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At least 163 records · Page 9

High-temperature oxidation and quenching of chromium-coated zirconium alloy ATF cladding tubes with and w/o pre-damage

Chromium-coated zirconium alloys are one of the promising candidates for accident-tolerant fuel cladding (ATF) tubes for light water reactors (LWRs). In this study, the high temperature oxidation and degradation of two types of Cr coatings (cold spray and physical vapor deposition) with and without pre-damage by scratches were investigated on prototype rod segment samples filled with ZrO 2 pellets and tightly sealed with welded end caps. Isothermal tests at 1100 and 1200 °C were terminated by quenching with water; transient tests were performed up to 1500–1600 °C until complete coating failure. The positive effect of both types of Cr coatings was observed in all tests. Pre-damaged specimens showed only locally increased oxidation of the scratched zone, but no negative effects on the adjacent Cr coating. Finally, the behavior of the two types of coatings is compared and the degradation mechanisms are discussed based on hydrogen release data, extensive metallographic post-test examinations, and the current state of global research.

36 MATERIALS SCIENCE↗

Renewable biohydrogen production from lignocellulosic biomass using fermentation and integration of systems with other energy generation technologies

Biohydrogen is a clean and renewable source of energy. It can be produced by using technologies such as thermochemical, electrolysis, photoelectrochemical and biological, etc. Among these technologies, the biological method (dark fermentation) is considered more sustainable and ecofriendly. Dark fermentation involves anaerobic microbes which degrade carbohydrate rich substrate and produce hydrogen. Lignocellulosic biomass is an abundantly available raw material and can be utilized as an economic and renewable substrate for biohydrogen production. Although there are many hurdles, continuous advancements in lignocellulosic biomass pretreatment technology, microbial fermentation (mixed substrate and co-culture fermentation), the involvement of molecular biology techniques, and understanding of various factors (pH, T, addition of nanomaterials) effect on biohydrogen productivity and yield render this technology efficient and capable to meet future energy demands. Further integration of biohydrogen production technology with other products such as bio-alcohol, volatile fatty acids (VFAs), and methane have the potential to improve the efficiency and economics of the overall process. In this study, various methods used for lignocellulosic biomass pretreatment, technologies in trends to produce and improve biohydrogen production, a coproduction of other energy resources, and techno-economic analysis of biohydrogen production from lignocellulosic biomass are reviewed.

09 BIOMASS FUELS↗

High Efficiency PEM Water Electrolysis Enabled by Advanced Catalysts, Membranes and Processes

In this project, advanced membranes and catalysts were integrated into membrane electrode assembles (porous transport electrodes (PTE) or catalyst coated membranes (CCM)) leveraging precision coating methods to enable control of electrode structures and demonstration of the best component performance possible with these materials. Partner collaborations allowed for advanced characterization of the formed interfaces and degradation mechanisms. New methods of forming hydrogen recombination layers were also developed, to move away from wet chemistry processes that would have limited realization and implementation of the optimized electrode configurations in a commercial environment.

08 HYDROGEN↗

Sintered plaque characteristics

The structural transformations occurring during sintering, the fabrication of a slurry produced sintered plaque, are detailed. Degradation of the positive electrode in performance in cycling in a nickel hydrogen battery were traced to the quality of the sintered plaque. Electrode degradation was found to be a limiting factor in the battery cycle life. Details of microstructural characterization and distribution of pores, examination of plastic flow during shrinkage, and observations of the rounding of nickel powder particles during the slurry process are presented.

Vaidyanathan, H.↗

Effect of hydrogen on the strength and microstructure of selected ceramics

Ceramics in monolithic form and as composite constituents in the form of fibers, matrices, and coatings are currently being considered for a variety of high-temperature applications in aeronautics and space. Many of these applications involve exposure to a hydrogen-containing environment. The compatibility of selected ceramics in gaseous high-temperature hydrogen is assessed. Environmental stability regimes for the long term use of ceramic materials are defined by the parameters of temperature, pressure, and moisture content. Thermodynamically predicted reactions between hydrogen and several monolithic ceramics are compared with actual performance in a controlled environment. Morphology of hydrogen attack and the corresponding strength degradation is reported for silicon carbide, silicon nitride, alumina, magnesia, and mullite.

