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At least 397 records · Page 22

Development of a radiation-hard CMOS process

It is recommended that various techniques be investigated which appear to have the potential for improving the radiation hardness of CMOS devices for prolonged space flight mission. The three key recommended processing techniques are: (1) making the gate oxide thin. It has been shown that radiation degradation is proportional to the cube of oxide thickness so that a relatively small reduction in thickness can greatly improve radiation resistance; (2) cleanliness and contamination control; and (3) to investigate different oxide growth (low temperature dry, TCE and HCL). All three produce high quality clean oxides, which are more radiation tolerant. Technique 2 addresses the reduction of metallic contamination. Technique 3 will produce a higher quality oxide by using slow growth rate conditions, and will minimize the effects of any residual sodium contamination through the introduction of hydrogen and chlorine into the oxide during growth.

Power, W. L.↗

Impact of Mars sand on dust on the design of space suits and life support equipment: A technology assessment

Space suits and life support equipment will come in intimate contact with Martian soil as aerosols, wind blown particles and material thrown up by men and equipment on the Martian surface. For purposes of this discussion the soil is assumed to consist of a mixture of cominuted feldspar, pyroxene, olivine, quartz, titanomagnetite and other anhydrous and hydrous iron bearing oxides, clay minerals, scapolite and water soluble chlorides and sulfates. The soil may have photoactivated surfaces that acts as a strong oxidizer with behavior similar to hydrogen peroxide. The existing data about the Mars soil suggests that the dust and sand will require designs analogous to those uses on equipment exposed to salty air and blowing sand and dust. The major design challenges are in developing high performance radiators which can be cleaned after each EVA without degradation, designing seals that are readily cleaned and possibly in selecting materials which will not be degraded by any strong oxidants in the soil. The magnitude of the dust filtration challenge needs careful evaluation in terms of the trade off between fine-particle dust filters with low pressure drop that are either physically large and heavy, like filter baghouses require frequent replacement of filter elements, of low volume high pressure thus power consumption approaches, or washable filters. In the latter, filter elements are cleaned with water, as could the outsides of the space suits in the airlock.

Simonds, Charles H.↗

Multi-Constituent Airborne Contaminants Capture with Low Cost Oxide Getters and Mitigation of Cathode Poisoning in Solid Oxide Fuel Cell

The technical effort and scientific findings, discussed in this report, documents operational barriers and associated long term performance stability challenges posed by the presence of trace airborne multi-constituent contaminants present in high-temperature electrochemical systems, including Solid Oxide Fuel Cells (SOFCs), Solid Oxide Electrolysis Cells (SOECs), Ion Transport Membranes, and Gas Separation systems. Above systems, offering promises for cleanliness and energy efficiency, face challenges with electrode poisoning stemming from the presence of trace contaminants including gaseous Cr/B/Si vapors in the presence of intrinsic contaminants SO 2 /CO 2 /H 2 O gases. The study indicates that the long-term electrical performance degradation in SOFC systems can be traced to electrochemical, structural, and mechanical changes across cell, stack, and balance of plant components resulting from interactions with trace contaminants leading to increase in both ohmic and non-ohmic polarizations. The degradation primarily results from solid-state and gas-phase materials migration, electrode poisoning, and interactions at the cell and stack levels. Cathode degradation emerges as a significant factor impacting overall SOFC performance, especially related to the presence of intrinsic and extrinsic airborne impurities such as SOx, CrOx(OH)y, SOx, Si(OH)x, and HBOx. Although at trace levels, prolong systems operation at higher airflow (3-10X stoichiometric) allow the accumulation of contaminants within the cell components leading to electrical performance degradation through poisoning and electrode deactivation.

