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At least 199 records · Page 11

Effects of annealing temperature on morphology and thickness of samarium electrodeposited thin films

Electroplated depositions of Sm were prepared using a vertical well-type electrodeposition unit with an aqueous ammonium acetate electrolyte system, with an average deposition yield just over 87%. The depositions were analyzed for morphology and thickness by scanning electron microscopy (SEM) and chemical composition by energy dispersion X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) before and after firing. The depositions were fired at 125–700 °C, while varying the heating rate from 0.5 to 10 °C/min in either an oxidizing or reducing atmosphere. A heating rate of 10 °C/min was slow enough to prevent disruption of the deposition morphology during firing. Furthermore, a gas sweep enhanced the removal of any organic substituents, with an oxidizing environment being more advantageous than a reducing environment.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Potential of electrolytic processes for recovery of molybdenum from molten salts for 99 Mo production

Molten salt reactor (MSR) technologies are receiving significant interest for commercialization because of their potential safety features and efficient energy production. In addition to producing reliable and clean energy, high-value radioisotopes could be harvested from MSRs as an additional revenue stream. Although significant quantities of 99 Mo will be produced in MSRs through fission, how accessible 99 Mo will be for direct recovery from a fuel salt is unclear. Electrolytic processes in fused salts have been used extensively for processing molten salts and have the potential to enable the extraction of 99 Mo directly from the fuel salt. This paper reviews the behavior of 99 Mo in the molten salt reactor experiment and summarizes theoretical aspects of the electrolytic process in high-temperature fused salt and the published experimental results on Mo extraction through electrolytic processes. Here, the general principle of fused-salt electrolytic processes is described, by electrodeposition of Mo with the following aspects: electrowinning, electrorefining, electroplating, and electroextraction with several experimental considerations. Finally, important considerations for recovery of 99 Mo from MSR relevant molten salts via electrodeposition are discussed.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Assessment of Protective Coatings for Metal-Supported Solid Oxide Electrolysis Cells

Green hydrogen is essential to achieving carbon neutrality, and solid oxide electrolysis cells can produce hydrogen using renewable power and waste heat. Insufficient long-term durability of solid oxide electrolysis cells has impeded their commercialization. Here, coatings in the porous stainless steel support of metal-supported solid oxide electrolysis cells (MS-SOECs) are used to dramatically improve their performance and durability. The long-term degradation rate of uncoated MS-SOECs is highly dependent on the current density, with the fastest degradation occurring at the highest current density tested, 0.5 A cm -2 . At this current density, coatings are quite effective. Three protective coatings, Co 3 O 4 deposited by atomic layer deposition (ALD), Co 3 O 4 deposited by electroplating deposition (ED), and CuMn 1.8 O 4 (CMO) deposited by electrophoretic deposition (EPD), are explored to enhance the performance of MS-SOECs with La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 -Sm 0.2 Ce 0.8 O 3 (LSCF-SDC) as the oxygen catalyst and SDC-Ni as the fuel catalyst. The initial average current density at 1.4 V is increased with coatings. It is 0.83 mA cm -2 for the ALD cells, 1.05 mA cm -2 for the ED cells, and 1.13 mA cm -2 for the EPD cells, compared to 0.65 mA cm -2 for the bare cells at 700 °C with 50% H 2 -50% H 2 O. The degradation rate over 1000 h of continuous operation is reduced from 36% to 26%, 27%, and 19% kh -1 with the three coatings, respectively. Furthermore, these improvements are ascribed to reduced Cr poisoning on the oxygen catalyst, which is one of the primary degradation modes for this type of MS-SOEC.