Herbell, Thomas P.↗

Effect of hydrogen on the strength and microstructure of selected ceramics

Ceramics in monolithic form and as composite constituents in the form of fibers, matrices, and coatings are currently being considered for a variety of high-temperature applications in aeronautics and space. Many of these applications involve exposure to a hydrogen-containing environment. The compatibility of selected ceramics in gaseous high-temperature hydrogen is assessed. Environmental stability regimes for the long term use of ceramic materials are defined by the parameters of temperature, pressure, and moisture content. Thermodynamically predicted reactions between hydrogen and several monolithic ceramics are compared with actual performance in a controlled environment. Morphology of hydrogen attack and the corresponding strength degradation is reported for silicon carbide, silicon nitride, alumina, magnesia, and mullite.

Herbell, Thomas P.↗

Ultrastable reference frequency distribution utilizing a fiber optic link

The Frequency Standards Laboratory at the Jet Propulsion Laboratory (JPL) is responsible for the generation and distribution of ultra-stable reference frequency in NASA's Deep Space Network (DSN). Certain assemblies and components of the Radio Science and VLBI systems are located in the cones of tracking antennas hundreds of meters from the Frequency and Timing Subsystem's frequency standards. The very stringent requirements of these users challenge the performance of state-of-the-art frequency sources as well as the associated signal distribution system. The reference frequency distribution system described is designed around a low temperature coefficient of delay (TCD) optical fiber. On-site measurements of the fiber optic link alone indicate 100 MHz phase noise performance on the order of -120 dBc at 1 Hz from the carrier and Allan deviation on the order of parts in 10(exp 16) at 1000 seconds averaging time. The measured phase noise and stability of the link indicate that the performance characteristics of the hydrogen maser frequency standards are not degraded by the distribution system. Thus, optical fibers and electro-optic devices as distribution media appear to be a viable alternative to the classical coaxial cable distribution systems.

Calhoun, Malcolm↗

Thermomechanical behavior of a polynorbornadiene

A high-temperature linear amorphous hydrocarbon polymer synthesized cationically from 2,5-norbornadiene was studied thermomechanically with respect to physical transitions and stability in nitrogen. The glass transition temperature was determined to be 320 C (at less than 1 cps), which is probably the highest known for a linear hydrocarbon addition polymer. The thermomechanical technique of torsional braid analysis, together with thermogravimetric analysis, differential thermal analysis, infrared analysis, and solubility studies, was used to investigate the sequential events of the glass transition and degradation. The polymer is of particular interest since it is a high-temperature plastic which in the bulk form would probably need to be processed at high speeds in the vicinity of the glass transition temperature in an inert atmosphere. The presence of tertiary hydrogen atoms should render it amenable to degradation by the earth's environment.

Roller, M. B.↗

Thermal oxidative degradation reactions of perfluoroalkylethers

The mechanisms operative in thermal oxidative degradation of Fomblin Z and hexafluoropropene oxide derived fluids and the effect of alloys and additives upon these processes are investigated. The nature of arrangements responsible for the inherent thermal oxidative instability of the Fomblin Z fluids is not established. It was determined that this behavior is not associated with hydrogen end groups or peroxy linkages. The degradation rate of these fluids at elevated temperatures in oxidizing atmospheres is dependent on the surface/volume ratio. Once a limiting ratio is reached, a steady rate appears to be attained. Based on elemental analysis and oxygen consumption data, CF2OCF2CF2O2, no. CF2CF2O, is one of the major arrangements present. The action of the M-50 and Ti(4 Al, 4 Mn) alloys is much more drastic in the case of Fomblin Z fluids than that observed for the hexafluoropropene derived materials. The effectiveness of antioxidation anticorrosion additives, P-3 and phospha-s-triazine, in the presence of metal alloys is very limited at 316 C; at 288 C the additives arrested almost completely the fluid degradation. The phospha-s-triazine appears to be at least twice as effective as the P-3 compound; it also protected the coupon better. The Ti(4 Al, 4 Mn) alloy degraded the fluid mainly by chain scission processes this takes place to a much lesser degree with M-50.

