplored mechanism in PL formation, solvent–solvent clustering, is identified as a critical factor for the accelerated discovery of liquid phase carbon capture materials.

Carbon capture↗

The Effects on Non-Actinide Impurities from Aging Heat Source Plutonium in Stainless Steel Containers

Replacing the tantalum vials used for 238 PuO 2 sample collection and storage with stainless steel sample vials has several advantages. These advantages include a decreased cost, better material availability, and ease of fabrication. However, it must first be demonstrated that the alloying elements contained in stainless steel are not leached into the 238 PuO 2 such that product specifications are exceeded. In order to determine the suitability of stainless steel for this application, two seperate 238 PuO 2 fuel lots were investigated. These two fuel lots had been stored in stainless steel containers since their first sampling date of March of 2015, and were again sampled in February of 2019.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Aperture, A Large Telescope Using Magnetostriction For Post Deployment Corrections: Final Technical Report of NASA Innovative Advanced Concepts (NIAC) Phase I

In summary, astronomical as well as Earth observing applications of the future are counting on larger aperture telescopes than are currently available. Several groups have been working on the topic of enabling large (about 16-m diameter) UV-Vis telescopes for many years. The unique feature of our concept is that magnetic films are used rather than electrostatic films or piezo-electrostatic pads. Our magnetic film concept allows for contiguous correction along the surface, does not require a hard wire connection, and does not require continuous external application of the field. There are many unknowns related to the initial accuracy of the deployed figure prior to the magnetic write head corrections. The length scale over which the corrections need to be applied is also of concern. For, although approximately mm length scale corrections can be made with the MSM plus write head technology, the number of 1 mm² patches in a 16 m diameter mirror is too large to contemplate applying individual corrections to each individual patch. However, deployment strategies and the materials available continue to evolve, in particular shape memory composites (SMCs) [34] or alloys (SMAs) [41], such that at this time we see no show-stoppers for this concept. Furthermore, the ability to tune deformations down to much (factors of 10-100) smaller (m) scale opens the futuristic possibility of improving the figure well beyond Strehl values of 90%.

APERTURE↗

Assessing the Performance of a Circular Economy for Wind Energy Technologies: A Summary of Three Analytical Tools

A circular economy emphasizes the efficient use of all resources and presents opportunities for addressing series of economic and environmental objectives at local, regional, and national levels. Despite anticipated overall benefits to society, the transition to a circular economy is likely to create regional differences in impacts. As a result, it is important to evaluate the performance and tradeoffs associated with circular economy transitions. This poster summaries three previously published analytical tools that were used to assess the performance of developing a circular economy for wind energy technologies: the Renewable Energy Materials Properties Database (REMPD), a circular economy agent-based model for wind blades (CE Wind ABM), and the Circular Economy Lifecycle Assessment and Visualization (CELAVI) framework. The REMPD is a comprehensive database of materials used in wind and solar plants, including material quantities and physical materials availability. The CE Wind ABM allows us to understand how wind stakeholders' end-of-life behaviors influence wind blade circularity and evaluate the impact of regional variables (e.g., logistics and transportation). And, the CELAVI framework is a modular framework that can be used to evaluate the impacts associated with circular economy transitions. These three analytical tools have been applied to evaluate circular economy transitions for wind energy technologies and they could be expanded to other technologies and products.

agent-based modeling↗

Effects of material composition on the ablation performance of low density elastomeric ablators

The ablation performance of materials composed of various concentrations of nylon, hollow silica spheres, hollow phenolic spheres, and four elastomeric resins was determined. Both blunt-body and flat-panel specimens were used, the cold-wall heating-rate ranges being 0.11 to 0.8 MW/sq m, respectively. The corresponding surface pressure ranges for these tests were 0.017 to 0.037 atmosphere and 0.004 to 0.005 atmosphere. Some of the results show that (1) the addition of nylon significantly improved the ablation performance, but the nylon was not compatible with one resin system; (2) panel and blunt-body specimen data do not show the same effect of phenolic sphere content on ablation effectiveness; and (3) there appears to be an optimum concentration of hollow silica spheres for good ablation performance. The composition of an efficient, nonproprietary ablator for lifting body application is identified and the ablation performance of this ablator is compared with the performance of three commercially available materials.

