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At least 829 records · Page 46

Experimental determination of the speciation, partitioning, and release of perrhenate as a chemical surrogate for pertechnetate from a sodalite-bearing multiphase ceramic waste form

A key component to closing the nuclear fuel cycle is the storage and disposition of nuclear waste in geologic systems. Multiphase ceramic waste forms have been studied extensively as a potential host matrix for nuclear waste. Understanding the speciation, partitioning, and release behavior of radionuclides immobilized in multiphase ceramic waste forms is a critical aspect of developing the scientific and technical basis for nuclear waste management. In this study, we evaluated a sodalite-bearing multiphase ceramic waste form (i.e., fluidized-bed steam reform sodium aluminosilicate [FBSR NAS] product) as a potential host matrix for long-lived radionuclides, such as technetium (99Tc). The FBSR NAS material consists primarily of nepheline (ideally NaAlSiO4), anion-bearing sodalites (ideally M8[Al6Si6O24]X2, where M refers to alkali and alkaline earth cations and X refers to monovalent anions), and nosean (ideally Na8[AlSiO4]6SO4). Bulk X-ray absorption fine structure analysis of the multiphase ceramic waste form, suggest rhenium (Re) is in the Re(VII) oxidation state and has partitioned to a Re-bearing sodalite phase (most likely a perrhenate sodalite Na8[Al6Si6O24](ReO4)2). Rhenium was added as a chemical surrogate for 99Tc during the FBSR NAS synthesis process. The weathering behavior of the FBSR NAS material was evaluated under hydraulically unsaturated conditions with deionized water at 90 ?C. The steady-state Al, Na, and Si concentrations suggests the weathering mechanisms are consistent with what has been observed for other aluminosilicate minerals and include a combination of ion exchange, network hydrolysis, and the formation of an enriched-silica surface layer or phase. The steady-state S and Re concentrations are within an order of magnitude of the nosean and perrhenate sodalite solubility, respectively. The order of magnitude difference between the observed and predicted concentration for Re and S may be associated with the fact that the anion-bearing sodalites contained in the multiphase ceramic matrix are present as mixed-anion sodalite phases. These results suggest the multiphase FBSR NAS material may be a viable host matrix for long-lived, highly mobilie radionuclides which is a critical aspect in the management of nuclear waste.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of edge-seal design on the mechanical and thermal performance of vacuum-insulated glazing

Although vacuum-insulated glazing (VIG) has been proposed as a promising solution towards developing energy-efficient buildings, VIGs have not become popular in the market due to several technical challenges including the complexity of the fabrication process. In particular, the edge-seal is a key component that significantly affects the thermal insulation and mechanical performance, and the development of edge-seal with adequate thermal insulation, mechanical strength, and reasonable processing cost is essential to overcome such technical issues in VIG. For this purpose, effects of edge-seal design parameters on the VIG performance should be identified. In this research, we analyzed the edge-seal for thermal transport as well as structural stresses to study the effects, and then identified and evaluated the material mixes for the edge-seal requirements. Here, the finite element simulations showed the significance of VIG corner calculation on overall thermal transmittance and the importance of seal conductivity below 1 W/m.K. The experiments with the flexible seals with different ratios of fine glass powder demonstrated that the measured shear strength values for the seal with less than 30% glass powder were more than 10 times larger than the calculated shear stress values. Based on these simulation and experimental results, a flexible sealant was developed using a proprietary mix of ceramic materials that meets the requirements of the designed VIG edge-seal, including structural as well as thermal stress resistance and a low conductivity. Moreover, the sealant is self-curing under atmospheric conditions, and thus it does not require costly inline process of laser curing or oven baking.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Lightweight TiC–(Fe–Al) ceramic–metal composites made in situ by pressureless melt infiltration

Lightweight ceramic–metal (cermet) composites combine stiffness and hardness with fracture toughness and ductility. TiC and Al are ideal pairs among lightweight cermet composites because of their relatively high strength-to-weight ratios, but these materials are difficult to process in solid state or with Al melt infiltration without making an aluminum carbide phase, which is detrimental to mechanical properties. Here, Fe is added to a TiC powder preform to reduce the activity of Al with TiC during Al melt infiltration and to aid in pressing TiC preforms, making a lightweight TiC–(Fe–Al) composite while avoiding other, unwanted phases. The composites are made by first pressing TiC powder mixed with Fe followed by Al melt infiltration; the result is a composite with high TiC content in a two-phase matrix, both of which are Fe–Al-based. The composite has low density, low porosity, high hardness, no detectable Al 4 C 3 phase with X-ray diffraction and retains shape well during infiltration.

