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At least 523 records · Page 29

Polymer-iron oxide hybrid films for controlling electrokinetic properties

Electrokinetic phenomena at polymer-water interfaces are central to technologies for water purification, ion separations, and energy conversion, yet the ability to systematically control polymer surface charge and associated electrokinetic processes remains limited. Here, we demonstrate a simple liquid-phase infiltration (LPI) method to synthesize polymer–metal oxide hybrid films with controllable interfacial properties. Hydroxy-terminated poly(2-vinylpyridine) (P2VP-OH) brushes grafted to silicon substrates were infiltrated with iron nitrate from ethanolic solution, followed by low-temperature thermal treatment to convert the infiltrated precursor into iron oxide. Spectroscopic ellipsometry, X-ray photoelectron spectroscopy, and thermogravimetric analysis confirmed oxide incorporation and hybrid film formation without polymer degradation. Electrokinetic measurements reveal that the hybrid films acquire the electrokinetic properties of the infiltrated oxide, with concentration-dependent streaming potentials and surface conductivities closely matching those of pure iron oxide films. These results establish metal oxide infiltration as a scalable and low-cost strategy for controlling interfacial charge in polymer surfaces. The approach introduces new materials and design parameters for tailoring ion selectivity, transport, and energy conversion, with broad implications for the development of advanced membranes, electrokinetic harvesting devices, and polymer-supported oxide electrodes.

36 MATERIALS SCIENCE↗

Widespread detection of chlorine oxyacids in the Arctic atmosphere

Chlorine radicals are strong atmospheric oxidants known to play an important role in the depletion of surface ozone and the degradation of methane in the Arctic troposphere. Initial oxidation processes of chlorine produce chlorine oxides, and it has been speculated that the final oxidation steps lead to the formation of chloric (HClO 3 ) and perchloric (HClO 4 ) acids, although these two species have not been detected in the atmosphere. Here, we present atmospheric observations of gas-phase HClO 3 and HClO 4 . Significant levels of HClO 3 were observed during springtime at Greenland (Villum Research Station), Ny-Ålesund research station and over the central Arctic Ocean, on-board research vessel Polarstern during the Multidisciplinary drifting Observatory for the Study of the Arctic Climate (MOSAiC) campaign, with estimated concentrations up to 7 × 10 6 molecule cm -3 . The increase in HClO 3 , concomitantly with that in HClO 4 , was linked to the increase in bromine levels. These observations indicated that bromine chemistry enhances the formation of OClO, which is subsequently oxidized into HClO 3 and HClO 4 by hydroxyl radicals. HClO 3 and HClO 4 are not photoactive and therefore their loss through heterogeneous uptake on aerosol and snow surfaces can function as a previously missing atmospheric sink for reactive chlorine, thereby reducing the chlorine-driven oxidation capacity in the Arctic boundary layer. Our study reveals additional chlorine species in the atmosphere, providing further insights into atmospheric chlorine cycling in the polar environment.

54 ENVIRONMENTAL SCIENCES↗

Quantifying Properties for a Mechanistic, Predictive Understanding of Aqueous Impact on Aging of Medium and Low Voltage AC and DC Cabling in Nuclear Power Plants