Tompkins, S. S.↗

Evaluating Technology Adoption Risks in Early-Stage Materials Research

Development of new technologies often begins with fundamental materials science research. Decisions at this stage can shape factors related to the eventual adoption readiness of the technology, such as process scalability or materials availability. Here we present the early-Stage Technology Evaluation for Adoption Risks (STEAR) framework as a method for qualitatively assessing metrics spanning four categories of adoption risks: value proposition, market acceptance, resource maturity, and license to operate. We conduct a case study applying STEAR to different methanol production processes at a range of technology readiness levels and demonstrate how the assessment identifies key challenges related to adoption readiness. Finally, we discuss efforts to expand the applicability and utility of STEAR, including focus group feedback and complementary quantitative analysis methods.

36 MATERIALS SCIENCE↗

Iodine Removal from Carbonate-Containing Alkaline Liquids Using Strong Base Resins, Hybrid Resins, and Silver Precipitation

The ability of several material types to remove aqueous iodine from a mildly alkaline, carbonate-rich nuclear waste stream was evaluated: strong base anion exchange resins (SBAR), hybrid resins, Ag-containing materials and Bi-containing hybrid resins. A combination of batch testing and flow through column testing were used in the evaluation. In batch testing, hybrid resins CHM-20, SIR-110-CE and RTBI were shown to have high efficiency for the removal of both iodide and iodate simultaneously, while Ag-containing materials and SBAR demonstrated high capacity for iodide removal. One example of each material type (CHM-20, A532E and Ionex 400) were further evaluated for their sorption isotherms and column performance. The Langmuir isotherm, or a Langmuir-Freundlich hybrid isotherm, best described the sorption of iodide to the CHM-20 hybrid resin and Purolite A532E. The Freundlich isotherm best described the uptake of iodate to CHM-20 and A532E and for both iodide and iodate to the Ag-containing Ionex-400. In column testing the Purolite A532E had exceptional performance for overall iodide removal. With the capacity demonstrated the A532E resin would exceed Class C waste classification before breakthrough initiated, and column change outs in processing would be dictated by eventual waste classification, not breakthrough. The Ionex 400, a Ag-zeolite, was observed to degrade over time in the column in the mild alkaline conditions whereas the hybrid CHM-20 was limited in the single pass through design and would be best suited for applications where iodide and iodate are present and recirculation of the column effluent is feasible. Here this work highlights the feasibility of commercially available materials to separate radioiodine from liquid environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Study of Additive Manufacturing Applications to Geothermal Technologies Final Project Report

This report summarizes work performed to assess the potential for utilizing additive manufacturing (AM) to substantially improve either the availability, performance or cost basis for tools and components that are required for geothermal energy production. A systematic cataloging of geothermal activities, associated technologies, and current manufacturing methods was first undertaken. This included literature reviews as well as interviews with subject matter experts, service companies and OEMs. An industry workshop was held as part of this portion of the project to obtain input and concerns from a broad range of OEMs, service providers and end users. This workshop was also used to gage the current level of AM activity in industry, receptiveness to the use of AM manufactured parts, and any up front concerns that may exist. A summary of the workshop is presented in this report. Representative components and assemblies and their current manufacturing methods were then analyzed by additive manufacturing experts at a company called Senvol to determine the feasibility and required steps for producing parts by additive manufacturing. A step by step description of conventional manufacturing of the parts was also performed to establish a manufacturing baseline for comparison purposes. This analysis also considered and described the benefits of additively manufacturing the parts in terms of specific AM systems, material availability for AM, dimensional requirements and potential economic advantages. Details of the manufacturability assessment were summarized in a report which is included as a chapter in this document. The analysis of the AM subject matter experts was then be used by techno-economic analysts to perform a comparative economic evaluation of the manufacturing of select technologies by AM and conventional approaches. This activity leveraged ORNL expertise and prior experience in other applications. A framework based on assessing cost, volume production considerations, and time to manufacture was created to more easily discern the advantages or disadvantages of additive versus conventional manufacturing methods. The report concludes with a general assessment of the current applicability of AM for geothermal technologies, AM gaps and needs related to typical geothermal hardware, and the potential benefits and impacts of AM to geothermal energy production.