20 FOSSIL-FUELED POWER PLANTS↗

Environmental Testing Of High Temperature Materials and Coatings

Materials for today′s extreme environments have unique challenges and design requirements that require multi-faceted evaluations. Thermal and mechanical testing and analysis is important in design, but environmental effects are often the limiting factor of materials in service. Degradation modes such as oxidation, recession, erosion, foreign object damage, and chemical corrosion can negatively impact the materials thermo-mechanical behavior. While materials may ultimately fail under thermo−mechanical stresses, environmental effects are many times the root cause. Evaluation of materials systems under relevant conditions are critical.....start by identifying mechanisms and develop corresponding test methods. Comprehensive modeling begins with thermo-mechanical behavior, then considers environmental degradation modes that provide a “knock down” of that behavior.

Thermal testing Mechanical testing↗

Depth-resolved thermal conductivity and damage in swift heavy ion irradiated metal oxides

We investigated thermal transport in swift heavy ion (SHI) irradiated insulating single crystalline oxide materials: yttrium aluminum garnet- Y 3 Al 5 O 12 (YAG), sapphire (Al 2 O 3 ), zinc oxide (ZnO) and magnesium oxide (MgO) irradiated by 167 MeV Xe ions at 10 12 – 10 14 ions/cm 2 fluences. Depth profiling of the thermal transport on nano- and micro- meter scales was assessed by time-domain thermoreflectance (TDTR) and modulated thermoreflectance (MTR) methods, respectively. This combination allowed us to isolate the conductivities of different sub-surface damage-regions characterized by their distinct microstructure evolution regimes. Thermal conductivity degradation in SHI irradiated YAG and Al 2 O 3 is attributed to formation of ion tracks and subsequent amorphization, while in ZnO and MgO it is mostly due to point defects. Additionally, notably lower conductivity when probed by very low penetrating thermal waves is consistent with surface hillock formation. An analytical model based on Klemens-Callaway method for thermal conductivity coupled with a simplified microstructure evolution capturing saturation in defect concentration was used to obtain depth dependent damage across the ion impacted region. The studies showed that YAG has the highest damage profile resulting in the less dependence of thermal conductivity with the depth, while MgO on the contrary has the strongest dependence. The presented work sheds new light on how SHI induced defects affect thermal transport degradation and recovery of oxide ceramics as promising candidates for next generation nuclear reactor applications.

36 MATERIALS SCIENCE↗

Methylmercury Degradation by Trivalent Manganese

Methylmercury (MeHg) is a potent neurotoxin and has great adverse health impacts on humans. Organisms and sunlight-mediated demethylation are well-known detoxification pathways of MeHg, yet whether abiotic environmental components contribute to MeHg degradation remains poorly known. Here, in this paper, we report that MeHg can be degraded by trivalent manganese (Mn(III)), a naturally occurring and widespread oxidant. We found that 28 ± 4% MeHg could be degraded by Mn(III) located on synthesized Mn dioxide (MnO 2–x ) surfaces during the reaction of 0.91 μg·L –1 MeHg and 5 g·L –1 mineral at an initial pH of 6.0 for 12 h in 10 mM NaNO 3 at 25 °C. The presence of low-molecular-weight organic acids (e.g., oxalate and citrate) substantially enhances MeHg degradation by MnO 2–x via the formation of soluble Mn(III)-ligand complexes, leading to the cleavage of the carbon–Hg bond. MeHg can also be degraded by reactions with Mn(III)-pyrophosphate complexes, with apparent degradation rate constants comparable to those by biotic and photolytic degradation. Thiol ligands (cysteine and glutathione) show negligible effects on MeHg demethylation by Mn(III). This research demonstrates potential roles of Mn(III) in degrading MeHg in natural environments, which may be further explored for remediating heavily polluted soils and engineered systems containing MeHg.