To address the gap in knowledge in understanding degradation in relevant service conditions, this project aimed to develop a mechanistic, predictive model of medium and low voltage cable failure based on the primary environmental degradation parameters of aqueous immersion time, temperature, and the oxidation extent. To do so, we took a two-fold approach toward evaluating degradation as related to the aqueous condition. First, we evaluated the chemical, mechanical, and electrical properties of polymers that comprise the cabling insulation under varied aqueous conditions at different temperatures. Secondly, we evaluated the performance of insulation materials under similar accelerated aging conditions in addition to the dielectric breakdown of the cabling under submersion conditions. Thermal oxidation and immersion of LDPE thin films were done using a Parr vessel and the extent of oxidation was monitored using the carbonyl index from ATR-FTIR spectrum, a ratio quantifying the carbonyl functionality produced on the LDPE film surface. Increasing the temperature, oxidation time, and oxygen pressure increased the water-vapor permeability and the carbonyl content. Thermogravimetric analysis of the films confirmed that there is indeed an initial weight loss of the smaller molecular weight molecules and volatiles. At higher temperatures, there is a secondary mass loss. Up to 70°C, the mass loss curves were similar until 80°C, when the aged films decreased at a much greater rate with respect to increasing temperature. This was seen in the 10, 50, 90% weight loss temperatures. The mechanical properties of sheet PP and HDPE as well as injection molded LDPE, HDPE, HDPP dog bones were plotted with respect to the time spent in the Parr vessel during thermal oxidation. For the sheet PP and HDPE, the UTS and the modulus of elasticity decreased while the elongation increased. The injection-molded LDPE, HDPE, and HDPP dog bones experienced a similar trend where the changes in the properties were within experimental uncertainty. This analysis of LDPE in dry and immersive oxygen-rich environments is an important baseline for future experiments looking at other degradation mechanisms. A predictive aging model for low-density polyethylene insulative cable housings was developed. This model revealed a combination of physical and chemical processes which lead to an increase in permeability and a decrease in strength of the insulator. In creating this predictive model, a gap of knowledge in the literature was revealed in two areas: understanding how the crystallinity of a polymer changes with time and visualizing the predicted pores formed through the insulator which leads to failure. Developing and using an adapted ATR-FTIR method, crystallinity was monitored and compared to bulk crystallinity found via DSC. Inhomogeneity in crystallinity changes were observed but the FTIR method but was found to be less reliable. Pore visualization was found utilizing electrical impedance spectroscopy saturated aged polyethylene films with synthesized citrate-capped gold nanoparticles, and chloroauric acid precursor. results indicate a decreasing impedance of the polyethylene films caused by the transport of ions through the film. SEM imaging was then performed for elemental analysis of the films and counter electrodes for the presence of ions. Chloride and gold ions were detected; however, no nanoparticles were found. This gives an estimated pore size of at least 0.3 nm through the aged film. Cyclic submergence of polyethylene and polypropylene in aqueous solutions of copper sulfate and Harrison’s solution were examined. It was discovered that aging in these mixed conditions and at 90°C did cause a small, yet significant increase to tensile strength for both unaged polyethylene and polypropylene. The PE and PP in cycled and submerged conditions did not have tensile strengths significantly different from dry-aged after 16 weeks. For both solutions, it was determined that capacitance increases with both water tree depth and cable temperature and is relatively independent of changing water tree AR. As for resistance, there is no apparent change between depth percentages of 10 and 80 for both solutions. This is because the water tree has not yet entered the conductor and thus there is no shorting current flowing through the tree yet. Between 80 and 100% water tree depth, it is observed that for both solutions there is a rapid decrease in resistance because the tree is now impacting the conductor shield and allowing shorting current to flow through it. The relationship between resistance and temperature was found to be inversed. As temperature increases, resistance decreases for both water tree solutions with distilled water having the most apparent difference across the range of temperatures simulated. With regards to water tree AR, resistance was found to be relatively independent at depth percentages of 10, 50, and 70, but there was some relationship at 100% depth for both solutions. At this depth, as water tree AR increased, resistance was found to also increase. Through the examination of voltage and electric field distribution plots, it was confirmed for EPR cables that increasing water tree depth leads to increasing distortion. The increase in shorting current at 100% depth for aqueous copper sulfate compared to distilled water was also visualized. Lastly, the relationship between shorting current and temperature for narrow water trees was visualized and validated using the distribution plots. This study has led to a better understanding of the effect of cable temperature, water tree solution, and geometry of the tree region on cable degradation. Furthermore, this study has documented simulation results of water tree degradation in EPR MV cables, which had been previously lacking in information. Future work in this area will add frequency into the mix and examine what effect it has on the rate of cable degradation as a result of water treeing. To compliment the work being carried by UMD on different polymer chemistries, harvested medium voltage (MV) cables were selected for accelerated aging study at ORNL. These medium voltage cables are representative of the vintages and materials that are currently in use at existing nuclear power plants (NPPs). These cables were immersed in water at 90°C and energized for a period of two years at elevated voltage. Partial discharge was measured during this period of time to track potential degradation. Unfortunately, due to the absence of failure, the extent of integration between the UMD techniques and the harvested MV insulation was limited. However, based on the findings and from the UMD research in the previous sections on polyethylene and polypropylene, follow-on characterization for harvested MV cable insulation should focus on sample preparation to take advantage of the UMD techniques to better understand mechanistic degradation in MV cable insulations. This would include: 1.) Utilization of solutions and impedance measurement insulation to track permeability in harvested and accelerated aging insulation samples, 2.) Adaptation of gold nanoparticle synthesis for electrical impedance spectroscopy with supporting SEM characterization to study pore formation in harvested and accelerated aged insulation samples, & 3.) ATR-FTIR crystallinity with multiple temperature dependent harvested MV cable insulation under different air and submerged accelerated aging. In addition, low voltage dielectric spectroscopy and high voltage dissipation factor, tan δ, could be implemented as a condition monitoring tool for harvested MV cable insulation in submerged environments.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Understanding (La,Sr)(Co,Fe)O$_{3-δ}$ Phase Instability within SOECs Using a Combined Experimental and Atomistic Modeling Approach

