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Advanced low-cost intermetallic coatings for molten salt pump impeller. Final report

1.0 INTRODUCTION The use of solar energy to produce steam for the generation of electricity is an established technology, with multiple designs for concentrating solar power (CSP) steam generators available commercially and a number of such units currently operating. As part of the effort to improve the overall efficiency of this technology, designers have developed thermal energy storage (TES) mechanisms that employ molten salt to capture a portion of the solar energy available during the day-time hours and make that energy available for steam generation during periods when the sun’s energy is not available. In current TES systems, nitrate salts are used extensively as the medium of energy exchange. However, due to the chemical instability of these salts at temperatures above 600ºC, they are not being considered for use in the next more efficient generation of CSP plants, in which the energy exchange fluids will be required to operate in the range 600ºC to 800ºC. At these higher temperatures, molten chloride salts, such as KCl-MgCl2, are viewed as promising alternatives to the nitrate salts, but, of course, these chloride-based salts are highly corrosive to the engineering alloys commonly used in the construction of pressure vessels, heat exchangers, pumps and piping at high temperatures. Hence, a solution to the problem of material degradation is essential if the next generation of CSP plants is to be commercially viable (Ref 1). In order to effectively address the problem of molten chloride salt corrosion at high temperatures (≥ 750ºC) and thereby to reduce the cost of molten salt tanks and related apparatus, various options have been considered, with one of the most promising being an innovative coatings system developed and applied onto low alloy ferritic or austenitic stainless material. Development of such a coating system would reduce the capital costs of thermal energy storage (TES) and increase the overall efficiency of the concentrating solar power (CSP) system. Although high strength nickel base alloys are well suited for many high temperature applications, they have significant limitations when exposed to molten chloride salt conditions and they are very expensive. Monolithic materials such as the austenitic stainless steels (e.g., SS310 and SS347) and the more common nickel base alloys (e.g., IN625 and IN800H) have exhibited high corrosion rates in molten chloride salt environments (Ref1). Molten salt corrosion of IN625 in salts containing chlorides showed a catastrophic corrosion rate of 1.111”/year at 800ºC (Ref1). Hence, an innovative coatings solution to mitigate molten chloride salt corrosion is needed. Of the many coating techniques available in the market, no one technique appears to be capable of producing effective protection from molten salt corrosion at a relatively low cost. There are thermal spray coating techniques, in particular the twin wire-arc technology, that are attractive when considering the coating of large molten salt tanks because the coatings application rate is high, the overall application cost is low and repairs to the coating can readily be made either in the shop or in the field. However, the twin wire arc coating materials currently available in the market have certain inherent limitations, including porosity and mechanical bonding to the substrate, which limit their effectiveness in providing protection against molten chloride salt corrosion at high temperatures. What is required is an approach that combines the economy and versatility of thermal spray wire-arc technology with the superior resistance of advanced alloys to effectively combat molten chloride salt corrosion at elevated temperatures. Applied Thermal Coatings, Inc. (ATC) has investigated an innovative coatings technology to produce dual layer cermet/ceramic coatings that will be dense and impervious to any corrosive molten salts/fluids, thereby resisting the effects of molten salt corrosion. Development of coatings using this technology will make it possible to fabricate the molten salt systems using a relatively low-cost base material, which will reduce the overall cost of the power generating system and enhance the commercial viability of solar power. 2.0 PROJECT OVERVIEW Of the coating technologies available for the production of a cost-effective method of protection from the effects of high-temperature chloride attack, there are two that offer specific advantages for the CSP/TES application, particularly when used in a way that effectively complements the strengths of each coating method. The first of these is electroless nickel plating, through which a nickel-rich layer is produced on the surface of a component through chemical reduction. The second coating technology is aluminizing, in which aluminum is diffused into the surface of a component and, depending on the composition of the substrate, aluminides are formed. The objective of this project has been to demonstrate the feasibility of a low- cost coating for the protection of pump impellers used for the inductive transport of molten salts. Initial interest focused on an inter-metallic nickel aluminide coating and subsequently, for economic reasons, consideration also was given to a coating composed of iron aluminides. Applying such coatings to low alloy or austenitic stainless-steel substrates will provide the superior resistance to molten chloride salt corrosion and blade tip erosion that normally can be achieved only through the use of more highly alloyed – and, therefore, more expensive - nickel-base materials and it will do so at a substantially lower cost. The coating systems evaluated were designed to take advantage either of the combined strengths of the electroless nickel plating process and the aluminizing process to produce a nickel-aluminide intermetallic coating or to rely solely on the aluminizing process to produce, in conjunction with iron from the substrate, a protective layer consisting of iron aluminides. With respect to the nickel aluminide protection, this has been achieved by first depositing a layer of nickel-rich alloy onto an austenitic stainless substrate using the electroless nickel plating process and then aluminizing the nickel- coated surface to produce the nickel aluminide coating. With respect to the iron aluminide protection, this has been achieved by aluminizing bare austenitic stainless steel. Testing has supported the conclusion that the developed coatings will resist attack by molten chloride salts at high temperatures (550°C to 750°C) and have sufficient hardness to resist blade tip erosion.The steps taken to develop either a low-cost intermetallic nickel aluminide coating using electroless nickel plating and aluminizing or a low-cost iron aluminide coating using aluminizing only, and to demonstrate the quality of the coatings and their effectiveness against molten chloride salt corrosion and erosion at high temperatures (≤ 750ºC) have been as follows: 1. Design of the optimum electroless nickel plating and aluminizing mixtures using advanced thermodynamic analysis; 2. Development of processing parameters for the electroless nickel plating and aluminizing processes, to be used either together or separately; 3. Production of specimens coated using the designated electroless nickel plating process; 4. Production of samples with intermetallic nickel aluminide coating or iron aluminide coating; 5. Investigation of the performance of the intermetallic nickel aluminide coating and the iron aluminide coating when subjected to molten chloride salts corrosion at high temperatures (≥ 750ºC); and, 6. Metallurgical characterization of the microstructure of the coatings, both prior to and after exposure to molten salt environments at elevated temperatures.

