Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “CERIUM”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Reduction Thermodynamics of Sr 1– x Ce x MnO 3 and Ce x Sr 2– x MnO 4 Perovskites for Solar Thermochemical Hydrogen Production

Herein, the compositional families Sr 1–x Ce x MnO 3 (SCMX, X = 100x, x = 0.10, 0.20, and 0.30) and Ce x Sr 2–x MnO 4 (CSMX, X = 100x, x = 0.10, 0.20, and 0.30) are studied to determine the effects of perovskite structure and cerium content on thermal reduction thermodynamics and the resulting impact on solar thermochemical hydrogen production (STCH). Relying on thermogravimetric results from oxygen nonstoichiometry experiments, fits for various thermodynamic quantities are produced, including defect-reaction specific enthalpy (Δ H) and entropy (Δ S ), as well as the δ-dependent standard partial molar enthalpy, Δh¯$^{°}_{Ο}$, and entropy Δs¯$^{°}_{Ο}$, of oxygen as a function of composition within these two perovskite families. Here, the results of this thermodynamic study are also discussed in the context of structure and cerium dopant level. Experimental hydrogen production results show that the SCM family produces slightly larger amounts of hydrogen per mole of oxide compared with the CSM family under similar reduction and oxidation temperature conditions, however, a direct correlation between structure, cerium content, and water-splitting capacity could not be discerned.

08 HYDROGEN↗
DOE OSTI2020

Synergistic catalysis by Mn promoted ceria for molecular oxygen assisted epoxidation

Mesoporous manganese doped cerium oxide catalysts were prepared by an inverse micelle method with different manganese loadings. These materials exhibited superior activity for epoxidation of alkenes with molecular oxygen. Highest active 10MnCe material showed an activity of 80 % conversion and >99 % selectivity for cyclooctene epoxidation. The fluorite crystal structure which facilitates the high oxygen mobility, low temperature reducibility, homogeneous distribution of manganese on ceria, nanoparticle nature, higher number of oxygen vacancies, low valent states of manganese and cerium, and the ability to generate reactive oxygen species of the manganese doped cerium oxide could be correlated to the high catalytic activity. The reaction followed first order kinetics with a rate constant of 0.31 h –1 at 100 °C, and the activation energy turned out to be 10.5 kJ/mol. In conclusion, the mechanistic study revealed that the reaction proceeds via a unique mechanism which involves in situ generated superoxide and singlet oxygen species..

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Microwave-assisted ammonia synthesis over Cs-Ru/CeO 2 catalyst at ambient pressure: Effects of metal loading and support particle size

Industrially, ammonia is produced by Haber-Bosch process under high temperatures and pressures, consuming more than >2% of the world's energy production. This paper presents microwave-assisted catalytic synthesis of ammonia operated at atmospheric pressure and temperatures from 260 to 360 °C. A Cs-promoted Ru catalyst supported on cerium oxide with different metal loading (4–24 wt% Ru) and support particle size (25nm, 50nm and 5μm) was investigated. The small size cerium oxide support resulted in the highest activity while the large cerium oxide support was less favorable, leading to lower activity associated to large Ru particle size and lower dispersion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Binding of radionuclides and surrogate to 18-crown-6 ether by density functional theory

For this work, we use density functional theory to investigate the interactions of cerium, americium, and curium cations with crown ethers. Our calculations reveal that the modeled structure of cerium integrated within the crown ether is in good agreement with experimental data, with the negative binding energy indicating that capturing the cerium nitrates is thermodynamically favorable. Our results demonstrate that crown ethers can also bind americium and curium, providing insights into the potential applications of crown ether in radionuclide sequestration. Finally, we explore the impact of the skeleton modification of different crown ethers through by substitution of nitrogen atoms in the core of the crown ether for oxygen atoms and find that this structural modification significantly increases the radionuclide binding energies. These findings provide insights on the potential for the use of organic linkers such as crown ethers to address the urgent needs in radionuclide sequestration, separation and sensing.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Ce- and Ni-Codoped Double PrBaMn 2 O 5 Perovskite as a Ceramic SOFC Anode

