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At least 73 records · Page 4

Strength and microstructure of sintered Si3N4 with rare-earth-oxide additions

Room temperature, 700-, 1000-, 1200-, and 1370-C examinations of the effect of 1.7-2.6 mol pct rare earth oxide additions to sintered Si3N4 are conducted. While the room temperature-1000 C bend strengths were higher for this material with Y2O3 additions than with CeO2, La2O3, or Sm2O3, the reverse was true at 1200-1370 C. This phenomenon is explained on the basis of microstructural differences, since quantitative microscopy of SEM replicas showed the Si3N4-Y2O3 composition to contain both a higher percentage of elongated grains and a coarser microstructure than the other three alternatives. The elongated grains appear to increase this composition's low temperature strength irrespective of microstructural coarseness; this coarseness, however, decreases strength relative to the other compositions at higher temperatures.

Sanders, W. A.↗

Oxidation of silicon nitride sintered with rare-earth oxide additions

The effects of rare-earth oxide additions on the oxidation of sintered Si3N4 were examined. Insignificant oxidation occurred at 700 and 1000 C, with no evidence of phase instability. At 1370 C, the oxidation rate was lowest for Y2O3 and increased for additions of La2O3, Sm2O3, and CeO2, in that order. Data obtained from X-ray diffraction, electron microprobe analysis, and scanning electron microscopy indicate that oxidation occurs via diffusion of cationic species from Si3N4 grain boundaries.

Mieskowski, D. M.↗

Thermodynamic properties of some metal oxide-zirconia systems

Metal oxide-zirconia systems are a potential class of materials for use as structural materials at temperatures above 1900 K. These materials must have no destructive phase changes and low vapor pressures. Both alkaline earth oxide (MgO, CaO, SrO, and BaO)-zirconia and some rare earth oxide (Y2O3, Sc2O3, La2O3, CeO2, Sm2O3, Gd2O3, Yb2O3, Dy2O3, Ho2O3, and Er2O3)-zirconia system are examined. For each system, the phase diagram is discussed and the vapor pressure for each vapor species is calculated via a free energy minimization procedure. The available thermodynamic literature on each system is also surveyed. Some of the systems look promising for high temperature structural materials.

Jacobson, Nathan S.↗

Protective Coats For High-Temperature Strain Gauges

Addition of some rare-earth oxides to prior alumina (only) coating material increases maximum service temperature of palladium/chromium-wire strain gauges. Pd/Cr wires used at temperatures up to 800 degrees C without excessive drift in electrical resistance. Oxides used: zirconia (ZrO2), yttria (Y2O3), ceria (CeO2), and hafnia (HfO2). Addition of one of these oxides to decrease oxidation of wire at high temperature. Protection against oxidation increases with concentration of rare-earth oxide. Addition of ZrO2 at 4 to 6 weight percent or Y2O3 at 1 weight percent results in smallest drift in electrical resistance.

Lei, Jih-Fen↗

Large-area YBa2Cu3O(7-delta) thin films on sapphire for microwave applications

We have deposited YBa2Cu3O(7-delta) (YBCO) films with low microwave surface resistance (Rs) on 5-cm-diam, oxide-buffered sapphire substrates by planar magnetron sputtering. MgO buffer layers are used on M-plane (1 0 -1 0) sapphire, and R-plane (1 -1 0 2) sapphire is buffered by CeO2. Rs values of 450-620 microhms at 77 K and 10 GHz were measured across an entire 5-cm diam YBCO film on M-plane sapphire. For YBCO on R-plane sapphire, Rs values at 77 K and 10 GHz were 950 microohms for a 5-cm-diam wafer and 700 microohms for 1 x 1 sq cm samples.