25 ENERGY STORAGE↗

Patterning Metal Grids for GaAs Solar Cells with Cracked Film Lithography: Quantifying the Cost/Performance Tradeoff

We introduce cracked film lithography (CFL) as a way to reduce the cost of III–V photovoltaics (PV). We spin-coat nanoparticle suspensions onto GaAs thin-film device stacks. The suspensions dry in seconds, forming crack networks that we use as templates through which to electroplate the solar cells’ front metal grids. For the first time, we show that heating the crack template allows it to flow and refill cracks, which decreases crack footprint and improves final grid transmittance. We demonstrate 24.7%-efficient single-junction GaAs solar cells using vacuum-free CFL grids. These devices are only 1.7% (absolute) less efficient than the baseline grids patterned by photolithography with the loss mostly resulting from the reduced transparency of the CFL pattern. Additional optimization could decrease this difference. Initial cost modeling suggests that CFL is more scalable than photolithography: In particular, CFL’s lower materials and equipment costs could greatly reduce the levelized cost of electricity of III–V PV at scale, a potential step toward terrestrial deployment.

14 SOLAR ENERGY↗

Microstructure, impurity and metal cap effects on Cu electromigration

Electromigration (EM) lifetimes and void growth of pure Cu, Cu(Mn) alloy, and pure Cu damascene lines with a CoWP cap were measured as a function of grain structure (bamboo, near bamboo, and polycrystalline) and sample temperature. The bamboo grains in a bamboo-polycrystalline grained line play the key role in reducing Cu mass flow. The variation in Cu grain size distribution among the wafers was achieved by varying the metal line height and wafer annealing process step after electroplating Cu and before or after chemical mechanical polishing. The Cu grain size was found to have a large impact on Cu EM lifetime and activation energy, especially for the lines capped with CoWP. The EM activation energy for pure Cu with a CoWP cap from near-bamboo, bamboo-polycrystalline, mostly polycrystalline to polycrystalline only line grain structures was reduced from 2.2 ± 0.2 eV, to 1.7 ± 0.1 eV, to 1.5 ± 0.1 eV, to 0.72 ± 0.05 eV, respectively. The effect of Mn in Cu grain boundary diffusion was found to be dependent on Mn concentration in Cu. The depletion of Cu at the cathode end of the Cu(Mn) line is preceded by an incubation period. Unlike pure Cu lines with void growth at the cathode end and hillocks at the anode end of the line, the hillocks grew at a starting position roughly equal to the Blech critical length from the cathode end of the Cu(Mn) polycrystalline line. The effectiveness of Mn on Cu grain boundary migration can also be qualitatively accounted for by a simple trapping model. The free migration of Cu atoms at grain boundaries is reduced by the presence of Mn due to Cu-solute binding. A large binding energy of 0.5 ± 0.1 eV was observed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Diffusion phenomenon at the interface of Cu-brass under a strong gravitational field

To investigate diffusion phenomenon at the interface between Cu and brass under a strong gravitational field generated by ultracentrifuge apparatus, we performed gravity experiments on samples prepared by electroplating with interfaces normal and parallel to the direction of gravity. For the parallel-mode sample, for which sedimentation cannot occur thorough the interface, the concentration change was significant within the lower gravity region; many pores were observed in this region. Many vacancies arising from crystal strain due to the strong gravitational field moved into the lower gravity region, and enhanced the atoms mobilities. For the two normal-mode samples, which have interface normal to the direction of gravity, the composition gradient of the brass-on-Cu sample was steeper than that for Cu-on-brass. This showed that the atoms of denser Cu diffuse in the direction of gravity, whereas Zn atoms diffuse in the opposite direction by sedimentation. The interdiffusion coefficients became higher in the Cu-on-brass sample, and became lower in the brass-on-Cu sample. This rise may be related to the behavior of the vacancies.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Freestanding high-aspect-ratio gold masks for low-energy, phase-based x-ray microscopy

High-resolution, x-ray phase contrast microscopy, a key technique with promising potential in biomedical imaging and diagnostics, is based on narrow-slit high-aspect-ratio gold gratings. Here we present the development, fabrication details, and experimental testing of the freestanding 10 μm thick gold membrane masks with an array of 0.9–1.5 μm void slit apertures for a novel low-energy x-ray microscope. The overall mask size is 4 mm × 4 mm, with a grating pitch of 7.5 μm, 6.0–6.6 μm wide gold bars are supported by 3 μm wide crosslinks at 400 μm intervals. The fabrication process is based on gold electroplating into a silicon mold coated with various thin films to form a voltage barrier, plating base, and sacrificial layer, followed by the mold removal to obtain the freestanding gold membrane with void slit apertures. We discuss key aspects for the materials and processes, including gold structures homogeneity, residual stresses, and prevention of collapsing of the grid elements. We further demonstrate the possibility to obtain high-resolution, high contrast 2D images of biological samples using an incoherent, rotating anode x-ray tube.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Innovative coating of nanostructured vanadium carbide on the F/M cladding tube inner surface for mitigating the fuel cladding chemical interactions