This study explores the efficacy of cerium introduction, both on its own and in combination with nickel, into PrBaMn 2 O 5+δ (PBM) structures to enhance solid oxide fuel cell (SOFC) anodes. We synthesized Pr 1–x Ce x BaMn 2 O 5+δ compositions for x values of 0.05 (PrCe5) and 0.1 (PrCe10), as well as a nickel-doped variant (PrCe5Ni), assessing their performance under H 2 – 3% H 2 O reducing conditions pertinent to SOFC anode operations. Our findings reveal that the PrCe5 composition exhibits a thermal expansion coefficient (TEC) that not only improves upon that of the Ce-free counterpart but also aligns closely with the TEC standards of prevalent SOFC electrolytes. A notable advancement was achieved with the application of a 3.5 μm gadoliniadoped ceria (GDC) buffer layer through physical vapor deposition, effectively mitigating chemical interactions between PBM-based anodes and yttria-stabilized zirconia (YSZ) electrolytes, a concern highlighted by in situ neutron diffraction analyses. Electrochemical impedance spectroscopy, conducted over 220 h in a H 2 –3% H 2 O atmosphere at 750 °C, demonstrated that the optimal 3.5 μm thickness of the GDC buffer layer significantly minimizes the area-specific resistance (ASR) degradation rate to 0.002 Ω cm 2 /h, markedly outperforming both thinner (1 μm) and thicker (8 μm) GDC layers, which showed higher degradation rates of 0.15–0.2 Ω cm 2 /h due to the diffusion of Ba ions or delamination. Moreover, cerium doping fosters superior microstructural stability and obviates barium diffusion, thereby suggesting an enhanced durability of the doped anodes over their lifespan. Integrating nickel into the PrCe5 structure halved the ASR to 0.5 Ω cm 2 at 750 °C, situating it well within the ideal performance range for SOFC anodes. Furthermore, the enhancement brought about by simultaneously doping PBM with cerium and nickel, which fundamentally relies on the critical contributions of defect chemistry and crystal structure, highlights the significance of these fields in creating sophisticated materials for energy related applications.

25 ENERGY STORAGE↗
DOE OSTI2026

A point-particle-based hydride shell-shedding model for ejecta particle transport in reactive environments

A shock wave passing over a rough or perturbed metal surface will induce a limiting case of Richtmyer–Meshkov instability and will cause small particles to eject from the surface and transport into the surrounding medium. These particles are known as ejecta and can be either solid or liquid in nature. Recent experiments have shown that liquid cerium ejecta clouds exhibit unexpected non-monotonic acceleration behaviors as well as temperature plateaus after a brief temperature rise if they are transporting in a chemically reactive, hydrogen-based medium while they act as expected in an inert medium. This work details a point-particle model developed for reactive cerium ejecta transport, which attempts to account for these new physics through the behavior of a developing solid hydride shell, which is believed to form as a product of the reaction. The overall model incorporates the effects of the reaction on the particle properties as well as the effects of potential shedding of the shell into sub-micrometer scale flakes and potential phase change of the hydride if the ejecta particles reach the melt point of the hydride layer. The model is tested by performing simulations of the original motivating experiments and comparing quantities, such as ejected mass, velocimetry, and temperature profiles, against the experimental data. While the model is able to capture many general features of the observed anomalies, some inaccuracies still exist. These point to both missing physics in the model (such as a deuterium adsorption mechanism on the hydride layer) as well as a lack of knowledge of certain material properties (such as the strength of cerium hydride to determine dynamic fracture thicknesses) needed to fully reduce the uncertainties in the model by up to an order of magnitude and perform a true attempt at model validation.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Constraints on partial half-lives of 136 Ce and 138 Ce double electron captures