Cole, B. F.↗

Sintering and Creep Behavior of Plasma-Sprayed Zirconia and Hafnia Based Thermal Barrier Coatings

The sintering and creep of plasma-sprayed ceramic thermal barrier coatings under high temperature conditions are complex phenomena. Changes in thermomechanical and thermophysical properties and in the stress response of these coating systems as a result of the sintering and creep processes are detrimental to coating thermal fatigue resistance and performance. In this paper, the sintering characteristics of ZrO2-8wt%y2O3, ZrO2-25wt%CeO2-2.5wt%Y2O3, ZrO2-6w%NiO- 9wt%Y2O3, ZrO2-6wt%Sc2O3-2wt%y2O3 and HfO2-27wt%y2O3 coating materials were investigated using dilatometry. It was found that the HfO2-Y2O3 and baseline ZrO2-Y2O3 exhibited the best sintering resistance, while the NiO-doped ZrO2-Y2O3 showed the highest shrinkage strain rates during the tests. Higher shrinkage strain rates of the coating materials were also observed when the specimens were tested in Ar+5%H2 as compared to in air. This phenomenon was attributed to an enhanced metal cation interstitial diffusion mechanism under the reducing conditions. It is proposed that increased chemical stability of coating materials will improve the material sintering resistance.

Zhu, Dongming↗

Design of a Uranium Dioxide Spheroidization System

The plasma spheroidization system (PSS) is the first process in the development of tungsten-uranium dioxide (W-UO2) fuel cermets. The PSS process improves particle spherocity and surface morphology for coating by chemical vapor deposition (CVD) process. Angular fully dense particles melt in an argon-hydrogen plasma jet at between 32-36 kW, and become spherical due to surface tension. Surrogate CeO2 powder was used in place of UO2 for system and process parameter development. Particles range in size from 100 - 50 microns in diameter. Student s t-test and hypothesis testing of two proportions statistical methods were applied to characterize and compare the spherocity of pre and post process powders. Particle spherocity was determined by irregularity parameter. Processed powders show great than 800% increase in the number of spherical particles over the stock powder with the mean spherocity only mildly improved. It is recommended that powders be processed two-three times in order to reach the desired spherocity, and that process parameters be optimized for a more narrow particles size range. Keywords: spherocity, spheroidization, plasma, uranium-dioxide, cermet, nuclear, propulsion

Cavender, Daniel P.↗

Determining the Source of Water Vapor in a Cerium Oxide Electrochemical Oxygen Separator to Achieve Aviator Grade Oxygen

More than a metric ton of water is transported to the International Space Station (ISS) each year to provide breathing oxygen for the astronauts. Water is a safe and compact form of stored oxygen. The water is electrolyzed on ISS and ambient pressure oxygen is delivered to the cabin. A much smaller amount of oxygen is used each year in spacesuits to conduct Extra Vehicular Activities (EVAs). Space suits need high pressure (>1000 psia) high purity oxygen (must meet Aviator Breathing Oxygen "ABO" specifications, >99.5% O2). The water / water electrolysis system cannot directly provide high pressure, high purity oxygen, so oxygen for EVAs is transported to ISS in high pressure gas tanks. The tanks are relatively large and heavy, and the majority of the system launch weight is for the tanks and not the oxygen. Extracting high purity oxygen from cabin air and mechanically compressing the oxygen might enable on-board production of EVA grade oxygen using the existing water / water electrolysis system. This capability might also benefit human spaceflight missions, where oxygen for EVAs could be stored in the form of water, and converted into high pressure oxygen on-demand. Cerium oxide solid electrolyte-based ion transport membranes have been shown to separate oxygen from air, and a supported monolithic wafer form of the CeO2 electrolyte membrane has been shown to deliver oxygen at pressures greater than 300 psia. These supported monolithic wafers can withstand high pressure differentials even though the membrane is very thin, because the ion transport membrane is supported on both sides (Fig 1). The monolithic supported wafers have six distinct layers, each with matched coefficients of thermal expansion. The wafers are assembled into a cell stack which allows easy air flow across the wafers, uniform current distribution, and uniform current density (Fig 2). The oxygen separation is reported to be "infinitely selective" to oxygen [1] with reported purity of 99.99% [2]. Combined with a mechanical compressor, a Solid Electrolyte Oxygen Separator (SEOS) should be capable of producing ABO grade oxygen at pressures >2400 psia, on the space station. Feasibility tests using a SEOS integrated with a mechanical compressor identified an unexpected contaminant in the oxygen: water vapour was found in the oxygen product, sometimes at concentrations higher than 40 ppm (the ABO limit for water vapour is 7 ppm). If solid electrolyte membranes are really "infinitely selective" to oxygen as they are reported to be, where did the water come from? If water is getting into the oxygen, what other contaminants might get into the oxygen? Microscopic analyses of wafers, welds, and oxygen delivery tubes were performed in an attempt to find the source of the water vapour contamination. Hot and cold pressure decay tests were performed. Measurements of water vapour as a function of O2 delivery rate, O2 delivery pressure, and process air humidity levels were the most instructive in finding the source of water contamination (Fig 3). Water contamination was directly affected by oxygen delivery rate (doubling the oxygen production rate cut the water level in half). Water was affected by process air humidity levels and delivery pressure in a way that indicates the water was diffusing into the oxygen delivery system.