Understanding the onset of degradation in the air electrode within solid oxide electrolysis cells (SOECs), and the subsequent impact on cell performance, is a critical step in mitigating the performance losses and stability issues of SOECs. In an effort to identify early onset degradation phenomena, SOECs were characterized as fabricated and after testing potentiostatically at 1.3 V for 1000 h at 750 °C. SOEC air electrodes composed of a 1:1 composite of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3–δ (6428-LSCF) and Gd 0.1 Ce 0.9 O 1.95 (GDC) were studied using synchrotron X-ray diffraction (XRD), scanning transmission electron microscopy coupled with energy dispersive X-ray spectroscopy (STEM-EDS), and X-ray absorption near-edge spectroscopy (XANES) to evaluate the changes in the air electrode structurally and chemically. These techniques show the migration of Sr species from the air electrode through pores in the GDC barrier layer, progressing to the electrolyte boundary, where it accumulates and reacts with (Zr 0.84 Y 0.16 )O 2–δ (YSZ) to form SrZrO 3 . Microscopy results are paired with atomistic simulations to better understand the relationship between the thermodynamic instability of 6428-LSCF and cell fabrication/testing conditions. First-principles calculations reveal that LSCF-6428 is not stable during cell manufacturing and testing conditions, which supports the experimental identification of secondary phases in both as-fabricated and tested cells. Together, these results demonstrate that the challenging environments encountered by SOECs during cell manufacturing and operation lead to instabilities of the target 6428-LSCF anode material and underscore the need for more durable, high-performing SOEC components.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Device for steam cladding oxidation testing at TREAT

To compare the chemical degradation of conventional zirconium alloy (Zry) cladding to advance silicon carbide (SiC) cladding in a post loss of coolant accident (LOCA) environment, new nuclear testing capabilities are necessary. The Transient Reactor Test (TREAT) Facility at Idaho National Laboratory (INL) has matured its transient fuel testing capabilities since its 2017 restart. The most recent experiment architecture is the Transient Water Irradiation System in TREAT (TWIST), which is designed to support qualification of accident tolerant fuels in light water reactors. INL has designed and analyzed a natural circulation steam flow modification for TWIST to produce prototypic conditions of cladding oxidation. The in-situ device will be electrically heated to drive natural circulation. Moreover, the SiC cladding requires heating above 1700 °C to observe failure, thus internal prototypic nuclear heating with radiation effects will be used. Thermal hydraulic analysis with RELAP5-3D (Reactor Excursion and Leak Analysis Program) estimated steam fluxes greater than 50 mg cm −2 s −1 can be achieved. These fluxes are adequate to test Zry cladding according to draft regulatory guides and to test SiC cladding according to past experiments.

