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Canfield, Nathan L.

Publications and source records attributed to Canfield, Nathan L..

At least 37 records · Page 2

Role of Zeolite Structural Properties toward Iodine Capture: A Head-to-head Evaluation of Framework Type and Chemical Composition

This study evaluated zeolite-based sorbents for iodine gas [I2(g)] capture. Based on the framework structures and porosities, five zeolites, including two faujasite (FAU), one ZSM-5 (MFI), one mesoMFI, one ZSM-22 (TON), as well as two mesoporous materials, were evaluated for I2(g) capture at room temperature and 150 °C in an iodine-saturated environment. From these preliminary studies, the three best-performing zeolites were ion-exchanged with Ag+ and evaluated for I2(g) capture under similar conditions. Energy-dispersive X-ray spectroscopy data suggest that Ag-FAU frameworks were the materials with the highest capacity for I2(g) in this study, showing ~3× higher adsorption compared to Ag-mordenite (Ag-MOR) at room temperature, but X-ray diffraction measurements show that the faujasite structure collapsed during the adsorption studies because of dealumination. The Ag-MFI zeolites are decent sorbents in real-life applications, showing both good sorption capacities and higher stability. In-depth analyses and characterizations, including synchrotron X-ray absorption spectroscopy, revealed the influence of structural and chemical properties of zeolites on the performance for iodine adsorption from the gas phase.

aluminosilicate zeolites, iodine, porosity, acidit↗

Review and Experimental Comparison of the Durability of Iodine Waste Forms in Semi-Dynamic Leach Testing

To ensure the safe disposal of radioiodine-containing nuclear wastes, a durable iodine waste form (IWF) is required. Many IWFs have been developed and evaluated for chemical durability using a wide range of test methods, making direct comparisons difficult as highlighted in this work through a review of available IWF corrosion data. To move toward a common dataset, a semi-dynamic leach test suite was experimentally demonstrated using several IWF types, providing standard comparisons. The results highlighted clear differences in corrosion resistance between various IWFs. This test suite is suggested for future studies to generate comparable data for a common dataset.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of various post-extrusion tempering on performance of AA2024 tubes fabricated by shear assisted processing and extrusion

In this report aluminum alloy 2024 (AA2024) tubes were extruded using the shear assisted processing and extrusion (ShAPE) method. As a ubiquitous aerospace alloy, AA2024 has reached a high degree of maturity with respect to manufacturing processes, alloy chemistry and heat treatment to maximize material strength. Therefore, over the eight decades since the introduction of this alloy, the mechanical properties have plateaued, and the extrusion speed has reached a 3.5 m/min ceiling using conventional extrusion. The ShAPE technique enabled an extrusion speed of AA2024 up to 7.4 m/min at 480 °C which is surpassing the extrudability chart of this alloy. Variation of the standard T3510 and T8510 post extrusion heat treatments were applied to improve the mechanical performance of the ShAPE extruded AA2024 tube. The ultimate tensile strength and yield strength of AA2024-T8510 ShAPE extruded tube are 522.0 ± 3.3 MPa and 510.7 ± 3.3 MPa, which are respectively 18% and 32% higher than ASM-typical and ASTM minimum values. The elongation at break of ShAPE extruded AA2024-T8510 tubes is two times higher than the ASM-typical and ASTM-minimum values. This improved ductility is attributed to the refinement of grain size and secondary phases as well as due to the uniform dispersion of sub-micron strengthening precipitates formed during the ShAPE process.

42 ENGINEERING↗

Effect of post-extrusion heat treatment on mechanical property of aluminum alloy 2024 tube produced using Shear Assisted Processing and Extrusion (ShAPE)

The present work deals with the Shear Assisted Processing and Extrusion (ShAPE) of aluminum alloy 2024 tubes and mechanical property optimization via post extrusion heat treatments (T3510 and T8510). The ShAPE process enables extruding AA2024 at an extrusion speed of 7.4 m/min and extrusion temperature of 480 °C, which is otherwise beyond the extrudability limit of this alloy using conventional extrusion techniques. The ultimate tensile strength reaches 466 MPa for ShAPE+T3510 condition and 503 MPa for ShAPE+T8510 condition, both of which exceed the corresponding ASTM/ASM (minimum/typical) values for the studied tube geometry. The yield strength reaches 382 MPa for ShAPE+T3510 condition and 481 MPa for ShAPE+T8510 condition, both of which surpass any reported values in the literature or the highest industrial values. In addition, the ductility of AA2024 tube fabricated from ShAPE+T3510 or ShAPE+T8510 are evidently improved by the grain size refinement, second phase refinement, and enhanced uniformity in second phase distribution due to the severe plastic deformation of ShAPE process.