Graf, John↗

Coated U3Si2 pellets with enhanced water and steam oxidation resistance

A method of forming a water resistant boundary on a fissile material for use in a water cooled nuclear reactor is described. The method comprises coating the fissile material, such as a pellet of U3Si2 and/or the grain boundaries, to a desired thickness with a suitable coating material, such as atomic layer deposition or a thermal spray process. The coating material may be any non-reactive material with a solubility at least as low as that of UO2. Exemplary coating materials include ZrSiO4, FeCrAl, Cr, Zr, Al—Cr, CrAl, ZrO2, CeO2, TiO2, SiO2, UO2, ZrB2, Na2O—B2O3—SiO2—Al2O3 glass, Al2O3, Cr2O3, carbon, and SiC, and combinations thereof. The water resistant layer may be overlayed with a burnable absorber layer, such as ZrB2 or B2O3—SiO2 glass.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Mesoporous metal doped cerium oxide catalyst

A mesoporous metal doped cerium oxide catalyst is provided. The catalyst can contain nanotextured cerium oxide (CeO2) which can be utilized for hydrogen production or reformate gas purification in a water gas shift reaction. The catalyst may be advantageously used to remove CO from a gas containing CO. The catalyst may also be incorporated into a fuel processor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic Layer Deposition for Materials-Based H2 Storage: Mg(BH4)2 as a Case Study

To meet the requirements for vehicular solid-state hydrogen (H2) storage, novel materials such as metal borohydrides have increasingly been investigated, in particular, magnesium borohydride (Mg(BH4)2). While these materials have a high H2 capacity (> 14 wt%), poor hydrogenation-dehydrogenation cyclability and material degradation, (e.g., loss of boron), need to be overcome. Prior research has indicated that nano-encapsulation and chemical additives can address these challenges. Therefore, we pursued these two strategies simultaneously with atomic layer deposition (ALD) on Mg(BH4)2. We investigated the use of metal-oxides (e.g., Al2O3, TiO2, CeO2), Pt- group metals (e.g., Pd, Ru) as well as pulsing only one precursor molecule (e.g., Al(CH3)3, BBr3, TiCl4), and assessed these modified Mg(BH4)2 in terms of their H2 storage properties. This presentation will also present the benefits and limitations of using vapor-phase techniques to modify the properties of Mg(BH4)2.

atomic layer deposition↗

Method for preparation of nanoceria supported atomic noble metal catalysts and the application of platinum single atom catalysts for direct methane conversion

Described are methods for converting methane to olefins, aromatics, or a combination thereof using a single atom catalyst comprising CeO2 nanoparticles impregnated with individual atoms of noble metals including Pt, Pd, Rh, Ru, Ag, Au, Ir, or a combination thereof. These single atom catalysts of the present invention are heated with methane to form olefins and aromatics.