54 ENVIRONMENTAL SCIENCES↗

Challenges and opportunities to alloyed and composite fuel architectures to mitigate high uranium density fuel oxidation: Uranium mononitride

We see the challenges and opportunities to alloyed and composite fuel architectures designed and intended to mitigate oxidation of the fuel during a cladding breech of a water-cooled reactor are discussed in three review manuscripts developed in parallel, with the presented article focused on the oxidation performance of uranium mononitride. Several high uranium density fuels are under consideration for deployment as accident tolerant and/or advanced technology nuclear reactor fuels, including one on each: UN, U 3 Si 2 , UC and UB 2 . Presented here is the research motivation for the incorporation of additives, dopants, or composite fuel architectures to improve the oxidation/corrosion behavior of high uranium density nuclear fuels for use in LWRs. Furthermore, this review covers the literature on the degradation modes, thermodynamics, and oxidation performance of pure UN and UN-compounds as well as reported alloyed and composite architectures.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Oxidation stability of advanced reaction-bonded Si3N4 materials

Four slip-cast, injection-molded and isostatically-pressed specimens of reaction-bonded silicon nitride (RBSN) were subjected to static oxidation tests at 900 C for 10 hours. Specimens containing 8-10% interconnected open porosity of size greater than one micron exhibited a 20-30% decrease in average room temperature four-point flexure strength, while those with 10% open porosity of magnitudes much smaller than one micron as well as those with 2-4% interconnected open porosity of about one micron did not decrease in strength after 900 C exposure. It was determined that preoxidation treatment at 1350 C prevents the 20-30% strength degradation due to internal oxidation, and evidence is presented which suggests that surface pit formation in some RBSN may result from contamination by the furnace environment rather than any intrinsic material properties.

Lindberg, L. J.↗

Investigating the Adhesion Force of Lunar Regolith Particulates on Air Plasma Sprayed Alumina Coatings

Ceramic materials, often used to protect components due to their high strength, and wear resistance, have added benefits of being lightweight and providing multifunctional properties. They are, therefore, significant to provide durability and support during long-duration missions to the moon’s surface for rovers, landers, robotic systems, habitats, and many other components. Materials such as aluminum oxide with high mechanical strength and hardness can help to improve the durability of structures used in space exploration. Devices used for space exploration require the use of materials with the ability to withstand exposure to extreme environments. Lunar regolith is a constituent with the ability to adhere electrostatically and damage the components used to perform these missions due to adhesion of lunar dust projectiles that can cause delamination on surfaces, which may not be physically visible. The particulates of lunar dust are classified as corrosive material, leading to the degradation of structures. Aluminum oxide presents excellent resistance to different types of wear due to its high strength and hardness. Air plasma sprayed (APS) aluminum oxide coatings have demonstrated the potential to protect the surface to which they are applied. However, the parameters of roughness and porosity of the coatings need to be considered to establish if they can protect the components from extreme environments. Considering the electrostatic forces that the components are exposed to, the adhesion between the lunar regolith and the surface of the components needs to be investigated. In this work, the adhesion forces of lunar dust simulants with an average size of 30 𝜇m are investigated considering the roughness of the surface of the APS aluminum oxide. The centrifugal technique utilized here offers the advantage of establishing the adhesion force between particles with different shapes on smooth or rough surfaces. The simulants were deposited on the surface of APS aluminum oxide using an aerosolization technique to achieve a monolayer coating in three different locations across the specimen to determine the increments in adhesion force at the centrifuge. The roughness of the APS aluminum oxide was determined to be 2.257 𝜇m. The specimen was tested under an incremental centrifugal speed from 100 rpm to 3000 rpm for 20 seconds. Low magnification microscopy images were collected to cover a larger surface area of the test coating. The adhesion force was measured considering the distance from the centrifugal axis and the rotational speed. Due to the coating roughness, and the distance from the centrifugal axis, the results demonstrated a larger adhesion force in locations closer to the centrifugal axis. Smaller particles were entrapped within the roughness of the coating, and a stronger adhesion force was measured. In order to continue designing wear-resistant coating for structural protection in space missions, press-on experiments using a centrifuge will be performed. Future experiments will allow us to determine the design parameters for APS aluminum oxide coating to protect the structures from harsh space environments.