Paciorek, K. L.↗

Effects of Hydrogen on Tantalum Nitride Resistors

In this paper we report on observations of degradation of thin film Tantalum Nitride chip resistors in a hermetically sealed hybrid. The observations have been attributed to the reaction of residual Palladium with desorbed Hydrogen on the surface of the resistor film. Hydrogen gas has been observed to desorb from various sources within the sealed hybrid as a result of temperature elevation. The hydrogen gas has been reported to undergo a reaction with elements such as Platinum and Palladium causing device degradation in Gallium Arsenide Field Effect Transistors. The experimental procedures and data relating to this observation along with a discussion of available risk mitigation techniques will be presented.

Weiler, James↗

Operating Stresses and Their Effects on Degradation of LSM-Based SOFC Cathodes

The performance of solid oxides fuel cells (SOFCs) with four different Mn excess of lanthanum strontium manganite (LSM) -based cathodes were examined under different temperatures (1,000 °C, 900 °C), current densities (0, 380, and 760 mA cm -2 ), and cathode atmospheres (p O 2 )=0.1,0.15,0.21) for durations ranging from 58 to 1,008 h. Each yttria-stabilized zirconia (YSZ) electrolyte-supported “button” cell had a porous Ni/YSZ composite anode and a porous LSM/YSZ composite cathode. The cells’ output voltage versus time were recorded and electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) measurements were performed every 24 hours. The total area specific resistance (ASR) was calculated from these measurements. The values of ASR from both EIS and LSV were comparable between each other but lower than that from durability test. Distribution of relaxation times (DRT) analysis was performed to investigate the electrochemical processes and their corresponding relaxation frequencies as well as their attributions to the total ASR. The series resistance and parallel resistance that obtained from the equivalent circuit fit of the Nyquist plot were higher at low temperature and low p O 2 regardless of LSM compositions. The area of the peaks derived from DRT analysis increased with time during individual tests. The microstructures of the tested cells were examined using scanning electron microscopy and energy-dispersive x-ray spectroscopy (SEM/EDS). Manganese oxide particles were observed near the cathode-electrolyte interface after prolonged (1,008 h) testing in air of a cell with LSM of 11% manganese excess, and after a short test (58 h) under low oxygen (p O 2 = 0.10) in a cell with LSM of 5% manganese excess. However, the role of MnOx in cell degradation is still unknown.

08 HYDROGEN↗

Hydrogen Peroxide‐Induced Overoxidation of Fe−N−C Catalysts: Implications for ORR Activity

Fe−N−C (iron-nitrogen-carbon) electrocatalysts have emerged as promising alternatives to precious metals for the oxygen reduction reaction (ORR), but they remain insufficiently stable for widespread adoption in fuel cell technologies. One plausible mechanism to explain this lack of stability, and the associated catalyst degradation, is oxidative attack on the catalyst surface by hydrogen peroxide, a non-selective byproduct of the ORR. In this work, we perform a detailed analysis of this degradation mechanism, using a combination of periodic Density Functional Theory (DFT) calculations and ab-initio molecular dynamics (AIMD) simulations to probe the thermodynamics and kinetics of hydrogen peroxide activation on a series of candidate active sites for the Fe−N−C catalyst. The results demonstrate that carbon atoms neighbouring FeN 4 active sites can be strongly over-oxidized via formation of hydroxyl or epoxy groups when hydrogen peroxide is present in the electrolyte. In most cases, the interaction between the over-oxidizing groups and the ORR reaction intermediates reduces the ORR activity, and we further propose that the over-oxidized sites are likely precursors to irreversible carbon corrosion and further catalyst deactivation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of Microstructure on the Fatigue Crack Growth of A516 in Hydrogen