14 SOLAR ENERGY↗

Reaction Mechanisms and Particle Interaction in Burning Two-Phase Systems

The main objective of this research is to understand the mechanisms by which particle interactions affect ignition and combustion in the two-phase systems. Combustion of metal aerosols representing the two-phase systems is carried out in the microgravity environment enabling one to avoid the buoyant flows that mask the particle motion due to the particle-particle interaction effects. In addition, relatively large, e.g., 100 micron diameter particles can be used, that remain aerosolized (i.e., do not fall down as they would at normal gravity) so that their behavior ahead, behind, and within the propagating flame can be resolved optically. An experimental apparatus exploiting this approach has been designed for the 2.2-s drop tower microgravity experiments. A typical experiment includes fluidizing metal particles under microgravity in an acoustic field, turning off the acoustic exciter, and igniting the created aerosol at a constant pressure using a hot wire igniter. The flame propagation and details of the individual particle combustion and particle interactions are studied using high-speed movie and video cameras coupled with microscope lenses to resolve individual particles. Recorded flame images are digitized and various image processing techniques including flame position tracking, color separation, and pixel by pixel image comparisons are employed to understand the processes occurring in the burning aerosols. Condensed combustion products are collected after each experiment for the phase, composition, and morphology analyses. New experiments described in this paper address combustion of Ti and Al particle clouds in air and combustion of Mg particle clouds in CO2. In addition, microgravity combustion experiments have been conducted with the particles of the newly produced Al-Mg mechanical alloys aerosolized in air.

Dreizin, Edward L.↗

Techno-Economic Analysis and Life-Cycle Assessment of Emerging Technologies for Bioprocessing Separations

Limited availability, rising costs, and environmental concerns about fossil fuels have generated considerable interest in finding alternative, renewable sources including biomass, which can be converted into a number of biofuels and bioproducts. In comparison to petroleum-based products, high processing costs, mainly associated with bioprocessing separations, limit widespread implementation of biofuels and bioproducts. Bioprocess-related separations are also complicated, regardless of the conversion pathway, due to the dilute nature of products and the chemically complex mixtures that result from biomass deconstruction. In many cases, bioprocessing separation approaches lack a technology baseline, or definition of the state of technology (SOT). This work focuses on evaluating the technology readiness of novel separations technologies for the conversion of biomass into biofuels and bioproducts and will address three key topics: 1) SOT description, 2) economic viability analysis of both SOT and innovative separations, and 3) environmental impact assessment of both SOT and novel processes. The current SOT for lignin valorization, dilute carbon recovery, and impurity removal is used to identify potential opportunities for improvement and provide a baseline for comparison with the emerging technologies. Detailed techno-economic analysis (TEA) and life cycle assessment (LCA) are applied to understand the key drivers and challenges related to the economic feasibility and environmental impacts, respectively.

