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At least 739 records · Page 41

Mechanical evaluation of WC-Co materials with varying microstructures

Tungsten carbide–cobalt materials are useful in a variety of extreme applications due to a desirable blend of properties, yet the technology has not significantly changed since their initial development in the 1920s. The mechanical properties of this class of materials is highly dependent on two variables, the size of the tungsten carbide grains, and the amount of binder phase present in the final body. In this study, the amount of binder phase is isolated across three commercial materials from the same manufacturer with three different grain sizes to investigate the effect on mechanical properties. The mechanical properties investigated are indentation hardness, flexure and tensile strength, as well as fracture toughness. In general, an increase in hardness and tensile strength with decreasing grain size was observed, while the fracture toughness showed the opposite trend with toughness increasing with increasing grain size. The flexure strength results did not show a correlation to grain size. Fractographic analysis identified the dominant strength-limiting flaw for each sample, which largely were in the form of porosity. Other flaws types, such as inclusions from the milling process, clusters of large grains, and machining cracks from the surface finishing process, were also identified. Finally, Weibull analysis was performed and deemed appropriate for analysis of these materials, but strength-size scaling was not conducted due to the variability in the strength-limiting feature between the different specimen geometries.

36 MATERIALS SCIENCE↗

A non-isothermal breakage-damage model for plastic-bonded granular materials incorporating temperature, pressure, and rate dependencies

Plastic-bonded granular materials (PBM) are widely used in industrial sectors, including building construction, abrasive applications, and defense applications such as plastic-bonded explosives. The mechanical behavior of PBM is highly nonlinear, irreversible, rate dependent, and temperature sensitive governed by various micromechanical attributions such as grain crushing and binder damage. This paper presents a thermodynamically consistent, microstructure-informed constitutive model to capture these characteristic behaviors of PBM. Key features of the model include a breakage internal variable to upscale the grain-scale information to the continuum level and to predict grain size evolution under mechanical loading. In addition, a damage internal state variable is introduced to account for the damage, deterioration, and debonding of the binder matrix upon loading. Temperature is taken as a fundamental external state variable to handle non-isothermal loading paths. The proposed model is able to capture with good accuracy several important aspects of the mechanical properties of PBM, such as pressure-dependent elasticity, pressure-dependent yield strength, brittle-to-ductile transition, temperature dependency, and rate dependency in the post-yielding regime. Furthermore, the model is validated against multiple published datasets obtained from confined and unconfined compression tests, covering various PBM compositions, confining pressures, temperatures, and strain rates.

Breakage↗

Carbon dioxide integration into alkali aluminosilicate cement particles for achievement of improved properties

Alkali aluminosilicate cement developed using ground granulated blast furnace slag was produced mechanochemically in the presence of lime and sodium hydroxide. Processing of this cement in a carbon dioxide environment led to the incorporation of carbon dioxide into the resultant hydraulic cement as metastable carbonate complexes. The hydration reactions of cement were complemented with formation of crystalline carbonates; the resultant hydrates and carbonates made synergistic contributions towards the binding effects and stability of the inorganic binder. Analytical chemistry and physical test methods were performed on cements and their hydrates in order to understand the form of carbon dioxide in their corresponding structures. Here the test results indicated that carbon dioxide was integrated into the cement particles in metastable form, which formed carbonate crystallites integrated with the amorphous hydrates in the course of hydration of cement. This phenomenon led to significant improvements in the mechanical properties of the resulting binder.

54 ENVIRONMENTAL SCIENCES↗

Development of a high-temperature inorganic synthetic foam with recycled fly-ash cenospheres for thermal insulation brick manufacturing

In this study, a novel inorganic synthetic solid foam composed of recycled fly-ash cenospheres (FACs) is developed with low-density, good thermal insulation performance, and reasonable mechanical strength. The manufacturing process utilizes low-fraction clay binder materials diluted in water, enabling a self-assembling mechanism assisted by natural capillary effect to form minimal contacts among the FACs. The microstructure and minimal contact formation were confirmed by optical and electron microscope imaging. Both thermal and mechanical properties of the fly-ash cenosphere synthetic solid foam (FAC-SSF) materials were experimentally studied as functions of key material parameters including cenosphere particle size and clay content. A numerical model was developed to predict the effective thermal conductivity of FAC-SSF using a three-step homogenization method which takes into account different thermal percolation paths within the material. The inorganic synthetic foam developed has the potential for thermal insulation applications taking advantage of their relatively simple, low-cost, and scalable manufacturing process, minimal use of binder materials, and relatively high mechanical strength and highly tailorable properties.