Some day hydrogen may be used as a viable energy storage and transport medium within the United States. Hydrogen gas may be used to dilute and extend our present methane supply as a blend or may even be used in its pure elemental form as a primary fuel. Independent of the methods of production, storage, and distribution, the interaction of hydrogen with its containment material will play an integral role in the success of a hydrogen energy program. Presently, the selection of hydrogen containment materials can be made such that the material will remain reasonably free from environmental degradation; however, costly alloying additions are required. Unfortunately, high alloy steels are economically prohibitive when large-scale hydrogen energy storage, transmission, and conversion systems are desired. Therefore, in order to implement such hydrogen energy systems in the future, existing low-cost materials must be improved via mechanical, thermal, or thermo-mechanical processing methods or new low-cost materials which are compatible with hydrogen must be developed. Originally, low strength, low alloy steels at room temperature were thought to be immune to hydrogen gas embrittlement, since no sustained load crack growth is observed. However, results of Clark in HY8O and Nelson in SAE 1020 have shown that the fatigue crack growth rate can be greatly accelerated in the presence of hydrogen gas. In recent results reported by Louthan and Mucci, the smooth bar fatigue life of an A1068 pipeline steel was reduced up to a factor of ten when the tests were performed in a 13.8 MPa hydrogen environment. These results suggest that the selection of material for structures designed to operate in hydrogen under cyclic loads must include consideration of hydrogen/metal fatigue interaction. Although the hydrogen/metal fatigue interaction can be severe in low strength low alloy steels, the degree of degradation may be altered by the underlying ferrous microstructure. At present, no correlation between microstructure and degree of hydrogen susceptibility exists for low strength steels. However, in high strength steels, susceptibility to hydrogen embrittlement has been shown to be strongly sensitive to the metallurgical microstructure. In addition, compositional effects and grain size can 703 Some day hydrogen may be used as a viable energy storage and transport medium within the United States. Hydrogen gas may be used to dilute and extend our present methane supply as a blend or may even be used in its pure elemental form as a primary fuel. Independent of the methods of production, storage, and distribution, the interaction of hydrogen with its containment material will play an integral role in the success of a hydrogen energy program. Presently, the selection of hydrogen containment materials can be made such that the material will remain reasonably free from environmental degradation; however, costly alloying additions are required. Unfortunately, high alloy steels are economically prohibitive when large-scale hydrogen energy storage, transmission, and conversion systems are desired. Therefore, in order to implement such hydrogen energy systems in the future, existing low-cost materials must be improved via mechanical, thermal, or thermo-mechanical processing methods or new low-cost materials which are compatible with hydrogen must be developed.

Wachob, Harry F.↗

An isotope harvesting beam blocker for the National Superconducting Cyclotron Laboratory

Harvesting isotopes from beam stops and other activated materials at accelerator facilities is a promising source of environmentally, scientifically and socially important radionuclides. At the Facility for Rare Isotope Beams (FRIB), a multitude of short- and long-lived radionuclides will be collected in a synergistic manner by dumping unused beams into a flowing-water beam stop. Ongoing exploratory research at the National Superconducting Cyclotron Laboratory (NSCL) with an analogous beam blocker aims towards obtaining the necessary radiochemical expertise for this endeavor. Herein we present a beam blocker and an isotope harvesting system which allows collection of a wide variety of aqueous and gaseous radionuclides. The water which flows through the beam blocker functions as an isotope production target and concurrently transports the newly formed radionuclides to collection sites. The system includes analytical instruments for online measurements of conductivity, dissolved oxygen, temperature, pressure and for detection of radiolytic products. To limit the levels of radiolytically produced hydrogen peroxide, a stainless-steel based degradation system was designed and implemented. Here, the suitability of the constructed system for the anticipated radionuclide harvesting project was demonstrated by offline tests and under irradiation with 140 MeV/u 48 Ca 20+ ions at the NSCL Coupled Cyclotron Facility.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Effect of ATF Cr-coated-Zircaloy on BWR In-vessel Accident Progression during a Station Blackout