Oxidation↗

Metal Oxide-Induced Instability and Its Mitigation in Halide Perovskite Solar Cells

Halide perovskite solar cells (PSCs) have emerged as a promising photovoltaic technology for sustainable energy solutions due to their impressive power conversion efficiency and a path to be manufactured by low-cost, high-throughput methods. To reach PSCs’ full potential for practical implementation, it is crucial to solving the issues related to its long-term operational stability. Furthermore, given that PSCs consist of many layers of dissimilar materials which form multiple internal interfaces, it is prudent to examine whether there exist interfacial interactions, most importantly between transport layers and perovskite absorbers, that can trigger device performance and instability. In this perspective, we bring to the attention of the PSC research community the lesser-known interfacial degradation of halide perovskites promoted by contact with metal oxide transport layers and highlight the deleterious effects on the PSCs’ performance and stability. We also discuss various mitigation strategies that have shown promises to achieve high-performing and stable PSCs.

14 SOLAR ENERGY↗

Oxidized structure and Compositional properties of 1144 phase FBS by analytical electron microscopy

The 1144 phase (Ae1A1Fe4As4) shows a strong advantage of engineering fabrication among Fe Iron)-based superconductor (FBS) family due to the robustness of its superconducting properties with respect to chemical inhomogeneities, granted by its uniform crystalline-layered structure. This regularity is furthermore associated to crystalline defects capable of acting as efficient pinning centers, which high critical currents achieved at high fields for these superconductors. Like other FBS phases, its lossless current-carrying capability can be remarkably degraded by distractions at grain boundaries (GBs). GB oxidation is an issue of upmost importance to the realization of the practical FBS application for high field (> 20T) magnet. In this study, we explore oxidized grain boundary and intrinsic grain structural properties of 1144 polycrystalline samples by applying analytical electron microscopy such as atomic resolution scanning transmission electron microscopy and atom probe tomography. These structural properties of samples produced by a mechanochemically assisted synthesis are evaluated following the degradation of superconducting properties due to oxidation. We observe a strong correlation between the contamination at grain boundaries and the decrease of transport properties of the bulk sample, while the crystallin structure seems to be not affected by the oxidation.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

The stability of Cl-, Br-, and I-passivated Si(100)-(2 × 1) in ambient environments for atomically-precise pattern preservation

Abstract Atomic precision advanced manufacturing (APAM) leverages the highly reactive nature of Si dangling bonds relative to H- or Cl-passivated Si to selectively adsorb precursor molecules into lithographically defined areas with sub-nanometer resolution. Due to the high reactivity of dangling bonds, this process is confined to ultra-high vacuum (UHV) environments, which currently limits its commercialization and broad-based appeal. In this work, we explore the use of halogen adatoms to preserve APAM-derived lithographic patterns outside of UHV to enable facile transfer into real-world commercial processes. Specifically, we examine the stability of H-, Cl-, Br-, and I-passivated Si(100) in inert N 2 and ambient environments. Characterization with scanning tunneling microscopy and x-ray photoelectron spectroscopy (XPS) confirmed that each of the fully passivated surfaces were resistant to oxidation in 1 atm of N 2 for up to 44 h. Varying levels of surface degradation and contamination were observed upon exposure to the laboratory ambient environment. Characterization by ex situ XPS after ambient exposures ranging from 15 min to 8 h indicated the Br– and I–passivated Si surfaces were highly resistant to degradation, while Cl–passivated Si showed signs of oxidation within minutes of ambient exposure. As a proof-of-principle demonstration of pattern preservation, a H–passivated Si sample patterned and passivated with independent Cl, Br, I, and bare Si regions was shown to maintain its integrity in all but the bare Si region post-exposure to an N 2 environment. The successful demonstration of the preservation of APAM patterns outside of UHV environments opens new possibilities for transporting atomically-precise devices outside of UHV for integrating with non-UHV processes, such as other chemistries and commercial semiconductor device processes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Materials International Space Station Experiment (MISSE): Overview, Accomplishments and Future Needs