Wang, Chao↗

Studying Cerium Oxide and Uranium Oxide Using Particle Attached Microelectrodes

The conference proceeding presents results of CeO2 and UO2 particles as microelectrodes enclosed in the SALVI E-cell developed in Dr. Yu's lab. These microfluidic cells can be used to study spent fuel materials in minute amount. They offer a flexible and economic way to understand spent fuel oxidation and dissolution in waste storage conditions.

Son, Jiyoung↗

Electrochemical Characterization of Molten Salt Chemistry During Atmospheric Ingressions

This report describes the salt chemistry and sedimentation studies that were completed in FY23 as part of the Pyrochemical Fuel Cycles – ANL project. The primary objective of these activities was to employ electrochemical methods in order to quantify and gain insights into the reaction mechanisms associated with the interaction of O2 and moisture impurities with the molten chloride salts used for the pyrochemical processing of nuclear materials. If not monitored and controlled, the ingression of these atmospheric impurities can lead to changes in the salt redox conditions and initiate the formation of oxide particles, potentially resulting in operational and safeguards challenges. By elucidating the mechanisms underlying the formation of oxide particles, we can effectively monitor the conditions of the salt and design systems to mitigate the influence of atmospheric O2 and H2O. To achieve these goals, we designed a test system that allowed for precisely controlled gas ingressions into the molten salt vessel. This system included on-line monitoring provided by electrochemical probes that enable near real-time measurements of the salt conditions throughout the course of the experiment. Using this system, we systematically varied experimental conditions, including O2/Ar flow rates and O2 concentrations, to comprehensively understand their impact on solid particle formation. We also used a particle size and shape analyzer to characterize the particles that were generated. Tests in FY23 concentrated on the formation of CeO2 particles, but we also prepared a separate apparatus targeting UO2 particles for use in FY24. We additionally conducted extensive modeling activities in support of this work. This included multiphysics simulations of the gas ingressions along with the development of a machine learning workflow to enable accelerated molecular dynamics modeling of the molten salt chemistry of LiCl-KCl-UCl3. The combination of experimental and modeling tools has allowed us to begin to get a more complete understanding of the reactions that occur when atmospheric ingressions occur in pyroprocessing systems.

Guo, Jicheng↗

Fiber-Based Distributed Hydrogen Measurement at High Temperatures

In this work, we discuss the implementation of evanescent field optical fiber sensors for distributed gas sensing of H2, focusing on results using a Ni / Gd-doped CeO2 nanocomposite sensing material for detection of low levels of H2 (0-4%) at 700 °C. This approach utilizes sensors prepared using a low-cost, wet chemical deposition process, in conjunction with a custom-built interrogator system leveraging optical time domain reflectometry (OTDR). Using a specially designed dual-gas flow reactor system, the sensor is tested by establishing a controlled equilibrium gradient of gas concentration. Initial results are shown using silica fiber, but provides a pathway for utilization with high temperature stable single crystal optical fiber for operation at higher temperatures and higher levels of H2 relevant for solid oxide fuel cell (SOFC) operating conditions.

Wuenschell, Jeffrey↗

Time resolved X-ray diffraction using the FIDDLE diagnostic at NIF: Preliminary assessment of diffraction precision

The Flexible Imaging Diffraction Diagnostic for Laser Experiments (FIDDLE) is a new diagnostic at the National Ignition Facility (NIF) designed to observe in situ solid-solid phase changes at high pressures using time resolved X-ray diffraction. FIDDLE currently incorporates five Icarus Ultrafast X-ray Imager sensors that take 2 ns snapshots and can be tuned to collect X-rays for tens of ns. The platform utilizes the laser power at NIF for both the laser drive and the generation of 10 keV X-rays for ~10 ns using a Ge backlighter foil. We aim to use FIDDLE to observe diffraction at different times during compression to probe the kinetics of phase changes. Pb undergoes two solid-solid phase transitions during ramp compression: from FCC to HCP and HCP to BCC. Results will be reported on some of the first shots using the FIDDLE diagnostic at NIF on ramp compressed Pb to a peak pressure of ~110 GPa and a single undriven CeO2 calibration shot. A discussion of the uncertainties in the observed diffraction is included.