36 MATERIALS SCIENCE↗

High-Efficiency and Low-Carbon Energy Storage and Power Generation System for Electric Aviation

This report summarizes the work performed by University of California San Diego (UCSD) – Honeywell Aerospace (Honeywell) team for the U.S. Department of Energy/Advanced Research Projects Agency-Energy (DOE/ARPA-E) under Phase 1 (April 2021 – October 2023) project, Cooperative Agreement DE-AR0001347 entitled “High-Efficiency and Low-Carbon Energy Storage and Power Generation System for Electric Aviation”. The main objective of this project is to develop and demonstrate an energy storage and power generation (ESPG) system operating on bio liquid natural gas (LNG) for electric aviation applications. The ESPG system concept in this project is a fuel cell, battery, and gas turbine hybrid system that incorporates an innovative solid oxide fuel cell (SOFC) technology. This SOFC technology has two main novel elements: (i) a lightweight and compact stack architecture that consists of cells and cell modules in electrical parallel and series connections (the module design) and (ii) exceptionally high performance, direct methane thin-film cells on porous substrate made by sputtering deposition process. This fuel cell has the specific power and volumetric power density suitable for electric aviation applications. Based on the current status of the SOFC technology, the Phase 1 work focused on the following activities: (i) ESPG System Modeling – to design and optimize an aircraft SOFC-based ESPG system concept that met the performance, weight and cost targets; (ii) Cell Material Development and Scaleup – to demonstrate scalability of the sputtering process for manufacture of thin-film SOFC cells of practical sizes, confirm the exceptional performance of sputtered cells, improve cell stability and durability for operation with hydrogen and methane fuel, and develop a suitable electrically conducting porous substrate to replace the current non-conducting ceramic substrate; (iii) Stack Development – to design and manufacture stack components for the stack architecture, evaluate and select a suitable sealant, and build and operate multi-cell stacks to demonstrate stack operation, and (iv) Technology to Market – to develop business models and commercialization plans, conduct various market and technology analysis and estimate SOFC and ESPG system costs.

25 ENERGY STORAGE↗

The Nature of the Nonsingularity of Inner Interfaces in Hydroxyapatite Ceramics

The morphology of inner interfaces in hydroxyapatite (HA) based calcium phosphate ceramics has been studied by transmission electron microscopy. Grain boundaries in the ceramics have been shown to have a vicinal character, which is related to the mechanism of secondary recrystallization in the material: layer growth of grains via sequential motion of elementary steps on planes corresponding to the {11̄00} HA prism faces, which grow through transitions of atoms from adjacent grains that are in contact through their planes with large Miller indices. The recrystallization process may be accompanied by a “collision” of vicinal growth surfaces of grains with relatively large misalignment angles and the formation of grain boundaries nanofaceted by prism planes of adjacent grains. The recrystallization process in such a case should be expected to continue in the grain with a smaller nonsingularity of the growth front. Grain boundaries may allow for a match between planes differing in Miller indices, nd{sub h1k1l1} ≈ md{sub h2k2l2}, and the formation of grain-boundary Pumphrey dislocations, which compensate for the size mismatch between interplanar spacings and/or misalignment of the planes. The observed characteristic grain match configurations are typical of both ceramics produced by sintering HA powders and HA films produced by ion sputtering.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Predictive modeling of crystal accumulation in high-level waste glass melters processing radioactive waste