Shear Assisted Processing and Extrusions (ShAPE), ↗

Shear Assisted Processing and Extrusion (ShAPE) of Aluminum Alloy 7075, 2024, and Al-12.4TM

The most common aluminum alloys utilized in the aerospace industry are 7075 and 2024 due to their high strength-to-weight ratio compared to advanced high strength steels and other aluminum alloys. Despite excellent performance, these aluminum alloys have seen limited use outside of the aerospace industry due in part to high cost. If high-performance aluminum extrusions could be made more cost effectively by eliminating energy intensive process steps typical of conventional extrusion, then numerous opportunities exist for more widespread adoption. A key reason for the high cost of 7075 and 2024 extrusions (25-75% higher than 6061) is their slow extrusion speed. 7075 and 2024 are limited to 2 m/min and 3.5 m/min respectively, in contrast to 6061 which can be extruded at 20–80 m/min. In addition to slow speed, aluminum alloys require numerous thermal treatments throughout the extrusion process including homogenization and pre-heating prior to extrusion, and solution heat treating and artificial aging after extrusion. Each of these steps contribute to the total energy consumed during manufacturing of extruded components. This project investigates the use of ShAPE to improve extrusion speed and reduce, or even eliminate, the typical thermal treatments for high strength aluminum alloys, all while improving material performance. The overarching goal of this project was to demonstrate that Shear Assisted Processing and Extrusion (ShAPE) can manufacture high-performance aluminum alloy tubing with lower manufacturing energy and improved mechanical properties compared to conventional extrusion. Unlike conventional extrusion where the billet is rammed against a stationary die using a strictly linear motion, the ShAPE process superimposes a rotational shear force by spinning the die while the billet is plunged. Compared to conventional linear extrusion, the ShAPE process imparts significantly more strain into the feedstock material, which enables the formation of novel microstructures. These microstructures manifest an array of property and process improvements for extrusion of high-performance aluminum alloys. The following accomplishments were achieved for this project: Extrusion of 7075 at 12.2 meters/min compared to 2 meters/min for conventional extrusion; Elimination of 7075 billet homogenization (430 °C for 20 hours) which is required prior to conventional extrusion; Elimination of 7075 billet pre-heating (400 °C for 1 hour) in a separate furnace which is required prior to conventional extrusion; Achieved 7075-T6with yield strength = 595 MPa, ultimate tensile strength = 531MPa, and elongation = 17.4% for extrusions made from unhomogenized billets. Exceeds the ASTM and ASM standard, and typical industry values; Achieved 7075-T5 (i.e., no solution heat treatment) with yield strength = 588 MPa, ultimate tensile strength = 535 MPa, and elongation = 14.8% for extrusions made from homogenized billets; Extrusion of 2024 at 7.4 meters/min compared to 3.5 meters/min for conventional extrusion; Achieved 2024-T8510 yield strength = 522 MPa, ultimate strength = 510MPa, and elongation = 7.1% for extrusions made from wrought billets. Exceeds the ASTM and ASM standard, and typical industry values; Extrusion of Al-12.4TM high-performance aluminum powder directly into tubing, in a single step, which eliminates process steps typical of powder metallurgy extrusion.

36 MATERIALS SCIENCE↗

Applying laboratory methods for durability assessment of vitrified material to archaeological samples

Abstract Laboratory testing used to assess the long-term chemical durability of nuclear waste forms may not be applicable to disposal because the accelerated conditions may not represent disposal conditions. To address this, we examine the corrosion of vitrified archeological materials excavated from the near surface of a ~1500-year old Iron Age Swedish hillfort, Broborg, as an analog for the disposal of vitrified nuclear waste. We compare characterized site samples with corrosion characteristics generated by standard laboratory durability test methods including the product consistency test (PCT), the vapor hydration test (VHT), and the EPA Method 1313 test. Results show that the surficial layer of the Broborg samples resulting from VHT displays some similarities to the morphology of the surficial layer formed over longer timescales in the environment. This work provides improved understanding of long-term glass corrosion behavior in terms of the thickness, morphology, and chemistry of the surficial features that are formed.