Perla Latorre-Suarez↗

Bulk Diffusion of Cl through O Vacancies in α-Cr 2 O 3 : A Density Functional Theory Study

Many metals form passive oxides which are broken or weakened by anionic-induced degradation leading to material failure and anionic diffusion is an important step of this degradation process. The diffusion of anionic species through oxides involves a combination of diffusion along grain boundaries, cracks, and channels, as well as bulk diffusion via point defects which is the focus of this study. Using density functional theory, we study bulk diffusion of Cl through O vacancies in α -Cr 2 O 3 as a model system for passive metal oxides. Little is known about Cl diffusion and bonding characteristics, so we benchmark our work through comparison to numerous studies on O diffusion in α -Cr 2 O 3 to analyze similarities and differences between the O and Cl diffusion in the passivation and degradation process of α -Cr 2 O 3 respectively. Unlike O diffusion, the lowest diffusion barrier for Cl is cross-plane diffusion between two (0001) planes through a vacant cation site but the much shorter in-plane diffusion path within the same coordination polyhedron has 35% higher barrier. This work provides the basis for considering the contributions of Cl bulk-diffusion in the overall diffusion kinetics of Cl through α -Cr 2 O 3 .

Oware Sarfo, Kofi↗

Geochemical and mineralogical interpretation of the Viking inorganic chemical results

The current status of geochemical, mineralogical, petrological interpretation of refined Viking Lander data is reviewed, and inferences that can be drawn from data on the composition of Martian surface materials are presented. The materials are dominantly fine silicate particles admixed with, or including, iron oxide particles. Both major element and trace element abundances in all samples are indicative of mafic source rocks (rather than more highly differentiated salic materials). The surface fines are nearly identical in composition at the two widely separated Lander sites, except for some lithologic diversity at the 100-m scale. This implies that some agency (presumably aeolian processes) has thoroughly homogenized them on a planetary scale. The most plausible model for the mineralogical constitution of the fine-grained surface materials at the two Lander sites is a fine-grained mixture dominated by iron-rich smectites, or their degradation products, with ferric oxides, probably including maghemite and carbonates (such as calcite), but not such less stable phases as magnesite or siderite.

Toulmin, P., III↗

Multiphysics modeling of SOFC performance degradation caused by interface delamination and active layer cracking

In solid oxide device operation, delamination and cracking cause more catastrophic damage to cell life than other degradation mechanisms, leading to more rapid cell failure. The electrochemical performance degradation caused by electrode/electrolyte interface delamination and active layer cracking were investigated through in-house developed three-dimensional multiphysics simulations. Here the multiphysics simulations, fully calibrated against experimental datasets for button cells in a previous study, were extended to quantitatively investigate the effects of electrode/electrolyte interface delamination and active layer cracking. The simulated polarization curves and impedance behavior with various levels of delamination and cracking provided insights of the performance degradation. Furthermore, the local current distributions within the cell were analyzed for three different operating modes: constant voltage, constant current, and constant power. Finally, a practical strategy was proposed to mitigate the performance degradation in the realistic cell operations, extending overall cell lifetime.

08 HYDROGEN↗

Electron microscopy characterization of the fuel-cladding interaction in medium burnup annular fast reactor MOX

In this work, we present electron microscopy data focused on the fuel-cladding interaction layer in annular fast reactor MOX with HT-9 cladding at medium burnup. In agreement with previous literature data, the volatile fission products Cs, Te and I have migrated radially into the extreme fuel periphery and partially interacted with the cladding. The accumulation of Cs has occurred in the outermost rim of the fuel pellet, where grain recrystallization has also been observed. Significant amounts of Pd have been found in the interaction zone, particularly in the sample taken from the upper half of the fissile column where the cladding temperatures are higher. At this axial location, Cr has been enriched at the cladding inner surface and diffused into the fuel. Furthermore, chromium remains mainly in metallic form, but locally formed oxides. The fission products Cs, Te and I are found, with variable composition, in form of nanocrystalline regions dispersed in the metallic Cr-rich layer. The morphology and chemical characteristics of the layer suggest a non-oxidative corrosion mechanism as principal cladding degradation phenomenon occurring in this sample, with local onset of Cr oxidation within the nanocrystalline precipitates.