The effectiveness of HLW vitrification is limited by precipitation/accumulation of spinel crystals [(Fe, Ni, Mn, Zn)(Fe, Cr)2O4] in the glass discharge riser of Joule-heated ceramic melters during idling. These crystals do not affect glass durability; however, if accumulated in thick layer, they can clog the melter and prevent discharge of molten glass into canisters. To address this problem, an empirical model was developed that can predict thicknesses of accumulated layers as a function of glass composition. This model predicts well the accumulation of single crystals and/or small-scale agglomerates, but, excessive agglomeration observed in high-Ni-Fe glass resulted in an under-prediction of accumulated layers, which gradually worsen over time as an increased number of agglomerates formed. Accumulation rate of ~53.8 ± 3.7 µm/h determined for this glass will result in ~26 mm thick layer in 20 days of melter idling.

Crystal accumulation↗

Coal-Waste-Enhanced Filaments for Additive Manufacturing of High-Temperature Plastics and Ceramic Composites

In the United States, coal waste from over a century of mining and burning coal for heat and electricity has accumulated as mountains of coal fly ash and bottom ash and acre-size ponds, coal fines and gob. These materials can be a problem for local communities and water systems. A cost-effective process to utilize high volumes of these coal wastes in a high-value product would be beneficial to those communities by reducing the amount of waste and providing jobs, manufacturing components, and materials from the waste. Many coal-to-products technologies (e.g., carbon fibers, graphene, carbon foam) rely on carefully choosing the starting material and then altering it chemically or thermally to make the products work. Due to the wide variability of composition and coal content in typical coal waste streams, many high-volume coal waste streams are likely to be unsuitable for use in those technologies. Semplastics’ technology has been shown to utilize most types of coal waste successfully without any pre-selection or pre-processing requirements other than a nominal particle-size reduction for wastes like bottom ash. This characteristic of Semplastics’ solution may enable the use of much larger volumes of a wider range of coal wastes than other coal-to-products technologies. In this project, Semplastics leveraged its unique experience with both coal waste (fly ash or coal combustion residuals), resin materials, and 3D printing to develop 3D printer filaments using common coal wastes – bituminous coal fines and fly ash – and researched the feasibility of using other forms of coal waste as fillers. Simple 3D-printed parts were successfully produced from the coal waste enhanced filaments, which were found to have improved strength and stiffness.

01 COAL, LIGNITE, AND PEAT↗

Quantification of complex protective surface oxide layer formed during plasma jet exposure of multicomponent ultra-high temperature carbides

Multicomponent ultra-high temperature ceramics (MC-UHTCs) has garnered attention due to their improved thermo-mechanical and oxidation properties. MC-UHTC was progressively formed by adding a UHTC component at each step, producing binary, ternary and quaternary UHTC systems, processed by spark plasma sintering (SPS). Here, we investigate the role of multi-elements and thermochemical stability of the surface oxide layer formed during plasma arc jet exposure (T > 2500 °C) of MC-UHTCs using core-level X-ray photoelectron spectroscopy (XPS) correlated with the structural investigation. The results indicate that adding a UHTC component improves oxidation resistance due to the assemblage of refractory phases forming complex mixed oxides via preferential oxidation. XPS spectra of Ta4f, Nb3d, Ti1p, and Hf4f showed that the nature of the chemical bonds switched from metal carbides to metal oxides (metal oxy-carbides) in the binary system with retained metal carbides in ternary and quaternary UHTCs. The absence of a metal carbide peak in the high-resolution C1s scan of the binary system also supports this finding. The principal complex mixed oxide phases emanate in the exiguous oxidation of MC-UHTCs are quantified using Rietveld analysis. Overall, this study suggests that MC-UHTC is a promising material for possible application in thermal protection systems (TPS).