36 MATERIALS SCIENCE↗

Manufacturing Dissolvable Alloy Components using ShAPE: A Study on Solid Phase Processing of Mg-W Composites and WJ11 Alloys

Dissolvable alloys and composites are an emerging class of materials that demonstrate tailored sorptivity in corrosive environments. This work explored the viability of solid phase processing (SPP) techniques, namely the shear assisted processing and extrusion (ShAPETM) method, to manufacture dissolvable magnesium composites and alloys components such as rods and tubes. The study also determined the effects of material composition and manufacturing process conditions on material microstructures developed during SPP and the resulting performance of the components. Explicit properties of interest included ultimate tensile strength, ultimate compressive strength, and yield strength. The application fields of interest for dissolvable alloys were identified as oil-and-gas operations and biomedical implants. Accordingly, PNNL collaborated with industrial and academia partners, Fortek Industries, Houston and University of Pittsburgh, during the course of this project for material and ShAPE process development. PNNL determined the viability of the using ShAPE to process the custom-designed materials provided by the project partners. This was done by identifying process parameters such as tool rotation rate, tool plunge rate, and process cooling optimal for manufacturing components with consolidated microstructures. Subsequently, PNNL also performed microstructural characterization on unprocessed and processed samples and mechanical property testing. One of the major findings from this work is that ShAPE was able to manufacture dissolvable magnesium composite and alloy rods and tubes with consolidated homogeneous microstructures and minimal macroscale defects on component surfaces. It was observed that samples processed via ShAPE demonstrated an average grain size < 2 - 5 µm, which was markedly lower than that of the precursors with 8 – 13 µm grains. Results showed that the ShAPE synthesized dissolvable magnesium composite and alloy strength was on par with or better than those components that were manufactured using traditional manufacturing processes such as forging and extrusion. It is noteworthy that the ShAPE samples were made with considerably lower number of process steps.

36 MATERIALS SCIENCE↗

Lanthanum Strontium Cobaltite-Alumina Fiber Composite Contact Material for Solid Oxide Fuel Cells

Short alumina fibers were added to LSCo contact material to enhance the contact strength and improve thermal cycle stability. Alumina fiber from 2.5 v% to 20 v% were mixed with LSCo and sintered at elevated temperatures. Sintering study showed retardation in densification of LSCo matrix with increasing alumina content. Sintered bulk strength exhibited similar behavior where strength greatly reduced at high alumina v%. Coefficient of thermal expansion showed consistent results with prediction from rule of mixture. Contact strength using anode supported YSZ bilayer coupons improved greatly with the presence of small amount (2.5-5 v%) alumina fibers and no substantial reduction after 10 deep thermal cycles. Candidate LSCo-Al2O3 contact materials was validated in a generic stack test fixture for 1000h at 800oC followed by 10 thermal cycles. Results of impedance analysis showed substantial improvement in thermal cycle stability as compared to LSCo parent materials.

SOFC cathode, strength, LSCo, alumina↗

Electrically Conductive and Protective Coating Compatibility with LSCF Cathodes

Ferritic stainless-steel interconnect materials are used in intermediate or high-temperature SOFCs because of their oxidation resistance, high formability, and low cost. Their corrosion resistance is due to the formation of a protective chromium oxide scale during operation. However, the protective oxide layer produces Cr-containing volatile species at SOFC operating temperatures and conditions, which can cause cathode poisoning. Spinel coatings have been developed to prevent cathode poisoning while maintaining an electrically conductive pathway through SOFC stacks. Generally, Mn-Co-O spinel has been the material of choice, but PNNL has developed an Mn-Cu-O spinel protective coating to remove the costly Co and enhance the electrical conductivity. This paper will focus on the electrically conductive coating’s compatibility with LSCF in high-temperature operating environments.