15 GEOTHERMAL ENERGY↗

Initiation of Experimental Campaign to Address Knowledge Gaps Related to Simultaneous Thermal and Gamma Radiation Aging of Crosslinked Polyethylene and Ethylene-Propylene Rubber Cable Insulation

Key cable knowledge gaps identified in the Expanded Materials Degradation Assessment (EMDA) volume on Aging of Cables and Cable Systems (Volume 5) specifically relate to the combined effects of thermal and gamma irradiation stresses on cable insulation materials. These include dose rate effects (DRE), inverse temperature effects (ITE), and synergistic effects (S/E). Extent of radiation-induced polymer degradation is proportional to absorbed dose, but DRE describe the phenomenon in which degree of damage is based not only on total dose, but also on the dose rate experienced during dose accumulation. This can be particularly complicated in the presence of thermal stress as a material spends more time at elevated temperature to receive the same total dose at a lower dose rate. Rates of cable polymer degradation generally increases with temperature, but ITE describes the situation in which polymer material damage under irradiation is greater at lower temperatures than at higher temperatures. Finally, S/E describe the concept that the mechanism of polymer material degradation when exposed to thermal aging and radiation aging in succession may be different than when exposed to thermal and radiation aging concurrently. The experimental campaign at the Pacific Northwest National Laboratory (PNNL) described in this report seeks to address these knowledge gaps through investigation of the degradation of relevant cable insulation materials at select conditions using controlled temperatures, dose rates and total doses. Insulation materials considered were chosen to represent those most commonly found in U.S. nuclear power plants in terms of manufacturers and polymer systems. They include products from manufactures including The Rockbestos Company; The Okonite Company; Boston Insulated Wire & Cable Company; Kerite Company; Anaconda Company; Brand Rex, Inc.; and Samuel Moore Company. The products include the most ubiquitous cross-linked polyethylene (XLPE) and ethylene-propylene rubber (EPR) classes of insulation polymer. Circulating air ovens with remote temperature sensing and control are positioned within the gamma irradiation beam to enable controlled temperatures during radiation exposure. Dose rates are controlled through repeatable positioning of specimens at determined distances from the Cobalt-60 gamma source. Total absorbed doses for comparing temperature and dose rate effects are controlled by removing samples from exposure at pre-determined time points. The effects of gamma beam geometry, source decay and attenuation due to samples, ovens and racks are determined and controlled for using local point dosimetry. The temperature, dose and dose rates selected for the experimental campaign described in this report were determined following input from a range of stakeholders and intended to balance the constraints of the experimental capabilities, available material, project timeline and project funding with the value of the effort in narrowing EMDA-identified knowledge gaps. Results from this campaign are anticipated to reduce uncertainty in the understanding of cable material degradation behavior in nuclear power plant environments and thereby support cable aging management in long term operation.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Human Space Exploration: The Moon, Mars, and Beyond