Fuel cladding chemical interactions (FCCI) have been acknowledged as a critical issue in a metallic fuel/steel cladding system due to the formation of low melting intermetallic eutectic compounds between the fuel and cladding steel, resulting in reduction in cladding wall thickness as well as a formation of eutectic compounds that can initiate melting in the fuel at lower temperature. In order to mitigate FCCI, diffusion barrier coatings on the cladding inner surface have been considered. In order to generate the required coating techniques, pack cementation, electroplating, and electrophoretic deposition have been investigated. However, these methods require a high processing temperature of above 700 oC, resulting in decarburization and decomposition of the martensites in a ferritic/martensitic (F/M) cladding steel. Alternatively, organometallic chemical vapor deposition (OMCVD) can be a promising process due to its low processing temperature of below 600 oC. The aim of the project is to conduct applied and fundamental research towards the development of diffusion barrier coatings on the inner surface of F/M fuel cladding tubes. Advanced cladding steels such as T91, HT9 and NF616 have been developed and extensively studied as advanced cladding materials due to their excellent irradiation and corrosion resistance. However, the FCCI accelerated by the elevated temperature and high neutron exposure anticipated in fast reactors, can have severe detrimental effects on the cladding steels through the diffusion of Fe into fuel and lanthanides towards into the claddings. To test the functionality of developed coating layer, the diffusion couple experiments were focused on using T91 as cladding and Ce as a surrogate lanthanum fission product. By using the customized OMCVD coating equipment, thin and compact layers with a few micron between 1.5 µm and 8 µm thick and average grain size of 200 nm and 5 µm were successfully obtained at the specimen coated between 300oC and 500 oC, respectively. The coating layer contains both carbon and vanadium elements as quantified by WED, and the phases mainly consist of a mixture of V2C and VC, which was confirmed using X-ray diffraction patterns. In addition, the ratio between V and C varies with processing temperature, and it was observed that a higher temperature promotes the carbon adsorption and increases thickness of the coating. With optimized deposition conditions, we can apply the coating technique toward the actual T91 cladding materials, and provide the possibilities for the real application in sodium-cooled fast reactors (SFRs). Diffusion couple experiments were performed at both 550 oC and 690 oC, which corresponds to normal and aggressive operating temperatures, respectively. The results show that vanadium carbide coating with wider thickness (8 µm) and lower carbon concentration (27 at.%) reduced the width of the inter diffusion region, indicating that vanadium carbide coating can mitigate FCCI effectively. In specific, inter-diffusion between Fe and Ce was prohibited over most area, but Ce diffusion occurred toward the coating and the Fe substrate through thinner coating layer, which needs further optimization in terms of uniform coating thickness. Overall, it is concluded that this coating process can be successfully applied onto the inner surface of HT9 cladding tubes and the FCCI can be effectively mitigated if not totally eliminated.