BASIC BIOLOGICAL SCIENCES,BIOMASS FUELS↗

Integrated lunar materials manufacturing process

A manufacturing plant and process for production of oxygen on the moon uses lunar minerals as feed and a minimum of earth-imported, process materials. Lunar feed stocks are hydrogen-reducible minerals, ilmenite and lunar agglutinates occurring in numerous, explored locations mixed with other minerals in the pulverized surface layer of lunar soil known as regolith. Ilmenite (FeTiO.sub.3) and agglutinates contain ferrous (Fe.sup.+2) iron reducible by hydrogen to yield H.sub.2 O and metallic Fe at about 700.degree.-1,200.degree. C. The H.sub.2 O is electrolyzed in gas phase to yield H.sub.2 for recycle and O.sub.2 for storage and use. Hydrogen losses to lunar vacuum are minimized, with no net hydrogen (or any other earth-derived reagent) consumption except for small leaks. Feed minerals are surface-mined by front shovels and transported in trucks to the processing area. The machines are manned or robotic. Ilmenite and agglutinates occur mixed with silicate minerals which are not hydrogen-reducible at 700.degree.-1,200.degree. C. and consequently are separated and concentrated before feeding to the oxygen generation process. Solids rejected from the separation step and reduced solids from the oxygen process are returned to the mine area. The plant is powered by nuclear or solar power generators. Vapor-phase water electrolysis, a staged, countercurrent, fluidized bed reduction reactor and a radio-frequency-driven ceramic gas heater are used to improve thermal efficiency.

Gibson, Michael A.↗

Analysis and Design for Sustainable Circularity of Barrier Films Used in Sheet Molding Composites Production

Sheet molding composites (SMC) are thermoset based molding compounds with a global market size of USD 2.1 billion in 2020. SMC is usually processed with multilayer barrier/carrier films to prevent emissions from volatile organic compounds (VOC). The plastic barriers are separated from SMC after the curing process and discarded. To illustrate the high consumption volume of SMC barrier/carrier films, Kohler Co., a company which uses SMC in their bath and showering product lines, alone generates over 1M lb/year of SMC barrier/carrier film waste. Therefore, high amount of SMC barrier/carrier film plastic waste creates a great opportunity for reusing, recycling, or valorization at its end of life. This can be achieved through transition from a linear to a circular supply chain design. However, this transition will not be feasible without overcoming the technical and economic barriers. This project aims to tackle this by making the film circular. Different end of life alternatives will be evaluated experimentally. The reusability of the film will be studied through applying different mechanical and solvent cleaning techniques. The operability concerns regarding the utilization of the cleaned film for long run operations will be addressed by thermally stitching the film. Pelletizing of the cleaned film will also be investigated as a viable technique for recycling or downcycling of the film as molded products. In addition to technical barriers, designing a sustainable circular supply chain for SMC carrier film products requires uncovering the collaboration opportunities between suppliers and users at different stages of the value chain to expand its use to other products. These opportunities will be investigated by finding companies willing to buy or treat the plastic film waste. Finally, the economic viability and environmental impacts of these circular design alternatives will be evaluated through techno-economic assessment (TEA) and life cycle analysis (LCA). Techno-economic and life cycle inventory data for various pathways will also be made available as one of the main outcomes of this project. Preliminary LCA results indicate that the current SMC film supply chain (base case) emits 5.81 tonne CO2 eq. and consumes 104 GJ energy per tonne of SMC film. It is estimated that alternative circular pathways result in 14-20% less CO2 emissions and 34-44% reduction in embodied energy. This project will develop a tool to analyze the circularity and sustainability of hundreds of combinations of alternatives in different life cycle stages. Users of this tool will be able to choose the best combination among these alternatives with respect to the selected economic, environmental and circularity objectives.

circular economy↗

25 years of environmental remediation in the general separations area of the Savannah river site: lessons learned about what worked and what did not work in soil and groundwater cleanup - 15270