America is returning to the Moon in preparation for the first human footprint on Mars, guided by the U.S. Vision for Space Exploration. This presentation will discuss NASA's mission, the reasons for returning to the Moon and going to Mars, and how NASA will accomplish that mission in ways that promote leadership in space and economic expansion on the new frontier. The primary goals of the Vision for Space Exploration are to finish the International Space Station, retire the Space Shuttle, and build the new spacecraft needed, to return people to the Moon and go to Mars. The Vision commits NASA and the nation to an agenda of exploration that also includes robotic exploration and technology development, while building on lessons learned over 50 years of hard-won experience. Why the Moon? Many questions about the Moon's potential resources and how its history is linked to that of Earth were spurred by the brief Apollo explorations of the 1960s and 1970s. This new venture will carry more explorers to more diverse landing sites with more capable tools and equipment for extended expeditions. The Moon also will serve as a training ground before embarking on the longer, more difficult trip to Mars. NASA plans to build a lunar outpost at one of the lunar poles, learn to live off the land, and reduce dePendence on Earth for longer missions. America needs to extend its ability to survive in hostile environments close to our home planet before astronauts will reach Mars, a planet very much like Earth. NASA has worked with scientists to define lunar exploration goals and is addressing the opportunities for a range of scientific study on Mars. In order to reach the Moon and Mars within a lifetime and within budget, NASA is building on common hardware, shared knowledge, and unique experience derived from the Apollo Saturn, Space Shuttle and contemporary commercial launch vehicle programs. The journeys to the Moon and Mars will require a variety of vehicles, including the Ares I Crew Launch Vehicle, which transports the Orion Crew Exploration Vehicle, and the Ares V Cargo Launch Vehicle, which transports the Lunar Surface Access Module. The architecture for the lunar missions will use one launch to ferry the crew into orbit, where it will rendezvous with the Lunar Module in the Earth Departure Stage, which will then propel the combination into lunar orbit. The imperative to explore space with the combination of astronauts and robots will be the impetus for inventions such as solar power and water and waste recycling. This next chapter in NASA's history promises to write the next chapter in American history, as well. It will require this nation to provide the talent to develop tools, machines, materials, processes, technologies, and capabilities that can benefit nearly all aspects of life on Earth. Roles and responsibilities are shared between a nationwide Government and industry team. The Exploration Launch Projects Office at the Marshall Space Flight Center manages the design, development, testing, and evaluation of both vehicles and serves as lead systems integrator. A little over a year after it was chartered, the Exploration Launch Projects team is testing engine components, refining vehicle designs, performing wind tunnel tests, and building hardware for the first flight test of Ares I-l, scheduled for spring 2009. The U.S. Vision for Space Exploration lays out a roadmap for a long-term venture of discovery. This endeavor will inspire and attract the best and brightest students to power this nation successfully to the Moon, Mars, and beyond. If one equates the value proposition for space with simple dollars and cents, the potential of the new space economy is tremendous, from orbital space delivery services for the International Space Station to mining and solar energy collection on the Moon and asteroids. The Vision for Space Exploration is fundamentally about bringing the resources of the solar system within the economic sphere of humaind. Given the immense size of our solar system, the amount of available material and energy within it present an enormous economic opportunity.

Sexton, Jeffrey D.↗

Vertically Self-Oriented, Ultrafast 1D ZnO:Li Nanorods as Scintillators for Thermal Neutron Detection

Detection of special nuclear materials (SNMs) is of vital importance in the prevention of nuclear terrorism and to secure states’ national security. Neutron detection is a particularly useful tool to identify SNM, and neutron-sensitive scintillators have many promising properties, such as ease of use, good time resolution, and high detection efficiency. In this work, we develop highly stable, self-oriented, ultrafast 1D ZnO:Li (and codoped with Al, Ga, and In) nanorods (NRs) as thermal neutron-sensitive scintillators. Lithium-6 has high thermal neutron cross section for the (n, α) reaction in ZnO:Li scintillators which have a vertical nano array design greatly increasing the effective surface area and scintillation efficiency. Cost-effective low-temperature (95 °C) hydrothermal growth is used to obtain highly crystalline ZnO:Li nano scintillators by combining nuclear range data and electron transport mechanisms. Among the studies using low-temperature hydrothermal synthesis and a relatively low annealing temperature (≈350 °C) along with optimized NRs (length ≈ 5–8 μm, mean diameter ≈ 700 nm) for thermal neutron detection, this study reports the shortest scintillation decay time (≈ 470 ps) so far to the best of our knowledge. In conclusion, this nano array scintillator combines the advantages of a low-cost growth technique with environmentally friendly and widely available materials.