36 MATERIALS SCIENCE↗

Micro-crack Pinning and Interfacial Fracture in Mixed Metal Oxide Reinforced Epoxy Nanocomposite

The effects of mixed metal oxides (Ce{sub x}Zr{sub 1−x}O{sub 2}) nanoparticle dispersion on the mechanical properties and fracture mechanisms of epoxy polymer matrix and its composite with glass fiber system are reported in this paper. Ce{sub x}Zr{sub 1−x}O{sub 2} nanoparticles are synthesized using sol–gel method, and its crystallinity is optimized. Epoxy nanocomposites are synthesized by a dispersion technique, and the compressive properties are optimized. The glass transition temperature has been improved. Epoxy with 5 wt.% of Ce{sub 0.75}Zr{sub 0.25}O{sub 2} shows optimal results with an increase of 17.4% in compressive modulus, and an increase of 23.4% in compressive strength with respect to those of neat epoxy. This improvement attributes to higher strength of shearing of polymer during the fracture of the nanoparticle interface. Micro-crack kinks at the interfaces can further delay fracture under compression. E-glass fabric-reinforced 5 wt.% Ce{sub 0.75}Zr{sub 0.25}O{sub 2}–epoxy nanocomposite also shows improvement in the mechanical properties via nanoscale interface with fibers. This type of ceramic nanocomposites has useful applications in thermal/electrical insulations besides improving the compressive/buckling properties.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Structural stability of BiFeO{sub 3} by chemical modification in Bi as well as Fe sites

Lanthanum and titanium doped BiFeO{sub 3} ceramics Bi{sub 1-x}La{sub x}Fe{sub 1-x}Ti{sub x}O{sub 3} (x and 0.0, 0.03 and 0.06) were synthesized by using the Sol-gel method. The phase purity has been studied by powder X-ray diffraction technique. No secondary phases were evident after lanthanum and titanium addition in certain proportion. The XRD patterns have been analyzed by employing Rietveld refinement technique with the help of Fullprof program. The XRD pattern could be refined by R3c space group in rhombohedral symmetry. The electrical characteristics for all samples have been studied by ferroelectric hysteresis loop at room temperature in the applied electric field of 60 kV/cm.

36 MATERIALS SCIENCE↗

Modeling the electrode geometry of co-planar capacitors for the microwave dielectric characterization of ceramic thin films

This paper describes the influence of co-planar electrode geometry on the measurement accuracy of microwave dielectric properties of sol-gel-derived Na{sub 0.5}Bi{sub 0.5}TiO{sub 3}-NaTaO{sub 3} thin films. The interdigital, co-planar capacitor configurations were prepared with E-beam lithography. A combination of analytical and numerical modelling was used for the optimization of co-planar, interdigital electrode structures for the thin-film characterization. We observed that the number of fingers, their length, as well as the gap between the fingers of the interdigital electrode structure of the co-planar capacitor have a pronounced influence on the accuracy of measurements.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Fabrication of PVDF-TrFE based bilayered PbTiO{sub 3}/PVDF-TrFE films capacitor

Development of high performance capacitor is reaching towards new generation where the ferroelectric materials take places as the active dielectric layer. The motivation of this study is to produce high capacitance device with long life cycle. This was configured by preparing bilayered films where lead titanate as an active dielectric layer and stacked with the top dielectric layer, poly(vinyledenefluoride-trifluoroethylene). Both of them are being referred that have one in common which is ferroelectric behavior. Therefore the combination of ceramic and polymer ferroelectric material could perform optimum dielectric characteristic for capacitor applications. The fabrication was done by simple sol-gel spin coating method that being varied at spinning speed property for polymer layers, whereas maintaining the ceramic layer. The characterization of PVDF-TrFE/PbTiO3 was performed according to metal-insulator-metal stacked capacitor measurement which includes structural, dielectric, and ferroelectric measurement.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Toughening materials: enhancing resistance to fracture