The γ-ray emissions from a radiopure cerium-bromide crystal with a mass of 4381 g were measured for a total of 497.4 d by means of high-resolution γ-ray spectrometry in the HADES underground laboratory at a depth of 500 m.w.e. A search for 0/2νϵϵ and 0/2νϵβ + double beta decay transitions of 136 Ce and 13 8Ce was performed using Bayesian analysis techniques. No signals were observed for a total of 35 investigated decay modes. 90% credibility limits were set in the order of 10 18 -10 19 yr. Existing constraints from a cerium oxide powder measurement were tested with a different cerium compound and half-life limits could be improved for most of the decay modes. The most likely accessible decay mode of the 136 Ce 2νϵϵ transition into the $0_{1}^{+}$ state of 136 Ba results in a new best 90% credibility limit of 5.0×10 18 yr.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2026

Design Trade-Offs in Composite Fuel Cell Membranes: Effects of Reinforcement and Chemical Additives

Perfluorosulfonic acid (PFSA) membranes are critical components in proton exchange membrane fuel cells, where performance depends on balancing ionic conductivity, mechanical durability, and chemical stability. This study characterizes a composite membrane (NC700) featuring PFSA-impregnated expanded polytetrafluoroethylene (ePTFE) reinforcement and cerium-based radical scavengers, benchmarked against unreinforced NR211. Complementary techniques, including electron microscopy, X-ray scattering, infrared spectroscopy, thermogravimetric analysis, and dynamic mechanical analysis, identify the structural and compositional strategies employed in NC700. Water sorption isotherms reveal lower water uptake for NC700 across all conditions, attributed to reinforcement and cerium incorporation. Reinforcement reduces in-plane swelling from 11% to 2.1% at 90% RH, confirming strong swelling anisotropy, while maintaining mechanical properties at elevated temperatures. While the ionic conductivity of NC700 is approximately 10% lower than that of NR211, the reduced thickness yields a 40% decrease in calculated area-specific resistance, suggesting the composite architecture can favorably shift the conductivity-stability trade-off. The composite structure also reduces gas permeability, indicating potential for improved separator function alongside favorable transport properties. Systematic deconvolution of reinforcement and additive contributions shows that conductivity losses from cerium incorporation are largely offset by gains from the lower equivalent-weight polymer, providing quantitative relationships that may guide composite membrane design for fuel cells and other electrochemical applications.

25 ENERGY STORAGE↗
NASA NTRS1973

Research Investigation on Dense Scintillation Glass for Use in Total Absorption Nuclear Cascade Detectors

Three approaches to the development of a high density scintillation glass were investigated: They include the increase of density of glass systems containing cerium - the only systems which were known to show scintillation, the testing of a novel silicate glass system containing significant concentrations of silver produced by ion exchange and never tested previously, and the hot pressing of a diphasic compact of low density scintillation glass with high density passive glass. In first two cases, while ultraviolet excited fluorescence was maintained in the glasses showing high density, scintillation response to high energy particles was not retained in the case of the cerium containing glasses or developed in the case of the silver containing glasses. In the case of the compacts, the extremely long path length caused by the multiple internal reflections which occur in such a body resulted in attenuation even with glasses of high specific transmission. It is not clear why the scintillation efficiency is not maintained in the higher density cerium containing glasses.

Hensler, J. R.↗
NASA NTRS1988

Examination of Martian sedimentary rocks to understand possible paleo-ocean and its age

It is well known that the terrestrial marine sediments have large cerium anomaly on their chondrite-normalized REE pattern. Siliceous shale and calcaleous sediments have negative Ce-anomaly. Ferromanganese nodule have positive or negative Ce-anomaly. The Ce-anomaly is considered to be a result of tetravalent state of cerium rather than common trivalent. Ferromanganese nodule which formed under reducing condition has negative Ce-anomaly. Then, combined study of Ce-anomaly with Ce isotopes is expected to play an important role in geochemistry. La-138 decays to Ce-138 and Ba-138 with a total half life of about 1 x 10 to the 11th years. Cerium anomalies (positive or negative) are expected in Martian paleo-ocean and in sediments as observed in the terrestrial environment. A list of things to be examined is given.