42 ENGINEERING↗

Green micromachining of ceramics using tungsten carbide micro-endmills

This paper presents an experimental analysis on micromachining of green-state silicon carbide (SiC) and aluminum nitride (AlN) using uncoated tungsten carbide (WC) micro-endmills. Although the unique properties of ceramics make them ideal materials for many applications involving micro-scale features, the industrial adaptation of ceramics at the micro-scale has been hindered due to the lack of viable ceramic micro-manufacturing techniques. Green micromachining (GMM), where micro-scale features are created by micromachining green-state ceramics that contain ceramic particles and a polymer binder, offers a potential solution for this problem by affording tremendous improvements in micromachinability with respect to sintered ceramics. After the completion of GMM, the green parts are debound and sintered to obtain the final component with the desired microscale features. In this work, we evaluated GMM characteristics of powder-injection molded green-state SiC and AlN to correlate process conditions and green-material compositions with the micromachining forces, quality, and tool wear. An experimental study that involves full immersion micromilling tests with 254 μm diameter micro-endmills at different cutting speeds and feed rates is conducted. For each of the two materials, two binder states (with and without wax) and two powder states (with micro particles only, or with both micro- and nanoparticles) are investigated. Green micromachining forces, specific energies and the resulting surface roughness are analyzed quantitatively. A qualitative analysis of burr formation and channel quality, as well as a preliminary study on micro-tool wear are also performed. Both the machining conditions and the material compositions are seen to have a strong effect on micro-machinability of green-state ceramics. Overall, we conclude that GMM can be a viable ceramic micro-manufacturing strategy if favorable (or optimal) micromachining and material parameters are identified through the presented (or a similar) micromachinability study.

36 MATERIALS SCIENCE↗

Aligned carbon fibers-carbon nanotube-polymer-based composite as lithium-ion battery current collector

High energy density demand is pushing the development of high-voltage cathode materials, which necessitates improved electrochemical stability of other battery components such as binders, electrolytes, and current collectors. Current collectors are considered to be an inactive component but still play an essential role. In this study, a metal-free composite film containing directionally aligned carbon fiber (CF), carbon nanotube (CNT), and polymer (P) was developed to replace aluminum foil as a cathode current collector, which relies on forming an Al 2 O 3 layer to ensure electrochemical stability at high voltage. Here, each component in the new cathode current collector played a functional role. The CNTs provided uniform current densities, and CFs improved the electronic conductivity and mechanical strength of the composite material. The polymer enhanced the adhesion of the cathode coating with the current collector and provided an impervious support to the cathode materials. The CF-CNT-P composite demonstrated excellent electrochemical and thermal stability. Cathodes coated on the CF-CNT-P composite exhibited lower charge transfer resistance, improved rate capability, and improved cyclic stability compared with the cathodes deposited on conventional aluminum foil. Additionally, the composite current collector was lighter (1.81 mg/cm 2 and 15 µm thick) than the commonly used aluminum foil (4.35 mg/cm2 and 15 µm thick), which can increase the cell energy density. Additionally, the CF-CNT-P did not need to be separated from the cathode coating during recycling and can be burnt out with binder, simplifying the recycling process.

25 ENERGY STORAGE↗

Discovery and Characterization of FMN-Binding β-Glucuronidases in the Human Gut Microbiome

The human gut microbiota encodes β-glucuronidases (GUSs) that play key roles in health and disease via the metabolism of glucuronate-containing carbohydrates and drugs. Hundreds of putative bacterial GUS enzymes have been identified by metagenomic analysis of the human gut microbiome, but less than 10% have characterized structures and functions. Here in this paper we describe a set of unique gut microbial GUS enzymes that bind flavin mononucleotide (FMN). First, we show using mass spectrometry, isothermal titration calorimetry, and x-ray crystallography that a purified GUS from the gut commensal microbe Faecalibacterium prausnitzii binds to FMN on a surface groove located 30 Å away from the active site. Second, utilizing structural and functional data from this FMN-binding GUS, we analyzed the 279 unique GUS sequences from the Human Microbiome Project database and identified 14 putative FMN-binding GUSs. We characterized four of these hits and solved the structure of two, the GUSs from Ruminococcus gnavus and Roseburia hominis, which confirmed that these are FMN binders. Third, binding and kinetic analysis of the FMN-binding site mutants of these five GUSs show that they utilize a conserved site to bind FMN that is not essential for GUS activity, but can affect KM. Lastly, a comprehensive structural review of the PDB reveals that the FMN-binding site employed by these enzymes is unlike any structurally characterized FMN binders to date. These findings reveal the first instance of an FMN-binding glycoside hydrolase and suggest a potential link between FMN and carbohydrate metabolism in the human gut microbiota.