It has been said that ‘God invented plasticity, but the Devil invented fracture!’ Both mechanisms represent the two prime modes of structural failure, respectively, plastic collapse and the rupture/breaking of a component, but the concept of developing materials with enhanced resistance to fracture can be difficult. This is because fracture resistance invariably involves a compromise—between strength and ductility, between strength and toughness—fundamentally leading to a ‘conflict’ between nano-/micro-structural damage and the mechanisms of toughening. Here, we examine the two major classes of such toughening: (i) intrinsic toughening, which occurs ahead of a crack tip and is motivated by plasticity—this is the principal mode of fracture resistance in ductile materials, and (ii) extrinsic toughening, which occurs at, or in the wake of, a crack tip and is associated with crack-tip shielding—this is generally the sole mode of fracture resistance in brittle materials. We briefly examine how these distinct mechanistic processes have been used to toughen synthetic materials—intrinsically in gradient materials and in multiple principal-element metallic alloys with the example of metallic glasses and high-entropy alloys, and extrinsically in ceramics with the example of ceramic-matrix composites—in comparison to Nature which has been especially adept in creating biological/natural materials which are toughened by one or both mechanistic classes, despite often consisting of constituents with meagre mechanical properties. The success of Nature has been driven by its ability to cultivate the development of materials with multiple length-scale hierarchical structures that display ingenious gradients and structural adaptability, a philosophy which we need to emulate and more importantly learn to synthesize to make structural materials of the future with unprecedented combinations of mechanical properties.

36 MATERIALS SCIENCE↗

TH-CD-207B-06: Swank Factor of Segmented Scintillators in Multi-Slice CT Detectors: Pulse Height Spectra and Light Escape

Purpose: Pulse height spectra (PHS) have been used to determine the Swank factor of a scintillator by measuring fluctuations in its light output per x-ray interaction. The Swank factor and x-ray quantum efficiency of a scintillator define the upper limit to its imaging performance, i.e. DQE(0). The Swank factor below the K-edge is dominated by optical properties, i.e. variations in light escape efficiency from different depths of interaction, denoted e(z). These variations can be optimized to improve tradeoffs in x-ray absorption, light yield, and spatial resolution. This work develops a quantitative model for interpreting measured PHS, and estimating e(z) on an absolute scale. The method is used to investigate segmented ceramic GOS scintillators used in multi-slice CT detectors. Methods: PHS of a ceramic GOS plate (1 mm thickness) and segmented GOS array (1.4 mm thick) were measured at 46 keV. Signal and noise propagation through x-ray conversion gain, light escape, detection by a photomultiplier tube and dynode amplification were modeled using a cascade of stochastic gain stages. PHS were calculated with these expressions and compared to measurements. Light escape parameters were varied until modeled PHS agreed with measurements. The resulting estimates of e(z) were used to calculate PHS without measurement noise to determine the inherent Swank factor. Results: The variation in e(z) was 67.2–89.7% in the plate and 40.2–70.8% in the segmented sample, corresponding to conversion gains of 28.6–38.1 keV{sup −1} and 17.1–30.1 keV{sup −1}, respectively. The inherent Swank factors of the plate and segmented sample were 0.99 and 0.95, respectively. Conclusion: The high light escape efficiency in the ceramic GOS samples yields high Swank factors and DQE(0) in CT applications. The PHS model allows the intrinsic optical properties of scintillators to be deduced from PHS measurements, thus it provides new insights for evaluating the imaging performance of segmented ceramic GOS scintillators.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

A Diffuse-Interface Model for Predicting the Evolution of Metallic Negative Electrodes and Interfacial Voids in Solid-State Batteries with Homogeneous and Polycrystalline Solid Electrolyte Separators

Here, this paper presents a novel diffuse-interface electrochemical model that simultaneously simulates the evolution of the metallic negative electrode and interfacial voids during the stripping and plating processes in solid-state batteries. The utility and validity of this model are demonstrated for the first time on a cell with a sodium (Na) negative electrode and a Na-β″-alumina ceramic solid electrolyte (SE) separator. Three examples are simulated. First, stripping and plating with a perfect electrode/electrolyte interface; second, stripping and plating with a single interfacial void at the electrode/electrolyte interface; third, stripping with multiple interfacial voids. Both homogeneous and polycrystalline SEs with low and high-conductivity grain boundaries (GBs) are considered for all three examples. Heterogeneous GB conductivity marginally impacts the thickness of the Na electrode in cases with a perfect electrode/electrolyte interface. Moreover, it results in local changes to void growth due to the interactions between the void edge and the GBs. The void growth rate is a linear function of the flux of Na atoms at the void edge, which in turn depends on the applied current density. We also show that the void coalescence rate increases with applied current density and can be marginally influenced by GB conductivity.