Tanaka, T.↗
DOE OSTI2020

Use of a Pressurized Water Treatment to Prevent Cracking of Internal Gelation Sol-Gel Microspheres

Pressurized water treatments were investigated as a means to prevent cracking of internal gelation sol-gel microspheres upon drying and heating. A batch of gelled cerium oxide microspheres was prepared, split into two samples that were processed with and without a pressurized water treatment, and dried in air at room temperature. Thermal gravimetric analysis was used to compare the mass loss profiles between the two samples and to understand volatile emissions from cerium oxide microspheres during heat treatments up to 600 °C. Microspheres that were processed without a pressurized water treatment lost approximately 4.6 times more mass upon heating than microspheres that were subjected to a pressurized water treatment. Comparison of the cracking behavior of microspheres prepared with and without a pressurized water treatment indicated that microspheres subjected to a pressurized water treatment were virtually crack-free after heat treatments. Conversely, microspheres processed without a pressurized water treatment, which is typical of traditional washing processes, exhibited extensive cracking. Analysis of residues dried from pressurized water treatment effluents indicated that hexamethylenetetramine and urea, which are excess reactants from the internal gelation process, were removed from gelled microspheres during the pressurized water treatment step. Traditional processing methods for preparing internal gelation microspheres use specific feed solution and gelation parameters to reduce subsequent cracking upon drying and heating. Results from this study indicate that more aggressive gel-forming conditions may be used to produce crack-free microspheres, if a pressurized water treatment step is included after washing and before air-drying.

cerium oxide, internal gelation, microsphere, TRIS↗
DOE OSTI2021

The role of precursor decomposition in the formation of samarium doped ceria nanoparticles via solid-state microwave synthesis

The impact on the final morphology of ceria (CeO 2 ) nanoparticles made from different precursors (commercial: cerium acetate/nitrate) and in house: cerium tri(methylsilyl)amide (Ce-TMSA)) via a microwave solid state reaction has been determined. In all instances, powder X-ray diffraction indicated that the cubic fluorite CeO 2 phase (PDF# 04–004-9150, with the space group Fm-3 m) had formed. Scanning electron microscopy (SEM) images revealed spherical nanoparticles were produced from the Ce-TMSA precursor. The commercial acetate and nitrate precursors produced particles with irregular morphology. The roles of the precursor decomposition and binding energy in the synthesis of the nanocrystals with various morphologies, as well as a possible growth mechanism, were evaluated based on experimental and computational data. The formation of spherical shaped nanoparticles was determined to be due to the preferential single-step decomposition of the Ce-TMSA as well as the low activation energy to overcome decomposition. Due to the complicated decomposition of the commercial precursors and high activation energy the resulting particles adopted an irregular morphology. Highly uniform samarium doped ceria (Sm x Ce 1-x O 2-δ ) nanospheres were also synthesized from Ce-TMSA and samarium tri(methylsilyl)amide (Sm-TMSA). The effects of reaction time and temperature, on the final morphology were observed through SEM. The rapid single-step decomposition of TMSA-based precursors as observed through thermogravimetric analysis (TGA) and confirmed through the calculation of potential energy surfaces and binding energies from density functional theory (DFT) calculations, indicated that nanoparticle formation follows LaMer’s classical nucleation theory.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Hybrid Sorbents for 129 I Capture from Contaminated Groundwater