Vennari, C. E.↗

LDRD poster - Identifying the speciation of salt-based actinides in the presence of contaminants

Molten salt reactors (MSRs) are among the most promising Generation IV nuclear reactors. The salts used in these reactors exhibit a high affinity for moisture and oxygen, and heating does not eliminate the oxides that are formed. Additionally, due to the high operating temperatures, reactor parts experience pronounced corrosion, and the resulting corrosion products integrate into the fuel salt system. It is hypothesized that the speciation of f-elements in molten salts would change in the presence of oxides and corrosion products. These changes in local structure can alter the rheological properties, which are critical to the operational and safety parameters of the reactors. Therefore, an in-depth understanding of how corrosion products influence lanthanide/actinide speciation is crucial. To test this hypothesis, lanthanides (as surrogates for actinides) and actinide chlorides were mixed with oxides (such as nickel oxide and lithium oxide) and/or corrosion products (e.g., nickel chloride) and reacted in molten salts. The resulting phases were analyzed using techniques such as powder X-ray diffraction, Raman spectroscopy, UV-Visible spectroscopy, and nuclear magnetic resonance spectroscopy. In the presence of oxides, due to the high oxophilicity of f-elements, these elements capture oxygen from the oxides, forming lanthanide/actinide oxide or oxychloride phases. Specifically, with cerium chloride, the introduction of lithium oxide to the formation of various final products depending on the oxide concentration. At lower oxide concentrations, cerium oxychloride (CeOCl) in the +3 oxidation state was observed, while an increase in the oxide concentration led to the formation of cerium dioxide (CeO2), where cerium is in the +4 oxidation state. In contrast, with nickel oxide, CeOCl formation was consistently observed, regardless of the oxide concentration. This project successfully determined that the speciation of f-elements change in the presence of oxides and different oxides in molten salts result in different final products. When the influence of nickel chloride was examined, changes in f-element speciation were not observed. However, it reacted with lithium chloride to generate a lithium-nickel-chloride (Li6NiCl8) phase, which was also observed when nickel oxide was reacted. Computational models were developed to simulate the phases anticipated under experimental conditions.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗

Enhancing Value-Added CO Production from CO 2 Hydrogenation by Tailoring the Ru-CeO 2 Interface on MgO

Catalytic CO 2 hydrogenation presents a promising route for converting CO 2 into valuable products, contributing to the mitigation of net CO 2 emissions. Supported Ru catalysts have recently gained considerable attention due to their tunability for 100% CO selectivity via the reverse water-gas shift pathway, effectively suppressing the competing methanation route. However, despite achieving full CO selectivity, the overall CO yield remains limited by low CO 2 conversion, necessitating further improvement. In this work, CeO 2 was introduced to modify a Ru/MgO single-atom catalyst for CO 2 hydrogenation. The resulting Ru-CeO 2 /MgO catalyst, featuring abundant Ru-CeO 2 interfacial sites, exhibited a favorable balance of CO 2 conversion and CO selectivity, delivering the highest CO yield (32.5% at 500 °C), which is 9.0 and 1.8 times higher than that on Ru/MgO (3.6%) and Ru/CeO 2 (18.4%), respectively. Although the CO selectivity was slightly compromised due to enhanced CO binding at Ru-CeO 2 interfacial sites, H 2 was more efficiently activated at these interfaces and readily reacted with CO 2 adsorbed on CeO 2 -MgO surfaces, thereby boosting the CO 2 hydrogenation activity and CO yield. This study underscores the critical role of Ru-metal oxide interface engineering in improving CO yield and advancing the rational design of highly efficient Ru catalysts for CO production from CO 2 hydrogenation.

36 MATERIALS SCIENCE↗