36 MATERIALS SCIENCE↗

Development of SiC-based Cladding for Accident Tolerant Fuels

Fuels and core structures in current light water reactors (LWR's) are vulnerable to catastrophic failure in severe accidents. This vulnerability is attributed primarily to the rapid oxidation kinetics of zirconium alloys in a water vapor environment at very high temperatures. Alternative materials to zirconium alloys with reduced oxidation kinetics are sought to enable enhanced accident-tolerant fuels and cores. Among the candidate alternatives, silicon carbide (SiC) - based materials, in particular continuous SiC fiber-reinforced SiC matrix ceramic composites (SiC/SiC composites), are considered to offer outstanding safety benefits. The primary objective of this work is to provide with updated overviews of the concepts, development status, and future prospect for the SiC-based accident-tolerant fuel (ATF) claddings. A systematic technology evaluation program plan was developed and updated to review the technologies needed, to identify and analyze critical gaps, and to lay out a road-map toward establishing key technologies. The technology review and the gap analysis in this exercise were based on an early study and community workshops. Many of the technical gaps identified are related with the three key feasibility issues: hydrothermal corrosion, mechanical failure, and fuel compatibility. Additional performance issues including accident-tolerance features and fission product retention during the normal operation have also been identified. The program plan was designed to systematically address the key gap issues and is formulated in a work breakdown structure. Simultaneously, the plan is being established to set a technical program for advancing the technological readiness levels of concept non-specific essential technologies in three top-level categories of Design and Failure, Environmental Effects, and Off-normal Behavior. The execution of the program plan is in progress across the U.S. Department of Energy laboratories, industries, universities, and international collaborators. The critical issues for SiC composite-based fuel cladding concepts were found to be related to the performance in the normal operation. In particular, radiation-assisted hydrothermal corrosion and the gaseous fission product (FP) retention are identified to be the most critical issues. The primary ORNL concept pursues the use of dual-purpose coating on the SiC composite cladding wall to mitigate the corrosion and the gas permeation issues at the same time, whereas the alternative approaches such as the dense monolithic SiC protective layer combined with the water chemistry control may be feasible. Surface metallization through variations of physical vapor deposition and electroplating are being demonstrated. The FP gas retention is an issue associated with the cracking for the ceramic matrix composite cladding. To establish the probabilistic failure behavior, the relevant test methods were developed in ASTM Committee C28 on Advanced Ceramics. Toward the end-plugging technology development, various methods for joining SiC to SiC had been developed and tested for mechanical properties, irradiation effects, and environmental effects. Multiple methods including the pressureless transient eutectic SiC joining and CVD-based SiC joining were identified particularly promising. In addition, a multi-physics, three-dimensional finite element-based modeling is in progress toward an integrated simulation of the SiC composite-cladded fuel evolutions. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Ultrahigh-Rate and Long-Life Zinc–Metal Anodes Enabled by Self-Accelerated Cation Migration

Aqueous zinc ion batteries are receiving unprecedented attention owing to their markedly high safety and sustainability, yet their lifespan particularly at high rates is largely limited by the poor reversibility of zinc (Zn) metal anodes, due to the random ion diffusion and sluggish ion replenishment at reaction interface. In this work, we propose a tunnel-rich and corona-poled ferroelectric thin film coating for Zn metal anode to tackle above conundra. It is demonstrated that the poled ferroelectric coating can better deconcentrate and self-accelerate ion migration at coating/Zn interface upon electroplating process than untreated ferroelectric coating and bare Zn, thus enabling a compact and horizontally-aligned Zn morphology even at ultrahigh rates. Notably, a maximal cumulative plating capacity of over 6500 mAh cm -2 (at 10 mA cm -2 ) is achieved for the surface-modified Zn metal anode, showing extraordinary reversibility of Zn plating/stripping. This work provides new insights in stabilizing Zn metal electrodeposition at the scale of interfacial ion diffusion.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A Universal Design of Lithium Anode via Dynamic Stability Strategy for Practical All‐Solid‐State Batteries

Abstract All‐solid‐state Li‐metal battery (ASSLB) chemistry with thin solid‐state electrolyte (SSE) membranes features high energy density and intrinsic safety but suffers from severe dendrite formation and poor interface contact during cycling, which hampers the practical application of rechargeable ASSLB. Here, we propose a universal design of thin Li‐metal anode (LMA) via a dynamic stability strategy to address these issues. The ultra‐thin LMA (20 μm) is in situ constructed with uniform highly Li‐ion conductive solid‐electrolyte interphase and composite‐polymer interphase (CPI) via electroplating process. As a result, the passivation layer with poor Li‐ion conduction on Li anode can be dissolved and small surface resistance can be achieved due to the good compatibility of CPI to SSEs. The cycling of Li symmetric cell with Li 6 PS 5 Cl thin film electrolyte (<100 μm) shows a high critical current density of >2.0 mA cm −2 with excellent cycling stability at 1.0 mA cm −2 . The ASSLBs paring with Ni‐rich LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode demonstrated the feasibility of engineered LMA design by presenting good rate capability from 0.1 C to 1.0 C at room temperature, as well as long‐term cycling stability (81 % retention after 100 cycles). This work represents a general pathway to make thin dendrite‐free LMA available for high‐energy‐density ASSLBs.