Ions↗

Operando bulk and interfacial characterization for electrochemical energy storage: Case study employing isothermal microcalorimetry and X-ray absorption spectroscopy

Abstract The global shift to electricity as the main energy carrier will require innovation in electrochemical energy storage (EES). EES systems are the key to the “electron energy economy,” minimizing losses and increasing reliability between energy supply and demand. However, steep challenges such as cost, cycle/calendar life, energy density, material availability, and safety limit widespread adoption of batteries for large-scale grid and vehicle applications. Battery innovation that meets today’s challenges will require new chemistries, which can originate from understanding charge transport phenomena at multiple time and length scales. The advancement of operando characterization can expedite this progress as changes can be observed during battery function. This article highlights progress in bulk and interfacial operando characterization of batteries. Specifically, a case study involving Fe 3 O 4 is provided demonstrating that combining X-ray absorption spectroscopy and isothermal microcalorimetry can provide real-time characterization of productive faradaic redox processes and parasitic interfacial reactions during (de)lithiation. Graphic abstract

36 MATERIALS SCIENCE↗

Design for Recycling Principles Applicable to Selected Clean Energy Technologies: Crystalline-Silicon Photovoltaic Modules, Electric Vehicle Batteries, and Wind Turbine Blades

Abstract The global growth of clean energy technology deployment will be followed by parallel growth in end-of-life (EOL) products, bringing both challenges and opportunities. Cumulatively, by 2050, estimates project 78 million tonnes of raw materials embodied in the mass of EOL photovoltaic (PV) modules, 12 billion tonnes of wind turbine blades, and by 2030, 11 million tonnes of lithium-ion batteries. Owing partly to concern that the projected growth of these technologies could become constrained by raw material availability, processes for recycling them at EOL continue to be developed. However, none of these technologies are typically designed with recycling in mind, and all of them present challenges to efficient recycling. This article synthesizes and extends design for recycling (DfR) principles based on a review of published industrial and academic best practices as well as consultation with experts in the field. Specific principles developed herein apply to crystalline-silicon PV modules, batteries like those used in electric vehicles, and wind turbine blades, while a set of broader principles applies to all three of these technologies and potentially others. These principles are meant to be useful for stakeholders—such as research and development managers, analysts, and policymakers—in informing and promoting decisions that facilitate DfR and, ultimately, increase recycling rates as a way to enhance the circularity of the clean energy economy. The article also discusses some commercial implications of DfR. Graphical Abstract

36 MATERIALS SCIENCE↗

Identification and characterization of extraterrestrial non-chondritic interplanetary dust

Interplanetary dust particles (IDPs) are among the most pristine and primitive extraterrestrial materials available for direct study. Most of the stratospheric particles selected for study from the JSC Curatorial Collection were chondritic in composition (major element abundances within a factor of two of chondritic meteorites) because this composition virtually ensures that the particle is from an extraterrestrial source. It is likely that some of the most interesting classes of IDP's have not been recognized simply because they are not chondritic or do not fit established criteria for extraterrestrial origin. Indeed, mass spectroscopy data from the Giotto Flyby of comet Halley indicate that a substantial fraction of the dust is in the submicron size range and that a majority of these particles contain C, H, O, and/or N as major elements. The preponderance of CHON particles in the coma of Halley implies that similar particles may exist in the JSC stratospheric dust collection. However, the JSC collection also contains a variety of stratospheric contaminants from terrestrial sources which have these same characteristics. Because established criteria for extraterrestrial origin may not apply to such particles in individual cases, and integrated approach is required in which a variety of analysis techniques are applied to the same particle. Non-chondritic IDP's, like their chondritic counterparts, can be used to elucidate pre- and early solar system processes and conditions. The study of non-chondritic IDP's may additionally yield unique information which bears on the nature of cometary bodies and the processing of carbonaceous and other low atomic number materials. A suite of complementary techniques, including Low Voltage Scanning Electron Microscopy (LVSEM), Energy-Dispersive X-ray Microanalysis (EDX), Secondary Ion Mass Spectrometry (SIMS) isotope-ratio imaging and Analytical Electron Microscopy (AEM), were utilized to accomplish the following two objectives: (1) to develop criteria for the unequivocal identification of extraterrestrial non-chondritic IDP's; and (2) to infer IDP parent body, solar nebula, and pre-solar conditions through the study of phases, textures, and components contained within non-chondritic IDP's. The general approach taken is designed to maximize the total information obtained from each particle. Techniques will be applied in order from least destructive to most destructive.