59 BASIC BIOLOGICAL SCIENCES↗

Solution-based approaches for making high-density sodalite waste forms to immobilize spent electrochemical salts

Three different solution-based approaches were taken to make sodalite minerals as a host for a mixed salt simulating the waste generated during the electrochemical separations process of nuclear fuel reprocessing that contains alkali, alkaline earth, and lanthanide chlorides plus trace iodine and actinides. All of the approaches included an aqueous solution of mixed chlorides (simulated waste) but the other reactants varied: (1) Al(OH)3 + NaOH + CS, (2) NaAlO2 + CS, and (3) Al2Si2O7 + NaOH, (CS = colloidal silica). The products were dried, ground, pressed into pellets, fired (650–950 °C), and characterized. Both 5 and 10 mass% of a Si-Na-B glass binder were introduced at different stages in the process. Route (2) proved the most successful at producing high sodalite fractions (up to 100%) with minimal glass binder additions and showed high consolidation potential (up to 91.4% of theoretical density). Detailed comparisons are provided of the results.

electrochemical↗

Glass-bonded iodosodalite waste form for immobilization of 129I

Immobilization of radioiodine (e.g., 129I, 131I) is an important need for current and future nuclear fuel cycles. For the current work, iodosodalite [Na8(AlSiO4)6I2] was synthesized hydrothermally from metakaolin, NaI, and NaOH. Following hydrothermal treatment, dried unwashed powders were used to make glass-bonded iodosodalite waste forms by heating pressed pellets at 650, 750, or 850 °C with two different types of sodium borosilicate glass binders, i.e., NBS-4 and SA-800. These heat-treated specimens were characterized with X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, thermal analysis, porosity and density measurements, neutron activation analysis, and inductively-coupled plasma mass spectrometry. The pellets mixed with 10 mass% of NBS-4 or SA-800 and heat-treated at 750 °C contained relatively high percentage iodine retention (~44-47 % of the maximum iodine loading) with relatively low porosities, while other pellets with higher percentages iodine retention either contained higher porosity or were not completely sintered. ASTM C1308 chemical durability tests of monolithic specimens showed a large initial release of Na, Al, Si, and I on the first day, possibly from water-soluble salt crystals or non-durable amorphous phases. Release rates of Na and Si were higher than for Al and I, probably due to a poorly durable Na-Si-O phase from the glass bonding matrix. The cumulative normalized release of iodine was 12.5 g m-2 for the first 10 1-d exchanges, suggestive of coherent dissolution. The average release rate from 10-24 days during the 7-d exchange intervals was 0.2336 g m-2 d-1.

sodalite, iodosodalite, waste forms, iodine↗

Site specific, high-resolution characterisation of porosity in graphite using FIB-SEM tomography

Graphite is used as a moderator of fast neutrons in some types of nuclear reactors and for other industrial applications. The influence of smaller pores on the mechanical and physical properties of graphite remains to be fully understood. Here in this work, focused ion beam-scanning electron microscopy (FIB-SEM) tomography was applied to characterise the porosity of AGX graphite – an electrode material. FIB-SEM tomography consists in alternating the ion milling and SEM imaging at an area of interest with the objective of creating a 3D reconstruction. Regions containing a filler and a mixture of filler and binder were selected as the areas of interest. Resolutions of a few nanometers were achieved in volumes up to 1400 μm 3 for both regions. Typical porous structures were detected in the filler and binder regions such as thermal cracks, gas evolution porosity and lenticular pores. The resolution achieved with these experiments made possible detection of pores smaller than 150 nm in diameter, that is of the length scale of voids generated by neutron irradiation, and an improvement in spatial resolution of traditional x-ray tomography studies. The resolution achieved by FIB-SEM tomography may be essential for the study of the microstructure of graphite, providing complimentary data to x-ray tomography experiments.