Radioiodine ( 129 I) poses a risk to the environment due to its long half-life, toxicity, and mobility. It is found at the U.S. Department of Energy Hanford Site due to legacy releases of nuclear wastes to the subsurface where 129 I is predominantly present as iodate (IO 3 – ). To date, a cost-effective and scalable cleanup technology for 129 I has not been identified, with hydraulic containment implemented as the remedial approach. Here, novel high-performing sorbents for 129 I remediation with the capacity to reduce 129 I concentrations to or below the US Environmental Protection Agency (EPA) drinking water standard and procedures to deploy them in an ex-situ pump and treat (P&T) system are introduced. Furthermore, this includes implementation of hybridized polyacrylonitrile (PAN) beads for ex-situ remediation of IO 3 – -contaminated groundwater for the first time. Iron (Fe) oxyhydroxide and bismuth (Bi) oxyhydroxide sorbents were deployed on silica substrates or encapsulated in porous PAN beads. In addition, Fe–, cerium (Ce)–, and Bi–oxyhydroxides were encapsulated with anion-exchange resins. The PAN–bismuth oxyhydroxide and PAN–ferrihydrite composites along with Fe- and Ce-based hybrid anion-exchange resins performed well in batch sorption experiments with distribution coefficients for IO 3 – of >1000 mL/g and rapid removal kinetics. Of the tested materials, the Ce-based hybrid anion-exchange resin was the most efficient for removal of IO 3 – from Hanford groundwater in a column system, with 50% breakthrough occurring at 324 pore volumes. The functional amine groups on the parent resin and amount of active sorbent in the resin can be customized to improve the iodine loading capacity. These results highlight the potential for IO 3 – remediation by hybrid sorbents and represent a benchmark for the implementation of commercially available materials to meet EPA standards for cleanup of 129 I in a large-scale P&T system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Unveiling Synergetic Photocatalytic Activity from Heterometallic Ti/Ce Clusters

Titanium-oxo clusters, with their robust structure and suitable optical and electronic properties, have been widely investigated as photocatalysts. Heterometallic Ti/M-oxo clusters provide additional tunability and functionality, which enable systematic structure-activity investigations to elucidate reaction mechanisms and improve catalyst de-sign. Incorporating cerium into Ti-oxo clusters can provide additional redox (Ce IV /Ce III ) and oxygen harvesting ability, but to date only limited number of structurally defined titanium-cerium (Ti/Ce) clusters have been reported due to their synthetic challenges. Herein, we report the synthesis and photocatalytic properties of two structurally defined Ti/Ce-oxo clusters, Ti 8 Ce 2 (BA) 16 and Ti 9 Ce 4 (BA) 20 , as well as a TiCe-BA cluster with a calculated formula of Ti 20 Ce 9 O 36 (BA) 42 . Photocatalytic study of these clusters demonstrates that the amount of Ce 3+ species greatly impacts its photocatalytic oxidation performance, and their superior photocatalytic reactivity towards aerobic alcohol oxidation can be contributed to the synergistic effects of the multiple radical species generated upon light absorption. Furthermore, this work represents a significant milestone in the construction of stable Ti/Ce-oxo clusters, enriching the current library of known heterometallic Ti/M-oxo clusters, and providing a series of crystalline materials with great promise of photo-luminescence and photovoltaic chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Rare Earth and Transition Metal Containing Glasses

Transition metal (TM) and rare earth (RE) ions have been incorporated into many glass systems such as silicate, phosphate, and borosilicate-based oxide glasses, as well as in halide and chalcogenide glasses, that find applications ranging from optical, photonic, and magnetic devices, solid-state battery, to nuclear waste disposal. Understanding the structural role of RE and TM in these glasses can help to develop glass compositions for targeted applications with either high-optical emission efficiency, electrical conductivity, or chemical durability. In this chapter, we first provide a general introduction of the applications and structural features of RE and TM in glasses, then the critical aspects of molecular dynamics (MD) simulations of these glasses such as interatomic potentials, structural analysis tools to study RE and TM ions in glasses and their clustering behaviors, Quantitative Structure–Property Analysis (QSPR), diffusion and dynamic property calculations, and electronic structure calculations to understand electronic defects such as charge trapping and radiation effects are introduced. Three representative case studies are presented: the first one is on MD simulations of erbium- and europium-doped silica and silicate glasses, as well as cerium doped aluminophosphate glasses, that revealed the effect of glass composition on RE ion local structure and clustering behavior. Electronic structure calculations of cerium-doped glass show how the existence of multioxidation states help to mediate radiation-induced damages caused by excited electron–hole pairs was also discussed. The second one focuses on alkali vanadophosphate glasses where the existence of two vanadium oxidation states help to provide electronic conduction in the glasses while alkali ions provide ionic conduction. MD simulations were used to understand vanadium environments and other structural aspects in the phosphate glasses, as well as the ionic transport behaviors of alkali ions. The third case study is on zirconium-containing borosilicate and aluminosilicate glasses that find wide applications in nuclear waste disposal. MD simulations help to provide structural details of zirconium ions that are validated by diffraction and EXAFS spectra. The structural information was used to interpret changes of mechanical properties and chemical durability by using QSPR and other analyses-based MD-generated structure models.