Blake, D. F.↗

Reduction of CO 2 Emissions Through Lightweight Body Panels (Project Final Report)

Lightweight construction is an integral part of Volkswagen’s overall strategy of reducing CO 2 emissions. Due to its low cost, steel is the most commonly used material for automotive exterior body panels today. Unfortunately, steel has a high density, resulting in a relatively low specific strength. Glass fiber based sheet molding compounds (SMC) provide high properties in combination with lower density. The high specific strength of SMC offers an enormous lightweight potential. To unlock the full potential of SMC materials in combination with cutting edge manufacturing processes, Volkswagen Group of America worked together with IACMI (Institute for Advanced Composites Manufacturing Innovation) and the academic partners: University of Tennessee Knoxville, Purdue University and Michigan State University; as well as the industry partners: Ashland, IDI, Owens Corning and Continental Structural Plastics. Leveraging the expertise of all project partners, reaching over the entire supply chain the project demonstrated the potential of these materials. This report will highlight the major steps in the development process on the way to technology readiness for SMC using the example of the Volkswagen Atlas Liftgate. Over the 36-month period of the project, the work focused on three R&D areas: material development, design and simulation, and development of the manufacturing process. Material selection included alternative fibers and resin systems, and accounted for material availability, properties, and cost-efficiency. The work undertaken in the field of design and simulation has pushed the envelope of short fiber reinforced thermoset molding compound process simulation. Design iterations were virtually tested, while the final design was used to validate the simulation software against physical parts. Manufacturing development used cutting-edge technology, while experts along the supply chain were working together to ensure the best possible results. In the final stage of the project, liftgates were molded, trimmed, bonded, painted and assembled before exhaustive testing. The result is an e-coat (electrophoretic dip coating) capable Class-A SMC liftgate, which is ready for high-volume production, and can be used as a technology demonstrator. The prototypes manufactured in the scope of this work have exhibited a mass reduction for the Volkswagen Atlas liftgate of up to 35% compared to the series production steel version, without a degradation of the functionalities.

36 MATERIALS SCIENCE↗

Identification and recovery of rare-earth permanent magnets from waste electrical and electronic equipment

Highlights: • Different WEEE were analyzed and the rare-earth permanent magnets were collected. • Chemical composition evolution of Nd-Fe-B alloys over the years is illustrated. • Loudspeakers from laptops and loudspeakers from flat TV contained Nd-Fe-B magnets. • The amount of Nd-Fe-B could double if the loudspeakers streams are included. - Abstract: Nd-Fe-B permanent magnets are a strategic material for a number of emerging technologies. They are a key component in the most energy efficient electric motors and generators, thus, they are vital for energy technologies, industrial applications and automation, and future forms of mobility. Rare earth elements (REEs) such as neodymium, dysprosium and praseodymium are also found in waste electrical and electronic equipment (WEEE) in volumes that grow with the technological evolution, and are marked as critical elements by the European Commission due to their high economic importance combined with significant supply risks. Recycling could be a good approach to compensate for the lack of rare earths (REs) on the market. However, less than 1% of REs are currently being recycled, mainly because of non-existing collection logistics, lack of information about the quantity of RE materials available for recycling and recycling-unfriendly product designs. To improve these lack of information, different waste streams of electrical and electronic equipment from an industrial recycling plant were analyzed in order to localize, identify and collect RE permanent magnets of the Nd-Fe-B type. This particular type of magnets were mainly found in hard disk drives (HDDs) from laptops and desktop computers, as well as in loudspeakers from compact products such as flat screen TVs, PC screens, and laptops. Since HDDs have been investigated thoroughly by many authors, this study focusses on other potential Nd-Fe-B resources in electronic waste. The study includes a systematic survey of the chemical composition of the Nd-Fe-B magnets found in the selected waste streams, which illustrates the evolution of the Nd-Fe-B alloys over the years. The study also provides an overview over the types of magnets integrated in different waste electric and electronic equipment.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Precision Oxygen Isotope Measurements of Two C-Rich Hydrated Interplanetary Dust Particles