36 MATERIALS SCIENCE↗

Glass-bonded ceramic waste forms for immobilization of radioiodine from caustic scrubber wastes

Glass-bonded sodalite composite waste forms have been developed for the immobilization of liquid radioactive wastes resulting from off-gas treatment during aqueous reprocessing of used nuclear fuel, with a particular focus on 129I. The proposed composite waste form is comprised of aluminosilicate ceramic phases containing volatile radionuclides bonded with a glassy matrix. In this work, a suite of ten candidate low-temperature glass binders (ZnO-Bi2O3-based glasses and a Na2O-B2O3-SiO2 glass) were examined. Six glasses were mixed with caustic scrubber waste simulant previously converted into a sodalite-rich material (to provide glass fractions of 10 and 20 wt.%), uniaxially pressed into pellets, and sintered at 350 °C or 550 °C for 8 h in air. Iodine retention after heat treatment was assessed by neutron activation analysis, showing retention of 67-100 % of expected iodine. The aqueous durabilities of the resulting materials were then determined, following the ASTM C1308 standard test, showing iodine releases of 1 to 23 g m-2 after 4 d. The cumulative iodine release for the best performing system (a zinc-bismuth-borate glass binder) was <1 g m-2, and its iodine retention from processing was 67 %. The iodine releases compared favorably with other waste forms. In parallel, this best-performing composition was also consolidated via hot isostatic pressing (HIP) in a stainless-steel canister at 550 °C for 2 h under 100 MPa pressure. The HIPed sample was produced at the ~20 g scale and showed improved densification and minimal reaction with the canister.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Through-thickness fracture behavior of neutron-irradiated nuclear graphite NBG-17 Using X-ray micro-CT

Achieving precise control over crack propagation in nuclear graphite and conducting quantitative analysis remain challenging. In this study, the through-thickness fracture behavior of pristine and neutron-irradiated (700 °C, ∼7 dpa) NBG-17 nuclear graphite was investigated using split-disc testing coupled with micro-computed tomography (micro-CT). A notably lower number of micropores was observed in the neutron-irradiated specimen. The fracture toughness of neutron-irradiated NBG-17 was measured to be 1.45 MPa√m, compared to 1.17 ± 0.05 MPa√m for the pristine specimen. In both materials, cracks were found to initiate at the filler–binder interface, and often correlated with microstructural features such as pores and thermal cracks. Crack bridging and deflections emerged as the primary toughening mechanisms in both unirradiated and irradiated NBG-17. However, compared with the pristine specimen, the cracks in the neutron-irradiated specimen were more likely to grow trans granularly, resulting in less deflected crack paths. The reduced micro-porosity and strengthened filler–binder boundaries were considered to be the cause of the observed differences in crack morphologies. In conclusion, this study provides a qualitative analysis of the fracture behavior of neutron-irradiated nuclear graphite in the absence of radiolytic oxidation.

36 - MATERIALS SCIENCE↗

Analysis of geometric and electrochemical characteristics of lithium cobalt oxide electrode with different packing densities

In order to investigate geometric and electrochemical characteristics of Li ion battery electrode with different packing densities, lithium cobalt oxide (LiCoO 2 ) cathode electrodes were fabricated from a 94:3:3 (wt%) mixture of LiCoO 2 , polymeric binder, and super-P carbon black and calendered to different densities. A synchrotron X-ray nano-computed tomography system with a spatial resolution of 58.2 nm at the Advanced Photon Source of the Argonne National Laboratory was employed to obtain three dimensional morphology data of the electrodes. The morphology data were then quantitatively analyzed to characterize their geometric properties, such as porosity, tortuosity, specific surface area, and pore size distribution. The geometric and electrochemical analysis reveal that high packing density electrodes have smaller average pore size and narrower pore size distribution, which improves the electrical contact between carbon-binder matrix and LiCoO 2 particles. The better contact improves the capacity and rate capability by reducing the possibility of electrically isolated LiCoO 2 particles and increasing the electrochemically active area. The results show that increase of packing density results in higher tortuosity, but electrochemically active area is more crucial to cell performance than tortuosity at up to 3.6 g/cm 3 packing density and 4 C rate.

25 ENERGY STORAGE↗

Long carbon fibers boost performance of dry processed Li-ion battery electrodes

Dry processing (DP) is an advanced manufacturing technique for lithium-ion battery (LIB) electrodes. Unlike conventional wet-process-based manufacturing that involves dissolving polyvinylidene fluoride (PVDF) binder in n-methyl-2-pyrrolidone (NMP) solvent for slurry-casting, DP involves fibrillation of polymer binders. This method offers environmental and cost benefits by eliminating the need for expensive and environmentally hazardous organic solvents. However, DP-produced electrode films often lack mechanical stability due to the absence of a current collector substrate during electrode material layer fabrication. This reduced mechanical instability results in difficulty during fabricating of thin electrodes (≈5 mAh/cm 2 ). To address this issue, long (>8 mm) carbon fiber (CF) has been incorporated to reinforce the mechanical strength of the electrode films. In conclusion, the study demonstrates that the inclusion of long carbon fiber boosts the mechanical, electrical, thermal, and electrochemical performance of DP electrodes.