The Savannah River Site, which is owned and administered by the US Department of Energy, covers approximately 900 square kilometers. The General Separation Area is located in the center of the site and includes: radioactive material chemical separations facilities, radioactive waste tank farms, radioactive seepage basins, and the radioactive waste burial grounds. Radioactive wastes were disposed in the General Separation Area from the mid-1950's through the mid-1990's. Operations at the F Canyon began in 1954 and at H Canyon began in 1955. Waste water disposition to the F and H Seepage Basins began soon after operations started in the canyons. The Old Radioactive Waste Burial Ground began operations in 1952 to manage solid waste that could be radioactive from all the site operations, and ceased receiving waste in 1972. The Mixed Waste Management Facility and Low Level Radioactive Waste Disposal Facility received radioactive solid waste from 1969 until 1995. Environmental legislation enacted in the 1970's through 1990's led to changes in waste management and environmental cleanup practices. The US Congress passed the Clean Air Act in 1970 and the Clean Water Act in 1972; the Resource Conservation and Recovery Act was enacted in 1976; the Comprehensive Environmental Response Compensation, and Liability Act was enacted by Congress in 1980; and the Federal Facilities Compliance Act was signed into law in 1992. Environmental remediation at the Savannah River Site essentially began with a 1987 Settlement Agreement between the Savannah River Site and the State of South Carolina. The site manages several of the larger groundwater remedial activities under the Resource Conservation and Recovery Act for facilities recognized early on as environmental problems. All subsequent remediation projects are managed under a tri-party agreement (Department of Energy, Environmental Protection Agency, and South Carolina Department of Health and Environmental Control) through the Federal Facilities Agreement. Environmental remediation activities during the past 25 years have stabilized and capped seepage basins as well as consolidated and capped waste units and burial grounds in the General Separation Area. Groundwater activities include: pump and treat systems in the groundwater, installation of deep subsurface barrier systems to manage groundwater flow, in situ chemical treatments in the groundwater, and captured contaminated groundwater discharges at the surface for management in a forest irrigation system. Concentrations of contaminants in the aquifers beneath the General Separation Area and in surface water streams in the General Separation Area have decreased over the past 25 years. Closure of 65 waste sites and 4 Resource Conservation and Recovery Act facilities has been successfully accomplished. Environmental clean-up has progressed to the stage where most of the work involves monitoring, optimization, and maintenance of existing remedial systems. Many lessons have been learned in the process of remediating the General Separations Area. Geo-textile covers outperform low permeability clay caps, especially with respect to the amount of repairs required to upkeep the drainage layers as the caps age. Passive and enhanced natural processes to address contamination are much more cost effective than pump and treat systems. Forest irrigation can be very effective in water management situations with non-accumulative contaminants such as tritium and volatile organic contaminants. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Metastable precipitation and ion–extractant transport in liquid–liquid separations of trivalent elements

The extractant-assisted transport of metal ions from aqueous to organic environments by liquid–liquid extraction has been widely used to separate and recover critical elements on an industrial scale. While current efforts focus on designing better extractants and optimizing process conditions, the mechanism that underlies ionic transport remains poorly understood. Here, we report a nonequilibrium process in the bulk aqueous phase that influences interfacial ion transport: the formation of metastable ion–extractant precipitates away from the liquid–liquid interface, separated from it by a depletion region without precipitates. Although the precipitate is soluble in the organic phase, the depletion region separates the two and ions are sequestered in a long-lived metastable state. Since precipitation removes extractants from the aqueous phase, even extractants that are sparingly soluble in water will continue to be withdrawn from the organic phase to feed the aqueous precipitation process. Solute concentrations in both phases and the aqueous pH influence the temporal evolution of the process and ionic partitioning between the precipitate and organic phase. Aqueous ion–extractant precipitation during liquid–liquid extraction provides a reaction path that can influence the extraction kinetics, which plays an important role in designing advanced processes to separate rare earths and other minerals.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

High-gradient magnetic separation of colloidal uranium oxide particles from soil components in aqueous suspensions