Choi, Jung-Pyung↗

Microstructural evolution in Cu-Nb processed via friction consolidation

Immiscible alloys, whether in well-mixed or layered forms, are of increasing interest based on their novel structural and functional properties, such as enhanced thermal stability against grain growth or radiation-induced defect trapping at the interfaces. To address the need for new approaches to tailor microstructures, the microstructural development of an immiscible Cu-Nb alloy processed via friction consolidation of elemental powders is investigated. Friction consolidation is a solid-phase processing technique that imparts severe plastic strain into a deforming volume resulting in elevated temperatures below the melting temperature of the alloy. Two distinct processing pathways were chosen to understand the effect of thermomechanical conditions on the final microstructure. The microstructure was characterized using scanning electron microscopy, scanning transmission electron microscopy, and X-ray diffraction techniques. Path 1 exhibited larger strain, strain rate, and temperature as compared with path 2. In path 1, agglomerated Nb particles were present in the recrystallized ultrafine-grained Cu matrix, while in path 2 extremely fine and dispersed Nb particles were present in a highly deformed Cu matrix. In both pathways, supersaturation of Cu in Nb lattices was noted, but not vice-versa. The asymmetry in mixing is explained based on deformation-based, thermodynamic and kinetic factors. These findings provide a pathway for creation of novel tailored microstructures and improved properties in any number of binary immiscible alloy systems.

Cu-Nb alloys, Microstructural refinement, Friction↗

Sr and Co Vapor-Phase Transport from LSCF Cathodes

A series of tests were performed to differentiate between surface diffusion and vapor-phase diffusion of chemical species from LSCF cathode material at typical sintering temperatures (up to 1100°C) in SOFC production. A GDC source substrate was printed with LSCF and separated by an air gap from a YSZ target substrate. Various geometries with long surface paths were employed to reduce the possibility of surface transport. Sr and Co were detected on the target substrates via energy dispersive spectroscopy (EDS) and x-ray photoelectron spectroscopy (XPS), including spatially resolved XPS. These results support a vapor-phase transport mechanism for Sr and Co. Sintering conditions and barrier layer requirements may need to be revisited to prevent the formation of undesired strontium zirconate at cathode/electrolyte interface due to vapor-phase transport.

vapor phase transport, SOFC cathode, Sr transport↗

Copper carbon composite wire with a uniform carbon dispersion made by friction extrusion

Copper-carbon composites are a group of materials with excellent mechanical, electrical, thermal, and tribological properties. However, bulk size copper-carbon composites made by the traditional manufacturing processes, like rolling or extrusion, fall short of reaching some of these properties predicted by theory or demonstrated only by samples at centimeter scale or smaller. The two main challenges to the successful scaling-up are: 1) to uniformly disperse carbon in the metal matrix; 2) to avoid degradation due to oxidation or reaction from overheating. In this work, we first demonstrate friction extrusion as a new method to make bulk-size void-free copper-carbon composite wires with homogenized carbon dispersion. Three different carbon varieties, graphite powder, graphene nanopowder, and carbon nanotubes, were added to the copper matrix with the concentration ranging from 0.5 wt% to 15 wt%. Special tooling, processing parameters, and procedures were developed, especially for high carbon content samples. Ten-fold reductions of both copper grain size and carbon particle size were achieved and attributed to the high shear deformation. Energy dispersive X-ray spectrometry indicates the carbon powder was refined to a sub-micron level and uniformly dispersed in the copper matrix. Compared with that of pure copper, the thermal capacity of the composite wire increases by 30 % while density reduces by 29 %.

Friction extrusion, Metal matrix composite, Graphe↗

Effects of water-based binders on electrochemical performance of manganese dioxide cathode in mild aqueous zinc batteries

In the majority of rechargeable batteries including lithium ion batteries (LIBs), polyvinylidene fluoride (PVdF) binders are the most commonly used binder for both anode and cathode. However, using PVdF binder requires the organic solvent of N-methyl-2-pyrrolidone (NMP) which is expensive, volatile, combustible, toxic, and has poor recyclability. Therefore, switching to aqueous electrode processing routes with non-toxic binders would provide a great leap forward towards the realization of ideally fully sustainable and environmentally friendly electrochemical energy storage devices. Various water-soluble binders (aqueous binders) were characterized and compared to the performance of conventional PVDF. Our study demonstrates that the electrochemical performance of Zn/MnO2 aqueous batteries is significantly improved by using sodium carboxymethyl cellulose (CMC) binder. Additionally, CMC binders offers desirable adhesion, good wettability, homogeneous material distribution, and strong chemical stability at certain pH levels (3.5~5) without any decomposition for long-cycle life.