Materials and devices used on the exterior of spacecraft in low Earth orbit (LEO) are subjected to environmental threats that can cause degradation in material properties, possibly threatening spacecraft mission success. These threats include: atomic oxygen (AO), ultraviolet and x-ray radiation, charged particle radiation, temperature extremes and thermal cycling, micrometeoroid and debris impacts, and contamination. Space environmental threats vary greatly based on spacecraft materials, thicknesses and stress levels, and the mission environment and duration. For more than a decade the Materials International Space Station Experiment (MISSE) has enabled the study of the long duration environmental durability of spacecraft materials in the LEO environment. The overall objective of MISSE is to test the stability and durability of materials and devices in the space environment in order to gain valuable knowledge on the performance of materials in space, as well as to enable lifetime predictions of new materials that may be used in future space flight. MISSE is a series of materials flight experiments, which are attached to the exterior of the International Space Station (ISS). Individual experiments were loaded onto suitcase-like trays, called Passive Experiment Containers (PECs). The PECs were transported to the ISS in the Space Shuttle cargo bay and attached to, and removed from, the ISS during extravehicular activities (EVAs). The PECs were retrieved after one or more years of space exposure and returned to Earth enabling post-flight experiment evaluation. MISSE is a multi-organization project with participants from the National Aeronautics and Space Administration (NASA), the Department of Defense (DoD), industry and academia. MISSE has provided a platform for environmental durability studies for thousands of samples and numerous devices, and it has produced many tangible impacts. Ten PECs (and one smaller tray) have been flown, representing MISSE 1 through MISSE 8, yielding long-duration space environmental performance and durability data that enable material validation, processing recertification and space qualification; improved predictions of materials and component lifetimes in space; model verification and development; and correlation factors between space-exposure and ground-facilities enabling more accurate in-space performance predictions based on ground-laboratory testing. A few of the many experiment results and observations, and their impacts, are provided. Those highlighted include examples on improved understanding of atomic oxygen scattering mechanisms, LEO coating durability results, and polymer erosion yields and their impacts on spacecraft design. The MISSE 2 Atomic Oxygen Scattering Chamber Experiment discovered that the peak flux of scattered AO was determined to be 45 deg from normal incidence, not the model predicted cosine dependence. In addition, the erosion yield (E(sub y)) of Kapton H for AO scattered off oxidized-Al is 22% of the E(sub y) of direct AO impingement. These results were used to help determine the degradation mechanism of a cesium iodide detector within the Hubble Space Telescope Cosmic Origins Spectrograph Experiment. The MISSE 6 Indium Tin Oxide (ITO) Degradation Experiment measured surface electrical resistance of ram and wake ITO coated samples. The data confirmed that ITO is a stable AO protective coating, and the results validated the durability of ITO conductive coatings for solar arrays for the Atmosphere-Space Transition 2 Explorer program. The MISSE 2, 6 and 7 Polymer Experiments have provided LEO AO Ey data on over 120 polymer and composites samples. The flight E(sub y) values were found to range from 3.05 x 10(exp -26) cu cm/atom for the AO resistant polymer CORIN to 9.14 x 10(exp -26) cu cm/atom for polyoxymethylene (POM). In addition, flying the same polymers on different missions has advanced the understanding of the AO E(sub y) dependency on solar exposure for polymers containing fluorine. The MISSE polymer results are highly requested and have impacted spacecraft design for WorldView-2 & -3, the Global Precipitation Measurement-Microwave Imager, and other spacecraft. The flight data has enabled the development of an Atomic Oxygen Erosion Predictive Tool that allows the erosion prediction of new and non-flown polymers. The data has also been used to develop a new NASA Technical Standards Handbook "Spacecraft Polymers Atomic Oxygen Durability Handbook." Many intangible benefits have also been derived from MISSE. For example, over 40 students have collaborated on Glenn's MISSE experiments, which have resulted in greater than $80K in student scholarships and awards in national and international science fairs. Students have also given presentations and won poster competition awards at international space conferences.

Flight Experiment↗

Overlay metallic-cermet alloy coating systems

A substrate, such as a turbine blade, vane, or the like, which is subjected to high temperature use is coated with a base coating of an oxide dispersed, metallic alloy (cermet). A top coating of an oxidation, hot corrosion, erosion resistant alloy of nickel, cobalt, or iron is then deposited on the base coating. A heat treatment is used to improve the bonding. The base coating serves as an inhibitor to interdiffusion between the protective top coating and the substrate. Otherwise, the protective top coating would rapidly interact detrimentally with the substrate and degrade by spalling of the protective oxides formed on the outer surface at elevated temperatures.