Introduction: Chondritic-smooth IDPs (Interplanetary Dust Particles) are low porosity objects whose mineralogy is dominated by aqueous alteration products such as Mg-rich phyllosilicates (smectite and serpentine group) and Mg-Fe carbonate minerals. Their hydrated mineralogy combined with low atmospheric entry velocities have been used to infer an origin largely from asteroidal sources. Spectroscopic studies show that the types and abundance of organic matter in CS IDPs is similar to that in CP IDPs. Although CS IDPs show broad similarities to primitive carbonaceous chondrites, only a few particles have been directly linked to specific meteorite groups such as CM and CI chondrites based on the presence of diagnostic minerals. Many CS IDPs however, have carbon contents that greatly exceed that of known meteorite groups suggesting that they either may derive from comets or represent samples of more primitive parent bodies than do meteorites. It is now recognized that many large, dark primitive asteroids in the outer main belt, as well as some trans-Neptunian objects, show spectroscopic evidence for aqueous alteration products on their surfaces. Some CS IDPs exhibit large bulk D enrichments similar to those observed in the cometary CP IDPs. While hydrated minerals in comets have not been unambiguously identified to date, the presence of the smectite group mineral nontronite has been inferred from infrared spectra obtained from the ejecta from comet 9P/Tempel 1 during the Deep Impact mission. Recent observations of low temperature sulfide minerals in Stardust mission samples suggest that limited aqueous activity occurred on comet Wild-2. All of these observations, taken together, suggest that the high-carbon hydrated IDPs are abundant and important samples of primitive solar system objects not represented in meteorite collections. Oxygen isotopic compositions of chondrites reflect mixing between a 16O-rich reservoir and a 17O,18O-rich reservoir produced via mass-independent fractionation. The composition of the 16O-rich reservoir is well constrained but material representing the 17O,18O-rich end-member is rare. Self-shielding models predict that cometary water, presumed to represent this reservoir, should be enriched in 17O and 18O by greater than 200 per mille. The high-carbon hydrated IDPs may be among the best materials available to search for preserved "cometary" H2O signatures. In order to better understand the origin and evolution of these particles, we have obtained 10 hydrated interplanetary dust particles for coordinated mineralogical, isotopic and organic analyses. We have previously reported the results of mineralogical and O isotopic measurements of two hydrated IDPs; here we present results of O isotopic measurements of three additional IDPs. Samples and Methods: Three interplanetary dust particles (L2079C35, L2083D46 and L2083E46) were embedded in S and partially ultramicrotomed into approximately 70 nanometer sections for analysis via transmission electron microscopy (TEM). The remainders of the unsliced particles were removed from S and pressed into high purity Au foil that was cleaned with HF acid and annealed at 800 degrees Centigrade. The pressed IDPs were analyzed via electron microprobe analysis (EPMA) for quantitative bulk chemical analysis. After EPMA analysis, the IDPs were subjected to precision O isotope analysis with the UCLA Cameca IMS-1270 ion probe. A 20 kiloelectronvolt, 0.5 nanoangstrom Cs+ primary beam of approximately 15 micrometers diameter was used for each measurement. Small particles of San Carlos olivine and Burma spinel were pressed into the Au foil for use as standards to correct for instrumental mass fractionation. The detection system was configured for multicollection, with 16O measured on a Faraday cup, and 17O and 18O measured on electron multipliers (EMs). Individual analyses consisted of 15 cycles of 10 seconds per cycle. Additionally, two microtome thin sections were measured for H isotopic compositions with the JSC NanoSIMS 50L ion probe. An 8 picoangstrom, 16 kiloelectronvolt Cs plus primary beam was used. Measurements consisted of H, C, 12C, 16O, and 18O collected with EMs in multicollection. Terrestrial biotite and kerogen were used for isotopic standards. A significant challenge in O isotope measurement of hydrated minerals is the interference from 16OH at mass 17O. We ensured that the 17O and 16OH peaks were fully resolved by using a mass resolution of greater than 7000 and by careful analyses of San Carlos olivine, Burma spinel and chlorite