Deng, Tao [Department of Chemical and Biomolecular↗

A Universal Design of Lithium Anode via Dynamic Stability Strategy for Practical All‐Solid‐State Batteries

Abstract All‐solid‐state Li‐metal battery (ASSLB) chemistry with thin solid‐state electrolyte (SSE) membranes features high energy density and intrinsic safety but suffers from severe dendrite formation and poor interface contact during cycling, which hampers the practical application of rechargeable ASSLB. Here, we propose a universal design of thin Li‐metal anode (LMA) via a dynamic stability strategy to address these issues. The ultra‐thin LMA (20 μm) is in situ constructed with uniform highly Li‐ion conductive solid‐electrolyte interphase and composite‐polymer interphase (CPI) via electroplating process. As a result, the passivation layer with poor Li‐ion conduction on Li anode can be dissolved and small surface resistance can be achieved due to the good compatibility of CPI to SSEs. The cycling of Li symmetric cell with Li 6 PS 5 Cl thin film electrolyte (<100 μm) shows a high critical current density of >2.0 mA cm −2 with excellent cycling stability at 1.0 mA cm −2 . The ASSLBs paring with Ni‐rich LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode demonstrated the feasibility of engineered LMA design by presenting good rate capability from 0.1 C to 1.0 C at room temperature, as well as long‐term cycling stability (81 % retention after 100 cycles). This work represents a general pathway to make thin dendrite‐free LMA available for high‐energy‐density ASSLBs.

Deng, Tao [Department of Chemical and Biomolecular↗

Tuning Catalyst Activation and Utilization Via Controlled Electrode Patterning for Low-Loading and High-Efficiency Water Electrolyzers

An anode electrode concept of thin catalyst-coated liquid/gas diffusion layers (CCLGDLs), by integrating Ir catalysts with Ti thin tunable LGDLs with facile electroplating in proton exchange membrane electrolyzer cells (PEMECs), is proposed. The CCLGDL design with only 0.08 mg Ir cm -2 can achieve comparative cell performances to the conventional commercial electrode design, saving ~97% Ir catalyst and augmenting a catalyst utilization to ~24 times. CCLGDLs with regulated patterns enable insight into how pattern morphology impacts reaction kinetics and catalyst utilization in PEMECs. A specially designed two-sided transparent reaction-visible cell assists the in situ visualization of the PEM/electrode reaction interface for the first time. Oxygen gas is observed accumulating at the reaction interface, limiting the active area and increasing the cell impedances. In this work, it is demonstrated that mass transport in PEMECs can be modified by tuning CCLGDL patterns, thus improving the catalyst activation and utilization. The CCLGDL concept promises a future electrode design strategy with a simplified fabrication process and enhanced catalyst utilization. Furthermore, the CCLGDL concept also shows great potential in being a powerful tool for in situ reaction interface research in PEMECs and other energy conversion devices with solid polymer electrolytes.

08 HYDROGEN↗

Development of Transition-Edge Sensor X-ray Microcalorimeter Linear Array for Compton Scattering and Energy Dispersive Diffraction Imaging

In this paper we present a strip transition-edge sensor microcalorimeter linear array detector developed for energy dispersive X-ray diffraction imaging and Compton scattering applications. The prototype detector is an array of 20 transition-edge sensors with absorbers in strip geometry arranged in a linear array. We discuss the fabrication steps needed to develop this array including Mo/Cu bilayer, Au electroplating, and proofof-principle fabrication of long strips of SiNx membranes. We demonstrate minimal unwanted effect of strip geometry on X-ray pulse response and showlinear relationship of 1/pulse height and pulse decay times with absorber length. For the absorber lengths studied, our preliminary measurements show energy resolutions of 40-180eV near 17 keV. Furthermore, we show that the heat flow to the cold bath is nearly independent of the absorber area and depends on the SiNx membrane geometry.