batteries↗

Task 2.1: Adsorption-Based ISPR for BETO-Relevant Bioproducts

This task focuses on the development of adsorption-based in situ product recovery (ISPR) integrated with simulated moving bed chromatography for the recovery and purification of carboxylate products that are relevant to BETO. ISPR has been pursued previously in the Separations Consortium to recover carboxylic acids near or below their pKa values with liquid-liquid extraction coupled to downstream distillation. However, there are many acid products in the BETO portfolio that require neutralization well above their pKa values wherein ISPR could still be a major benefit to the bioprocess performance, including muconic acid, beta-ketoadipic acid, 3-hydroxypropionic acid, itaconic acid, butyric acid, and others. In this task, we are combining dynamic filtration with a rotating ceramic disk, resin capacity measurements, tailored resin synthesis, and simulated moving bed chromatography into an ISPR system that can be used to recover BETO-relevant carboxylates from bioreactor cultivations. We are working across process scales and using computational modeling where applicable alongside techno-economic analysis and life cycle assessment to understand major cost, energy, and GHG emissions drivers. The impact of this project will be a bench-scale integrated approach to recover carboxylate products in situ, which will reduce the waste generation from biological carboxylate production processes and improve the productivities of biological systems.

bio-based acid↗

Fabrication of compact electron gun for 6 MeV X-ray source

The 6 MeV X-Ray source for container cargo scanning application has been designed and developed by the Accelerator and Pulse Power Division, BARC, Mumbai. This compact linac has been designed as a mobile system, to be mounted on a moving container. In linac-based cargo-scanning system, to work electron gun on a movable container, it has to be robust. Electron gun is to work at 10{sup -7} mbar vacuum and 2000 degree Celsius temperature. An effort is made to engineer the gun assembly to make it more robust and aligned. The linac acts as the source of X-rays, which fall on the cargo and are then detected by the detector system. Many components are indigenously developed like grid, insulating ring, Tungsten filament and filament guide, which are made from alumina ceramic and Tantalum which is to work at 1500 degree Celsius. Filament connector is made from Invar to reduce heat loss and to make rigid connection. It was CNC machined and wire cut by EDM. Invar and Copper electrode feed through is shrink fitted with the help of liquid Nitrogen. Shrink fit tolerances of 15 micrometer are achieved by jig boring machining processes. Tantalum cup for LaB6 cathode and heat shield are made from die and punch mechanism. For alignment of electron emitter with beam axis this Tantalum cup is a crucial component. Electron gun is assembled and aligned its components with the help of precision jigs. The whole assembly was Helium leak tested by MSLD up to 4 x 10{sup -10} mbar.l/s vacuum, no leak was found. This paper will describe the machining, Tantalum cup forming, ceramic components development, heat shields, ceramic feed through etc of electron gun. (author)

43 PARTICLE ACCELERATORS↗

Structural and transport properties of NdCrO{sub 3} nanoceramics

Reitveld refinement of the room temperature powder X-ray diffraction profile of NdCrO{sub 3} (NCO) nanoceramics synthesized by sol-gel processing shows orthorhombic Pnma (D{sub 2h}{sup 16}) space group symmetry. The refined lattice parameters are a = 5.482(3) A, b = 7.689(4) A and c = 5.416(3) A. Transmission electron microscopy (TEM) of NCO shows that the average particle size is around 70 nm. The electrical transport property of NCO is investigated by both conductivity and electric modulus formalism. The electrical data is taken by a LCR meter in a temperature range from 303 K to 573 K and in a frequency range from 42 Hz to 1.1 MHz. The ac conductivity follows a power law. The Cole-Cole plot of impedance at 303 K shows grain effect.

36 MATERIALS SCIENCE↗