25 ENERGY STORAGE↗

Zinc-in-titania waste form for immobilizing lanthanide fission products from electrochemical reprocessing

This paper provides microstructural, microchemical, and bulk X-ray diffraction information for a zinc-in-titania waste form for immobilizing rare-earth oxide (REOx) fission products recovered through precipitation from electrochemical salt wastes. This waste form can be used to immobilize REOx at loadings as high as 40 mass% in a chemically durable matrix consisting of glass-bonded minerals including Zn2TiO4 as well as RE-containing phases of REOx, RE2Ti2O7, and REPO4 (monazite). Chemical durability data is also provided, and comparisons are drawn between this waste form and one made using a similar process with half the REOx loading.

rare earth, rare earth waste form, electrochemical↗

Thermal, mechanical, and electrical properties of LSCo/mullite composite contact materials for solid oxide fuel cells

Lanthanum strontium cobaltite (LSCo) is considered as a good candidate cathode contact material for solid oxide fuel cells, due to high electrical conductivity. However, LSCo has a very large coefficient of thermal expansion (CTE) than the cells and metallic interconnects. As a result, poor mechanical stability is expected during thermal cycling. To minimize the CTE mismatch, we investigate a composite approach involving mixing LSCo with an inert material of low CTE, such as mullite at volume fractions from 0.1 to 0.4. Composite’s CTE shows a decreasing trend with increasing mullite volume fractions, and is consistent with model predictions. X-ray powder diffraction analysis of sintered LSCo/mullite composites exhibits no presence of other phases for samples aged for 500h at 800oC, indicating chemical compatibility. Electrical conductivity by a 4-pt method shows a decreasing trend with increasing mullite content. Contact strength of as-sintered and thermally cycled samples show that only the composite with 0.4 volume fraction has a measurable strength; the other composites have no strength. Overall, the composite approach is demonstrated in the LSCo/mullite system to lower the CTE and hence achieve thermal cycle stability. The addition of the inert phase to the LSCo matrix; however, also reduces the electrical conductivity.

Contact materials, LSCo, mullite, CTE, electrical ↗

Iodine Waste Form Corrosion: PNNL Summary Testing Report

A test method to correlate the laboratory corrosion behavior of iodine-containing waste forms (IWFs) to a conceptual long-term corrosion models is required. Several candidate methods have been evaluated previously, and each method presents unique challenges and limitations. Dynamic leach tests have emerged as the preferred candidate test method to evaluate IWFs and parameterize an eventual long-term corrosion model. This report was prepared in support of this effort to define the test suite to evaluate the corrosion of IWFs, with the goal of defining and parameterizing a conceptual long-term corrosion model. A review was presented highlighting the high degree of variability between the IWF corrosion data that is available in the literature and the need for a standardized test suite. The targeted test suite is composed of a single interval screening test, a dynamic leach test, and post-test solid characterization of the monolithic IWF samples. The data presented serves two purposes: to expand the range of IWFs evaluated with the test suite to assess method variability and to further understand the corrosion of IWFs to best inform conceptual long-term corrosion model development. A series of IWF types were included in the testing, including hot isostatically pressed Ag-mordenite, silver functionalized silica-based aerogels, iodosodalites (hot isostatic pressing, sintered, glass bonded ceramic), iodoapatite, tellurite glass and glass composite materials.

42 ENGINEERING↗

Probing the Radial Chemistry of Getter Components in Light Water Reactors via Controlled Electrochemical Dissolution

Getters are among the key functional components in the Tritium Producing Burnable Absorber Rods (TPBARs) of Light Water Reactors, and are used to capture the released tritium gas. They are cylindrical tubes comprised of the alloy zircaloy-4 which is coated with nickel plating both internally and externally. Their exposure to tritium as well as the irradiation environments in the light water reactors changes their structure, chemical composition and chemistry. Understanding the radial tritium distribution is key to gaining insight into the evolution of new chemistry upon irradiation in order to predict getter performance. Consequently, efforts are underway to devise a method that can allow selective probing into the getter core radially to probe the chemistry akin to carefully and selectively peeling of the layers of an onion. We have recently devised an electrochemical dissolution technique for controlled radial dissolution of zirconium based liners; this work describes the first proof-of-concept demonstration of the applicability of this technique on the controlled radial dissolution of nickel plated getters. The technique is complemented with periodic analysis of the electrolyte solution to measure the rates of release of the various elemental components and therefore glean information on their radial distribution across the getter; further complementary microscopy on the exposed surfaces allows us insight into the chemistry at the getter core.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