Du, Jincheng↗
DOE OSTI2023

Asymmetric vanadium-based aqueous flow batteries

Vanadium redox couples (V(II)/V(III) on a negative electrode or V(IV)/V(V) on a positive electrode) can be paired with other redox couples to form novel flow batteries (FBs). As an anolyte, the V(II)/V(III) redox couple can be paired with iron, manganese, cobalt, and cerium redox couples to form novel vanadium-iron (V-Fe), vanadium-manganese (V-Mn), vanadium-cobalt (V-Co), and vanadium-cerium (V-Ce) FBs, respectively. The V(IV)/V(V) redox couple as a catholyte can be coupled with hydrogen to form a vanadium hydrogen (V-H2) FB. In those new redox chemistries, redox reactions, energy density, round-trip efficiencies, crossover issues, and cell components (i.e., separator, ion exchange membrane, and electrode) are different from an all-vanadium flow battery discussed in previous chapters, and thus warrant a detailed discussion.

Vanadium, V-Fe, V-Ce, V-Co↗
DOE OSTI2023

The Sluggish Diffusion of Cations in CeO 2 Probed through Molecular Dynamics and Metadynamics Simulations

Cation diffusion in fluorite‐structured CeO 2 , though far slower than anion diffusion, is an important, high‐temperature process because it governs diverse fabrication and degradation phenomena. Herein, cation diffusion is studied by means of classical molecular dynamics and metadynamics simulations. Three different mechanisms are examined: migration involving an isolated cerium vacancy, migration involving a cerium vacancy in a defect associate with an oxygen vacancy, and migration involving a cation divacancy. For each mechanism, defect diffusion coefficients are calculated as a function of temperature, from which the respective activation enthalpy of defect migration is obtained. Through comparisons with experimental cation diffusion data (specifically, of the absolute magnitude of the cation diffusivity as well as its activation enthalpy), it is concluded that cation diffusion takes place predominantly neither by isolated vacancies nor by cation vacancy–oxygen vacancy associates but by cation divacancies.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Enhancing HT-WGS catalyst performance with stable monovalent copper species via electron supply from defect-induced MgO

Magnesium oxide (MgO) exhibits excellent synergy with cerium oxide (CeO2), serving as either textural or electronic promoters during catalytic reactions. However, achieving well-dispersed CeO2-MgO is technically challenging because they are known not to form solid solutions, and the crystal growth of CeO2 suppresses the structure formation of MgO, leading to MgO being in an inhomogeneous amorphous state within CeO2-MgO. For this reason, most of research groups have been struggling with synthesizing well-dispersed CeO2-MgO. This leads them to focusing on the interaction between the active metal and cerium, overlooking the true role of magnesium. In this study, we successfully synthesized well-dispersed CeO2-MgO via a spray pyrolysis-assisted evaporation-induced self-assembly method, followed by the impregnation of Cu. The location and dispersion of Cu nanoparticles were highly dependent on the MgO distribution. Additionally, we revealed that this significantly influenced the catalytic activity and stability towards the HTS reaction and furthermore supplies electrons to monovalent Cu species, helping maintain the stable electron structure and oxidation state of Cu species considered as active sites. These findings suggest that optimizing the MgO distribution in CeO2-MgO is a promising strategy for developing efficient catalysts for the HTS reaction, emphasizing the role of MgO in designing high-performance catalysts.

Kim, Min-Jae↗