The deposition of protective coatings on nuclear fuel cladding has been considered as a near-term Accident Tolerant Fuel (ATF) concept that will reduce the high-temperature oxidation rate and enhance accident tolerance of the cladding while providing additional benefits during normal and transient. In this study, the performance of the proposed ATF concept of Cr-coated-Zircaloy is assessed using a generic Boiling Water Reactor MELCOR plant model considering a Short-term Station Blackout (STSBO) scenario. Simulation results indicate that the use of Cr-coated-Zircaloy as cladding and canister material mitigates the core degradation process as compared to the traditional Zircaloy cladding and canister design. The onset of fuel degradation and collapse is delayed by over thirty minutes, and the extent of fuel degradation is reduced. Specifically, the gross in-vessel hydrogen generation decreased by almost a factor of three. Although the eutectic reaction between Cr-coating and Zircaloy could cause an early failure of the coating, the improvement in the delay of fuel degradation is still notable. In addition, a thicker coating is found helpful to obtain additional coping time and to decrease hydrogen generation. In addition to the eutectic formation that may compromise Cr-coated Zr, a different failure mode is identified for the Cr-coated-Zr when compared to Zircaloy; i.e., a complete melt of base material leads to component collapse before the coating is oxidized and consumed. These findings can help the industry focus on productive areas of research and development for accident-tolerant fuel concepts and enhancement of core safety margins.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Investigation of Membrane Chemical Degradation as a Function of Catalyst Platinum Loading

Membrane chemical degradation is one of many factors that can impact fuel cell durability. Additionally, the fuel cell’s lifetime heavily depends on the membrane and its ability to maintain chemical and mechanical integrity. Previous studies indicate that chemical degradation is due to the formation of hydroxyl radicals that attack the polymer structure resulting in membrane thinning, pinhole formation, and the release of fluoride and sulfate ions. Membrane durability was investigated using ultra-low Pt electrode loadings (≤ 0.1 mg Pt cm -2 ). Accelerated stress testing (US-DOE protocols) demonstrated that the degradation rate was found to increase with higher Pt loadings. This is most likely due to more heterogeneous sites for radical formation due to hydrogen crossover to the cathode. We also explored membrane degradation rates while varying catalyst layer thickness, ionomer to carbon ratio, and types of carbon support. All of the aforementioned variables impact the membrane degradation rates.

25 ENERGY STORAGE↗

Fiber optic reference frequency distribution to remote beam waveguide antennas

In the NASA/JPL Deep Space Network (DSN), radio science experiments (probing outer planet atmospheres, rings, gravitational waves, etc.) and very long-base interferometry (VLBI) require ultra-stable, low phase noise reference frequency signals at the user locations. Typical locations for radio science/VLBI exciters and down-converters are the cone areas of the 34 m high efficiency antennas or the 70 m antennas, located several hundred meters from the reference frequency standards. Over the past three years, fiber optic distribution links have replaced coaxial cable distribution for reference frequencies to these antenna sites. Optical fibers are the preferred medium for distribution because of their low attenuation, immunity to EMI/IWI, and temperature stability. A new network of Beam Waveguide (BWG) antennas presently under construction in the DSN requires hydrogen maser stability at tens of kilometers distance from the frequency standards central location. The topic of this paper is the design and implementation of an optical fiber distribution link which provides ultra-stable reference frequencies to users at a remote BWG antenna. The temperature profile from the earth's surface to a depth of six feet over a time period of six months was used to optimize the placement of the fiber optic cables. In-situ evaluation of the fiber optic link performance indicates Allan deviation on the order of parts in 10(exp -15) at 1000 and 10,000 seconds averaging time; thus, the link stability degradation due to environmental conditions still preserves hydrogen maser stability at the user locations. This paper reports on the implementation of optical fibers and electro-optic devices for distributing very stable, low phase noise reference signals to remote BWG antenna locations. Allan deviation and phase noise test results for a 16 km fiber optic distribution link are presented in the paper.

Calhoun, Malcolm↗