25 ENERGY STORAGE↗

High tensile alloy of copper to mitigate current collector deformation in silicon electrodes for lithium-ion batteries

The volumetric changes of silicon electrodes, along with the strong adhesive properties of certain binders, can lead to plastic deformation of the current collector and create damage in the electrode coating. Here, in this study, we report a detailed study of silicon coatings on a high-tensile alloy (HTA) foil of copper with strength over twice that of conventional copper foils. The HTA current collectors with high mechanical strength can mitigate plastic deformation upon continuous cycling. At moderate areal capacities (2.5–3 mAh cm −2 ), conventional copper foils show significant wrinkling after only a few electrochemical cycles, whereas the HTA foils remain intact. We demonstrate viability of the HTA foils in large format xx6395 pouch cells, in which the HTA current collectors remain intact even at an areal capacity of 4.5 mAh cm −2 ; in contrast, wrinkles form in conventional copper current collectors increasing the likelihood of lithium plating. Computational studies show that stresses generated during cycling of silicon electrodes are very high in the current collector and at the current collector-coating interface, explaining the wrinkling of conventional Cu foils. Our studies highlight importance of current collector to solve the electrochemical and chemo-mechanical performance challenges associated with high-loading silicon electrodes.

Chemo-mechanical degradation↗

Characterization of 430L porous supports obtained by powder extrusion moulding for their application in solid oxide fuel cells

The characterization of 430L stainless steel planar porous supports obtained by powder extrusion moulding was performed in this work. A thermoplastic multicomponent binder based on high density polyethylene and paraffin wax was selected for the process. Green supports were shaped by extrusion moulding, and subsequently the binder was removed by a thermal cycle previously optimized. Sintering was carried out at different temperatures in low vacuum. Density of sintered parts was measured by Archimedes' method and porosity was also evaluated through a microstructural analysis by optical microscopy. The porosity degree of samples sintered at low temperature was close to 35% which is a very suitable value for their application in SOFCs. Tensile tests were carried out in order to determine mechanical strength as a function of porosity degree. Based on these results, the best feedstock composition and processing parameters were selected. The oxidation behaviour in static air at high temperature was studied, and formed oxides were characterized in a scanning electron microscope equipped with energy dispersive analysis of X-rays. X-ray diffraction experiments were performed in order to identify the formed oxides based on formula Fe{sub 2−x}Cr{sub x}O{sub 3}. The results of these studies showed that this kind of ferritic stainless steel would be more suitable to be used as anodic supports where a rich hydrogen atmosphere is employed. Preliminary deposition tests allowed obtaining a homogeneous Ni–YSZ anode layer with a thickness of 10 μm on the porous metallic substrates. - Highlights: • 430L stainless steel porous supports were obtained by powder extrusion moulding. • Porosity degree was controlled sintering at different temperatures in low vacuum. • Tensile tests allowed determining mechanical strength of porous supports. • A study about its oxidation behaviour in static air at high temperature was realized. • After oxidation, formed oxides were characterized by EDS–SEM and XRD.

36 MATERIALS SCIENCE↗

Multiscale characterization and comparison of historical and modern nuclear graphite grades

Beginning with Chicago Pile I, graphite has been used as a moderator material in nuclear power stations and is considered a potential material for use in future Generation IV advanced reactors. The microstructure of graphite is responsible for much of its mechanical and thermo-physical properties, and how it responds to irradiation. To understand graphite microstructure, it is necessary to understand its porosity at the macro- and micro-scales; and to understand its porosity, it is necessary to characterize the morphological connectivity of the void content and the two main phases of graphite: filler and binder. Here, using several microscopy and analytical techniques, a detailed examination of the heterogeneity, microstructure and pore structure of different graphite grades and their binder and filler phases is presented. Significant differences were found between coarser and finer nuclear grades. Coarse grades have a more diverse range of filler particles, pores and thermal cracks. Finer grades have a more well-defined pore size distribution, fewer variations of filler particles sizes and do not contain as many large thermal cracks. Fine grades tend to have a well-connected network of pores whereas coarser grades contain a larger content of closed porosity. The framework developed within this work can be applied and used to assess the various graphite grades that would down-select materials for specific use in graphite moderated reactor designs.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