36 MATERIALS SCIENCE↗

Pre-Oxidation to Improve Liquid Metal Compatibility

Liquid metals represent an aggressive environment where selective degradation can attack structural alloys. Pre-oxidizing structural alloys, particularly those able to form alumina scales, have shown promise for Sn, Pb and Pb–Li concepts for fusion and fission applications. For Pb at 700 °C, a dramatic reduction in mass loss was observed for an alumina-forming austenitic (AFA) steel after pre-oxidation. Likewise, a ferritic FeCrAlMo alloy showed better compatibility in static Sn at 400–500 °C and flowing PbLi when pre-oxidized at 1000 °C to form α-Al2O3. Recent experiments with flowing PbLi at 675–700 °C has shown significant degradation suggesting that alumina-forming alloys are limited to ~ 650 °C in this environment. While the concept is promising, most experiments have been relatively short-term and long-term degradation mechanisms need to be evaluated.

Pint, Bruce↗

In-situ ellipsometric studies of optical and surface properties of GaAs(100) at elevated temperatures

A rotating-polarizer ellipsometer was attached to an ultrahigh vacuum (UHV) chamber. A GaAs(100) sample was introduced into the UHV chamber and heated at anumber of fixed elevated temperatures, without arsenic overpressure. In-situ spectroscopic ellipsometric (SE) measurements were taken, through a pair of low-strain quartz windows, to monitor the surface changes and measure the pseudodielectric functions at elevated temperatures. Real-time data from GaAs surface covered with native oxide showed clearly the evolution of oxide desorption at approximately 580 C. In addition, surface degradation was found before and after the oxide desorption. An oxide free and smooth GaAs surface was obtained by depositing an arsenic protective coating onto a molecular beam epitaxy grown GaAs surface. The arsenic coating was evaporated immediately prior to SE measurements. A comparison showed that our room temperature data from this GaAs surface, measured in the UHV, are in good agreement with those in the literature obtained by wet-chemical etching. The surface also remained clean and smooth at higher temperatures, so that reliable temperature-dependent dielectric functions were obtained.

Yao, Huade↗

Understanding and mitigating degradation in amine-based sorbents for CO 2 direct air capture

The success of direct air capture (DAC) of CO 2 depends on sorbents that combine high capacity, low energy requirements, and long-term durability. Amine-based sorbents-including solid-supported aminopolymers, grafted amines, and amine-functionalized resins-remain the leading candidates, but their limited lifetimes drive up costs and constrain deployment. In this review, we outline the current understanding of amine-based sorbent degradation with an emphasis on clearly identifying what is known about structure-property-performance relationships, as well as important knowledge gaps. More specifically, we discuss how polymer chemistry, sorbent design variables, and environmental and process conditions contribute to performance loss. In parallel, we outline how advances in spectroscopy, modeling, and accelerated testing are beginning to illuminate chemical and physical degradation mechanisms. Looking forward, we identify future research directions that will be critical for gaining a deeper understanding of degradation, as well as opportunities for developing innovative mitigation strategies for improving the lifetime of amine-based sorbents.

organic↗

Modeling Ni Coarsening and Migration in the Hydrogen Electrode of Solid oxide Cells under Operating Conditions

Ni coarsening and migration is the most important degradation in the hydrogen electrode of solid oxide cells. This presentation reviews our works on Ni coarsening and migration in NETL over the past years. We used simulation techniques including phase-field modeling and density function theory to investigate possible mechanisms of Ni coarsening and migration, including self-diffusion of Ni, diffusion of gaseous Ni(OH)2, surface diffusion of Ni(OH)x and Ni-YSZ wettability change, and examined the effect of operating conditions on these mechanisms. So far, none of the mechanisms can fully explain the experiments. Remaining questions and possible paths forward are summarized and discussed.

Lei, Yinkai↗