Gedwill, M. A.↗

Combined Cr and S poisoning behaviors of La 1-x Sr x MnO 3±δ and La 1-x Sr x Co 1-y FeyO 3-δ cathodes in solid oxide fuel cells

Although the individual effects of airborne Cr and S contaminants on SOFC cathode performance degradation have been extensively studied, the combined effects of Cr and S contaminants remain largely unexplored. Under the real SOFC operating condition where the Cr and S species coexist, their effects may compete, affecting the poisoning behavior. Here, our investigation reveals that the combined Cr and S poisoning behavior of LSCF remains different from those of individual Cr and S poisonings, while the combined poisoning mechanism of LSM is equivalent to the sum of those of individual Cr and S effects. For LSCF electrode, gaseous Cr species are deposited mainly at the LSCF/GDC interface by electrochemical reduction, rather than forming SrCrO 4 on LSCF surfaces (as in the case of Cr-only poisoning), indicating no reaction between Cr vapors and SrO on the LSCF surface. Thermodynamic analysis demonstrates that the SrO on LSCF surface absorbs SO 2 (g) and thereby loses the Cr-gettering effect, allowing Cr vapors to flow through LSCF and to reach the LSCF/GDC interface where the Cr deposition occurs. Unlike LSCF, LSM electrode shows cumulative effects of Cr and S, as Cr accumulation occurs at the triple-phase boundary and S absorption takes place at localized Sr-rich regions.

36 MATERIALS SCIENCE↗

A designed Copper Histidine-brace enzyme for oxidative depolymerization of polysaccharides as a model of lytic polysaccharide monooxygenase

The “Histidine-brace” (His-brace) copper-binding site, composed of Cu(His) 2 with a backbone amine, is found in metalloproteins with diverse functions. A primary example is lytic polysaccharide monooxygenase (LPMO), a class of enzymes that catalyze the oxidative depolymerization of polysaccharides, providing not only an energy source for native microorganisms but also a route to more effective industrial biomass conversion. Despite its importance, how the Cu His-brace site performs this unique and challenging oxidative depolymerization reaction remains to be understood. To answer this question, we have designed a biosynthetic model of LPMO by incorporating the Cu His-brace motif into azurin, an electron transfer protein. Spectroscopic studies, including ultraviolet-visible (UV–Vis) absorption and electron paramagnetic resonance, confirm copper binding at the designed His-brace site. Moreover, the designed protein is catalytically active towards both cellulose and starch, the native substrates of LPMO, generating degraded oligosaccharides with multiturnovers by C1 oxidation. It also performs oxidative cleavage of the model substrate 4-nitrophenyl-D-glucopyranoside, achieving a turnover number ~9% of that of a native LPMO assayed under identical conditions. This work presents a rationally designed artificial metalloenzyme that acts as a structural and functional mimic of LPMO, which provides a promising system for understanding the role of the Cu His-brace site in LPMO activity and potential application in polysaccharide degradation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coating with overlay metallic-cermet alloy systems

A base layer of an oxide dispersed, metallic alloy (cermet) is arc plasma sprayed onto a substrate, such as a turbine blade, vane, or the like, which is subjected to high temperature use. A top layer of an oxidation, hot corrosion, erosion resistant alloy of nickel, cobalt, or iron is then arc plasma sprayed onto the base layer. A heat treatment is used to improve the bonding. The base layer serves as an inhibitor to interdiffusion between the protective top layer and the substrate. Otherwise, the 10 protective top layer would rapidly interact detrimentally with the substrate and degrade by spalling of the protective oxides formed on the outer surface at elevated temperatures.