47 OTHER INSTRUMENTATION↗

Influences of superalloy composition and Pt content on the oxidation behavior of gamma–gamma prime NiPtAl bond coatings

Here, the effects of superalloy composition and Pt content on the high-temperature oxidation behavior of γ–γ’ NiPtAl diffusion coatings were investigated over the temperature range of 1050–1150 °C. Simple NiPtAl diffusion coatings with 7 or 12 µm electroplated Pt thickness were evaluated in 1-h cycles in dry O 2 for up to 2500 cycles on four superalloys: directionally solidified (DS) alloy 142, 1st generation single-crystal (SX) alloy 1483, and 2nd generation SX alloys X4 and N5. Coatings on high-Hf alloy 142 experienced severe internal oxidation of Hf at all temperatures. Coatings on ~5 at.% Ti alloy 1483 were protective at 1050 °C, but exhibited severe scale spallation at 1100 °C, with extensive formation of Ti- and Ni-rich oxides at the gas interface. Coatings with 7-µm Pt on X 4 were extremely protective at 1100 °C, but failed rapidly at 1150 °C, which also was associated with the formation of Ti-rich oxides. Increasing the coating Pt content on X 4 improved the 1150 °C oxidation behavior. Coatings on Ti-free N 5 showed the best performance at 1150 °C, especially with 12-µm Pt. Although γ–γ’ coatings can exhibit outstanding cyclic oxidation resistance with minimal Al depletion, they appear to be sensitive to substrate composition, as well as eventual Pt depletion due to interdiffusion.

36 MATERIALS SCIENCE↗

Visualization of Kirkendall Voids at Cu-Au Interfaces by In Situ TEM Heating Studies

Gold-plated copper alloys are used extensively in electrical contacts where diffusional processes are known to cause contact degradation. An in situ transmission electron microscopy (TEM) heating study was carried out to provide fundamental understanding of the aging phenomena in reasonable timescales. Samples to visualize the interface in TEM were prepared by focused ion beam (FIB) microscopy and heated in situ up to 350°C while holding at intermediate temperatures to enable imaging. The grain boundaries in Au coatings, specifically the columnar boundaries, provided rapid pathways for diffusion of Cu all the way to the Au surface. This unequal diffusion created vacancies in Cu which coalesced into Kirkendall voids. This in situ technique has been applied to visualize the diffusion pathways in electroplated and sputtered Au films deposited directly on Cu, as well the role of Ni and NiP as barrier layers for mitigating Cu diffusion.

36 MATERIALS SCIENCE↗

A Workflow for Accelerating Multimodal Data Collection for Electrodeposited Films

Abstract Future machine learning strategies for materials process optimization will likely replace human capital-intensive artisan research with autonomous and/or accelerated approaches. Such automation enables accelerated multimodal characterization that simultaneously minimizes human errors, lowers costs, enhances statistical sampling, and allows scientists to allocate their time to critical thinking instead of repetitive manual tasks. Previous acceleration efforts to synthesize and evaluate materials have often employed elaborate robotic self-driving laboratories or used specialized strategies that are difficult to generalize. Herein we describe an implemented workflow for accelerating the multimodal characterization of a combinatorial set of 915 electroplated Ni and Ni–Fe thin films resulting in a data cube with over 160,000 individual data files. Our acceleration strategies do not require manufacturing-scale resources and are thus amenable to typical materials research facilities in academic, government, or commercial laboratories. The workflow demonstrated the acceleration of six characterization modalities: optical microscopy, laser profilometry, X-ray diffraction, X-ray fluorescence, nanoindentation, and tribological (friction and wear) testing, each with speedup factors ranging from 13–46x. In addition, automated data upload to a repository using FAIR data principles was accelerated by 64x.

36 MATERIALS SCIENCE↗