The separation of uranium oxide (UO 2 ) particles from soil-surrogate particles in aqueous suspensions was achieved using filtration enhanced by a magnetic field. Enhanced attraction of paramagnetic UO 2 colloids to a ferromagnetic stainless-steel filter placed in a strong magnetic field arises because of the positive magnetic susceptibility of the particles and the high-gradient field generated near ferromagnetic fibers. Enhanced uptake of smaller particles over larger ones occurs through Brownian motion that promotes the collision of particles with the ferromagnetic fibers of the filter. Hence, this work focused on UO 2 particles in the colloidal size range. Experiments used a water-cooled electromagnet and an array of permanent magnets. Chemical analysis showed that the magnetic field increased the capture efficiency of uranium particles from a range of 27–53% with the magnet off up to 98% with the magnet on after a single pass of the suspension through the filter. Further, the recovery of the UO 2 particles from the filter, however, was more difficult to achieve. Small amounts of UO 2 , together with significant amounts of background SiO 2 particles, were removed from the filter during a first flush with the magnetic field on. A much larger recovery of UO 2 was not observed until a second out-of-field flush was performed, which also released some SiO 2 . The degree to which particle separation was enhanced through the use of multi-stage filtration compared to single pass-through filtration was also examined. A design was suggested that could be used to optimize the separation efficiency for a continuous process.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Evaluation of Inorganic/Organic Separators

Thirty-six (36) experimental 40AH sealed silver-zinc cells were constructed during phase I of this two (2) phase program. These cells were divided into six (6) groups of six (6) cells each. Each group of six (6) cells was evenly divided into two batches of three (3) cells each. Groups 1 through 4 each featured a different inorganic filler material in the slurry used to coat the separator substrate. Groups 5 and 6 featured an alternate method of separator bag construction. With the exception of the various separator materials, the parts and processes used to produce these thirty-six (36) cells were the same as those used to make the HR40-7 cell. The two (2) batches of cells in each cell group differed only in the lots of solutions and other separator slurry components used. Each cell was given two formation charge/discharge cycles prior to being shipped to NASA Lewis Research Center. Phase II of the program consisted of constructing another thirty-six (36) 40AH experimental cells in six (6) groups of six (6) cells each. Each group was distinguished by the type of precoated separator material used to fabricate separator bags. A new method of separator bag construction was used in this phase of the program. These cells were given two (2) formation cycles and shipped to NASA Lewis Research Center.

Donnel, C. P., III↗

Hanford site excavation permit application automation project - 15187

Mission Support Alliance, LLC (MSA), on behalf of the Department of Energy's Richland Operations Office (DOE-RL), recently implemented the Site Excavation Permit Application (SEPA) at Hanford. The SEPA automation replaced a 20-year-old manual excavation permit process that governed all Hanford Site excavation activities. The manual process required time consuming interaction between numerous resources for submitting an excavation permit to 15 separate permit organizations for approvals and signature. The process involved numerous information exchanges - usually by phone or E-mails, and substantial vehicle travel. It also generated large amounts of paper, lengthy wait periods and the need for continual status updates to permit reviewers until all approvals were obtained. The new SEPA automated system is an entirely paperless application that streamlines over 25 separate manual permit activities into five Web-based processes. The new application provides sizable environmental sustainability benefits in terms of avoiding: paper waste, air pollution and bio-fuel consumption. SEPA also deploys automated innovations that produce an approximate 50 percent operational cost reduction when compared to the manual permit process. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Revisiting metastable immiscibility in SiO 2 –Al 2 O 3 : Structure and phase separation of supercooled liquids and glasses

Understanding and controlling liquid–liquid phase separation in aluminosilicates is crucial for optimizing glass properties. However, the metastable nature of aluminosilicates’ phase separation has made it difficult to study experimentally, and uncertainty persists regarding the compositional and temperature extents of the miscibility gap. Here, we present new experimental evidence that suggests a consolute temperature between 1440 and 1590°C and endmember compositions of 7 and 62 mol.% Al 2 O 3 for the phase-separated glasses. Using containerless melt processing, deeply supercooled liquids over the 0–60 mol.% Al 2 O 3 range are probed with in situ small- and wide-angle X-ray scattering, which simultaneously reveals changes in nanoscale density heterogeneity and atomic structure. Correlations between phase separation and atomic coordination environments are compared for liquids and glasses. Pair distribution function analysis shows mean O–(Si + Al) coordination increases with Al 2 O 3 content and decreases with temperature.