Gedwill, M. A.↗

Effect of ionizing radiation on PuO2 and surrogate oxide materials under storage conditions

The stockpile of plutonium separated from used nuclear fuel amounts to many 100s of tonnes. The majority of this plutonium is stored as PuO2 powder packaged in multi-can containers. The conditions during the packaging of reprocessed PuO2 for long term storage are closely controlled to limit water uptake as radiolytic decomposition of any adsorbed water will lead to the formation of both a potentially flammable atmosphere containing molecular hydrogen as well as reactive oxygen species which may be incorporated into the oxide phase. Consequently, the safety case for the long-term storage of PuO2 requires a complete understanding of the fundamental physical, chemical and materials degradation processes occurring at the water-oxide interface inside the storage canisters. This study investigates the effect of ionizing radiation on PuO2 and various surrogate oxides under atmospheres potentially encountered in storage canisters.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Creating Hydride Rim Structures in Zircaloy 4 Cladding Tubes to Mimic High Burnup

During their long service in commercial light water reactors, zirconium alloy cladding tubes are subject to oxidation and subsequent hydrogen pickup which can degrade the materials mechanical properties [1]. These degradations can lead to premature cladding ruptures during reactor power transients [2] as well as negatively impact the claddings post quench ductility following high temperature steam oxidation in thermal hydraulic transients [3]. Hydrogen has low solid solubility in zirconium and usually precipitates as brittle zirconium hydride platelets in the cladding metal matrix. Due to temperature driven diffusion (Soret effect) and the grain texture of stress relieved zirconium metal tubes, these hydrides precipitate with a circumferential orientation near the outer surface of the cladding tubes forming a hydride rim which can serve as a site for crack initiation during circumferential ‘hoop’ loading of the cladding [4rim formation][5]. In order to better understand the effect of hydride rims on the fracture behavior of stress relieved zirconium alloy cladding tubes a procedure to produce these rim-like structures is being developed at Idaho National Laboratory (INL).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Differences in c-Si Solar Cell Metallization and Susceptibility to Series Resistance Degradation

In this case study, we investigate a degradation mode occurring at the cell level in fielded multi-Si modules. Affected cells in the module show a progressive, series-resistance-related power degradation observed in module- and cell-level IV curves along with EL and PL imaging at the module, cell, and cell core sample scale. SEM and elemental analysis via EDS reveal a difference in the oxides in the silver paste used in screen printing of the finger contacts. This suggests that the cells were screen printed with different silver paste compositions and possibly firing conditions. One of these combinations leads to degradation of the contact at the interface between the cell and contact finger, causing severe series resistance across the cell that continues to progress over time.

acetic acid↗

In situ self-ion (Fe + ) irradiation of ODS-FeCrAl alloy fuel cladding materials with different Cr contents: The early stages of Cr-rich α’ phase precipitation

Oxide-dispersion-strengthened FeCrAl (ODS-FeCrAl) alloys are candidate accident-tolerant fuel cladding materials for light water reactors because they demonstrate satisfactory resistance to materials degradation effects such as high-temperature oxidation, radiation-induced swelling, and creep. Their perspective deployment to market is challenged, however, by their inherent susceptibility to irradiation embrittlement caused by the precipitation of the brittle Cr-rich α’ phase at relatively low temperatures (≤475 °C). This work used in situ self-ion irradiation (150 keV Fe + ) in a transmission electron microscope to elucidate the early stages of Cr-rich α’ phase precipitation in three candidate ODS-FeCrAl alloy fuel cladding materials with different Cr contents (10, 12, and 20 wt.%) and microstructures. The early stages of the process resulting in the precipitation of the Cr-rich α’ phase in these three ODS-FeCrAl alloys under Fe + irradiation were investigated at room temperature and 300 °C up to total fluences of 1.7 × 10 15 ions·cm -2 (2 dpa) and 3.4 × 10 15 ions·cm -2 (4 dpa), using three damage dose rates (5 × 10 –5 , 3.3 × 10 –4 , and 2 × 10 –3 dpa·s -1 ). Post-irradiation examination via scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy suggested that the precipitation of the Cr-rich α’ phase might be promoted by the phase separation of the alloy matrix into Cr-rich and Fe-rich regions. Interestingly, oxygen impurities segregated preferentially in the Cr-rich regions, possibly promoting the radiation-assisted formation of the Cr-rich α’ phase. α’ phase precipitation was more pronounced at room temperature when compared to 300 °C, and it was clearly promoted by the progressive increase in the Cr content of the ODS-FeCrAl alloy.

36 MATERIALS SCIENCE↗