hydrated mineral standards. The hydride was further suppressed with a cold finger attached to an LN2 dewar to trap volatiles in the sample chamber. All sputtered ions were counted (i.e. presputtering was not used); after applying background, yield and deadtime corrections, we performed a change-point analysis on our data via R in order to determine when the sample reached sputtering equilibrium; data points collected prior to the change point were excluded. Change-point analysis was also used to determine whether the IDP had completely sputtered. Results: Mineralogy. IDPs C35 and E46 exhibited hydrated mineralogies, Fe-Ni sulfide grains, nanoglobules and occasional enstatite grains distributed throughout a fine-grained Mg-Fe saponite matrix. C35 also contained breunnerite (Mg,Fe)CO3; solar flare tracks were observed in enstatite, indicating minimal atmospheric entry heating. The mineralogy of D46 is dominated by a large FeS grain with a minor component of adhering silicate material. D46 was strongly heated during atmorpheric entry as evidenced by a well-developed magnetite rim. EPMA analyses show that both C35 and E46 have high carbon contents of 20 weight percentage (approximately 6X CI). D46 contains approximately 6 wt.weight percentage C. A significant amount of the carbon is present as carbon nanoglobules. Results: Hydrogen isotopes: Although the bulk delta D values of both sections of L2079C35 were within error of SMOW (minus 33 plus or minus 19 per mille, 1 plus or minus 14 per mille 1 sigma), several delta D-rich hotspots were also identified, reaching 2000 per mille. As shown in Fig. 1, these hotspots are clearly associated with discrete carbonaceous inclusions that are akin to nanoglobules found in many meteorites and other IDPs. Oxygen Isotopes. Results of the oxygen isotope measurements are shown in Figure 1. The oxygen isotope composition for L2079C35 was delta 18O equals plus11.6 plus or minus 1.9per mille, delta 17O equals plus 7.9 plus or minus 1.9per mille (2 standard errors). The oxygen isotope composition for L2083D46 was delta 18O equals minus 8.1 plus or minus 1.9 per mille, delta 17O equals minus 6.4 plus or minus 3.1 per mille (2 standard errors). The oxygen isotope composition for L2083E46 was delta 18O equals plus 12.0 plus or minus 1.9 per mille, delta 17O equals plus 9.2 plus or minus 2.0 per mille (2 standard errors). Discussion: Despite mineralogical similarities to highly aqueously altered carbonaceous chondrites, the hydrated IDPs we analyzed have oxygen isotopic compositions that are distinct from matrix materials in the CI, CM, and CR chondrites. The IDPs plot along the Young-Russell line, with delta 17O values for C35 and E46 suggestive of interaction with a 16O-poor reservoir. However, we have thus far not observed evidence of extreme 16O-poor reservoirs expected from self-shielding models and observed in Acfer 094 simplectite. The high carbon contents of the IDPs also set them apart from known meteoritic samples. The lack of atmospheric entry heating effects are consistent with low encounter velocities and suggest either an asteroidal source, or a low inclination, low eccentricity cometary origin. Conclusions: The unusual oxygen isotopic compositions, high carbon contents, and the abundance of Drich nanoglobules, together, suggest that the high-carbon, hydrated IDPs are derived from a primitive source that is not yet represented in meteorite collections.

Snead, C. J.↗

A Charge‐Separated State that Lives for Almost a Second at a Conductive Metal Oxide Interface

Abstract Transparent conductive oxides (TCOs) are widely used commercially available materials for opto‐electronic applications, yet they have received very little attention for dye‐sensitization applications. Now, mesoporous thin films of conductive indium‐doped tin oxide (ITO) nanocrystallites are shown to support long‐lived charge separation with first‐order recombination kinetics ( k =1.5 s −1 ). A layer‐by‐layer technique was utilized to spatially arrange redox and/or chromophoric molecular components on ITO. Spectroelectrochemical measurements demonstrated that upon light absorption, each component provided a free‐energy gradient to direct electron transfer at the conductive oxide interface. The long‐lived nature of the photogenerated charge separated states provide favorable conditions for photocatalytic solar fuel production. Furthermore, the first‐order recombination kinetics are most ideal for the fundamental understanding of interfacial charge separation dynamics.

Sampaio, Renato N.↗