36 MATERIALS SCIENCE↗

Revisiting Theoretical Tools and Approaches for the Valorization of Recalcitrant Lignocellulosic Biomass to Value-Added Chemicals

Biorefinery processes for converting lignocellulosic biomass to fuels and chemicals proceed via an integrated series of steps. Biomass is first pretreated and deconstructed using chemical catalysts and/or enzymes to liberate sugar monomers and lignin fragments. Deconstruction is followed by a conversion step in which engineered host organisms assimilate the released sugar monomers and lignin fragments, and produce value-added fuels and chemicals. Over the past couple of decades, a significant amount of work has been done to develop innovative biomass deconstruction and conversion processes that efficiently solubilize biomass, separate lignin from the biomass, maximize yields of bioavailable sugars and lignin fragments and convert the majority of these carbon sources into fuels, commodity chemicals, and materials. Herein, we advocate that advanced in silico approaches provide a theoretical framework for developing efficient processes for lignocellulosic biomass valorization and maximizing yields of sugars and lignin fragments during deconstruction and fuel and chemical titers during conversion. This manuscript surveys the latest developments in lignocellulosic biomass valorization with special attention given to highlighting computational approaches used in process optimization for lignocellulose pretreatment; enzyme engineering for enhanced saccharification and delignification; and prediction of the genome modification necessary for desired pathway fine-tuning to upgrade products from biomass deconstruction into value-added products. Physics-based modeling approaches such as density functional theory calculations and molecular dynamics simulations have been most impactful in studies aimed at exploring the molecular level details of solvent-biomass interactions, reaction mechanisms occurring in biomass-solvent systems, and the catalytic mechanisms and engineering of enzymes involved in biomass degradation. More recently, with ever increasing amounts of data from, for example, advanced mutli-omics experiments, machine learning approaches have begun to make important contributions in synthetic biology and optimization of metabolic pathways for production of biofuels and chemicals.

09 BIOMASS FUELS↗

Functional membranes. Present and future

The present situation and the future development of the functional membrane are discussed. It is expected that functional membranes will play increasingly greater roles in the chemical industry of the coming decade. These membranes are formed from polymer films, liquid membranes or bilayer membranes. The two most important technologies based on the polymeric membrane are reverse osmosis and ion exchange. The liquid membrane is used for separation of ionic species; an extension of the solvent extraction process. By using appropriate ligands and ionophores, highly selective separations are realized. The active transport is made possible if the physical and chemical potentials are applied to the transport process. More advanced functional membranes may be designed on the basis of the synthetic bilayer membrane.

Kunitake, T.↗

Modulating the Mixing Gibbs Free Energy to Enhance Solid–Liquid Phase Separation for High–Performance Organic Solar Cells

Organic solar cells (OSC) feature a hierarchical structure with the electron donor/acceptor layer sandwiched by anode and cathode, which raises the importance of controlling the molecular crystal orientation, domain size, and vertical distribution to facilitate the charge collection at electrodes. However, the similar conjugated backbone of donor/acceptor material and fast film–formation kinetics have led to spinodal–decomposition–orientated phase separation that result in the film presenting an intimately mixed morphology and random molecular orientation. To solve the issue, the mixing Gibbs free energy–triggered solid–liquid phase separation during the film formation process is enhanced by solidifying one component and solvating the other based on a liquid additive. Following the liquid evaporation process, a favorable vertical distribution is obtained. Meanwhile, the prolonged solvation process enlarges the domain size and assists the molecules to diffuse and orient properly, enabling better exciton/charge dynamics during the power conversion processes. As a result, the fabricated devices exhibit a fill factor over 80% and an efficiency of 18.72%, which is one of the top efficiencies for binary OSCs. In conclusion, insights and a methodology is provided here to manipulate the organic donor/acceptor phase separation in terms of mixing Gibbs free energy.

14 SOLAR ENERGY↗

Chromatographic separation of the theranostic radionuclide 111 Ag from a proton irradiated thorium matrix

Column chromatographic methods have been developed to separate no-carrier-added 111 Ag from proton irradiated thorium targets and associated fission products as an ancillary process to an existing 225 Ac separation design. In this paper, we report the separation of 111 Ag both prior and subsequent to 225 Ac recovery using CL resin, a solvent impregnated resin (SIR) that carries an organic solution of alkyl phosphine sulfides (R 3 P = S) and alkyl phosphine oxides (R 3 P = O). The recovery yield of 111 Ag was 93 ± 9% with a radiochemical purity of 99.9% (prior) and 87 ± 9% with a radiochemical purity of 99.9% (subsequent to) 225 Ac recovery. Both processes were successfully performed with insignificant impacts on 225 Ac yields or quality. Measured equilibrium distribution coefficients for silver and ruthenium (a residual contaminant) on CL resin in hydrochloric and nitric acid media are reported, to the best of our knowledge, for the first time. Finally and additionally, measured cross sections for the production of 111 Ag and 110m Ag for the 232 Th(p,f) 110m,111 Ag reactions are reported within.

111Ag↗

The use of multispectral sensing techniques to detect ponderosa pines trees under stress from insects or diseases

The detection of stress induced by bark beetles in conifers is reviewed in two sections: (1) the analysis of very small scale aerial photographs taken by NASA's RB-57F aircraft on August 10, 1969, and (2) the analysis of multispectral imagery obtained by the optical-mechanical line scanner. Underexposure of all films taken from the RB-57 aircraft and inadequate flight coverage prevented drawing definitive conclusions regarding optimum scales and film combinations to detect the discolored infestations. Preprocessing of the scanner signals by both analog and digital computers improved the accuracy of target recognition. Selection and ranking of the best channels for signature recognition was the greatest contribution of digital processing. Improvements were made in separating hardwoods from conifers and old-kill pine trees from recent discolored trees and from healthy trees, but accuracy of detecting the green infested trees is still not acceptable on either the SPARC or thermal-contouring processor. From six years of experience in processing line scan data it is clear that the greatest gain in previsual detection of stress will occur when registered multispectral data from a single aperture or common instantaneous field of view scanner system can be collected and processed.

Heller, R. C.↗

Hierarchical morphologies in co-sputter deposited thin films

Co-depositions of immiscible alloy films at specific processing conditions have yielded hierarchical microstructures which consist of distinct features at multiple length scales, often agglomerates and concentration modulations on the sub-micrometer-scale and fine nanoprecipitates in a matrix on the nanoscale. The present work examined a series of immiscible alloy systems: Cu-Mo, Cu-Ag, Cu-Fe, Cu-Ta, Mo-Ag, Cu-Mo-Ag, to determine the kinetic conditions favorable for hierarchical organization and the formation mechanism of such structures. Thin films of six immiscible systems were sputter co-deposited over a range of deposition rates from 0.12 to 2 nm/s and various temperatures from 400 to 800°C. The resulting microstructures indicate that hierarchical structures form with sufficient disparity in kinetic energy between the constituent atoms, one species being highly mobile (A) and the other relatively immobile (B). This condition arises typically at elevated deposition temperatures and reduced deposition rates but is also alloy dependent. The hierarchical structures form during deposition via phase separation and self-organization processes across the multiple length scales. The adatoms diffuse on the film surface with the highly mobile species swiftly agglomerating into A-rich domains within which B-rich nanoprecipitates form, often self-organizing into periodic arrays. The smallest B-rich nanoprecipitates in the A-rich domains are found to be coherent and in a metastable crystal structure (B taking the structure of A), but coarser precipitates that exhibit the equilibrium structure of B element. The A-rich domains are surrounded by a B-rich matrix that phase-separates into a concentration modulated structure. In conclusion, the observations are interpreted via a model incorporating material properties and process parameters.

36 MATERIALS SCIENCE↗

Separating Xylene Isomers with a Calcium Metal‐Organic Framework

Abstract The purification of p‐xylene (pX) from its xylene isomers represents a challenging but important industrial process. Herein, we report the efficient separation of pX from its ortho‐ and meta‐ isomers by a microporous calcium‐based metal–organic framework material (HIAM‐203) with a flexible skeleton. At 30 °C, all three isomers are accommodated but the adsorption kinetics of o‐xylene (oX) and m‐xylene (mX) are substantially slower than that of pX, and at an elevated temperature of 120 °C, oX and mX are fully excluded while pX can be adsorbed. Multicomponent column breakthrough measurements and vapor‐phase/liquid‐phase adsorption experiments have demonstrated the capability of HIAM‐203 for efficient separation of xylene isomers. Ab initio calculations have provided useful information for understanding the adsorption mechanism.

Yu, Liang↗