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At least 19 records

THERMAL EFFECTS ON MASS AND SPATIAL RESOLUTION DURING LASER PULSE ATOM PROBE TOMOGRAPHY OF CERIUM OXIDE

Cerium oxide (CeO2) is an ideal surrogate material for trans-uranic elements and fission products found in nuclear fuels due to similarities in their thermal properties; therefore, cerium oxide was used to determine the best run condition for atom probe tomography (APT). Laser pulse APT is a technique that allows for spatial resolution in the nm scale and isotopic/elemental chemical identification. A systematic study of the impact of laser pulse energy and specimen base temperature on the mass resolution, measurement of stoichiometry, multiples, and evaporation mechanisms are reported in this paper. It was demonstrated that using laser pulse APT stoichiometric field evaporation of cerium oxide was achieved at 1 pJ laser pulse energy and 20 K specimen base temperature.

36 MATERIALS SCIENCE↗

Induction of pulmonary fibrosis by cerium oxide nanoparticles

Cerium compounds have been used as a diesel engine catalyst to lower the mass of diesel exhaust particles, but are emitted as cerium oxide (CeO{sub 2}) nanoparticles in the diesel exhaust. In a previous study, we have demonstrated a wide range of CeO{sub 2}-induced lung responses including sustained pulmonary inflammation and cellular signaling that could lead to pulmonary fibrosis. In this study, we investigated the fibrogenic responses induced by CeO{sub 2} in a rat model at various time points up to 84 days post-exposure. Male Sprague Dawley rats were exposed to CeO{sub 2} by a single intratracheal instillation. Alveolar macrophages (AM) were isolated by bronchial alveolar lavage (BAL). AM-mediated cellular responses, osteopontin (OPN) and transform growth factor (TGF)-β1 in the fibrotic process were investigated. The results showed that CeO{sub 2} exposure significantly increased fibrotic cytokine TGF-β1 and OPN production by AM above controls. The collagen degradation enzymes, matrix metalloproteinase (MMP)-2 and -9 and the tissue inhibitor of MMP were markedly increased in the BAL fluid at 1 day- and subsequently declined at 28 days after exposure, but remained much higher than the controls. CeO{sub 2} induced elevated phospholipids in BAL fluid and increased hydroxyproline content in lung tissue in a dose- and time-dependent manner. Immunohistochemical analysis showed MMP-2, MMP-9 and MMP-10 expressions in fibrotic regions. Morphological analysis noted increased collagen fibers in the lungs exposed to a single dose of 3.5 mg/kg CeO{sub 2} and euthanized at 28 days post-exposure. Collectively, our studies show that CeO{sub 2} induced fibrotic lung injury in rats, suggesting it may cause potential health effects. -- Highlights: ► Cerium oxide exposure significantly affected the following parameters in the lung. ► Induced fibrotic cytokine OPN and TGF-β1 production and phospholipidosis. ► Caused imbalance of the MMP-9/ TIMP-1 ratio that favors fibrosis. ► Cerium oxide particles were detected in lung tissue and AM. ► Cerium oxide caused lung fibrosis in a dose- and time-dependent manner.

60 APPLIED LIFE SCIENCES↗

Enhanced Ferromagnetism from Organic–Cerium Oxide Hybrid Ultrathin Nanosheets

Room-temperature ferromagnetism in two-dimensional (2D) oxide materials is an intriguing phenomenon for spintronic applications. Here, we report significantly enhanced room-temperature ferromagnetism observed from ultrathin cerium oxide nanosheets hybridized with organic surfactant molecules. The hybrid nanosheets were synthesized by ionic layer epitaxy over a large area at the water–air interface. The nanosheets exhibited a saturation magnetization of 0.149 emu/g as their thickness reduced to 0.67 nm. This value was 5 times higher than that for CeO 2 thin films and more than 20 times higher than that for CeO 2 nanoparticles. The magnetization was attributed to the high concentration (15.5%) of oxygen vacancies stabilized by surfactant hybridization as well as electron transfer between organic and oxide layers. Lastly, this work brings an effective strategy of introducing strong ferromagnetism to functional oxide materials, which leads to a promising route toward exploring new physical properties in 2D hybrid nanomaterials.

36 MATERIALS SCIENCE↗

Geometry of electromechanically active structures in Gadolinium - doped Cerium oxides

Local distortions from average structure are important in many functional materials, such as electrostrictors or piezoelectrics, and contain clues about their mechanism of work. However, the geometric attributes of these distortions are exceedingly difficult to measure, leading to a gap in knowledge regarding their roles in electromechanical response. This task is particularly challenging in the case of recently reported non-classical electrostriction in Cerium-Gadolinium oxides (CGO), where only a small population of Ce-O bonds that are located near oxygen ion vacancies responds to external electric field. We used high-energy resolution fluorescence detection (HERFD) technique to collect X-ray absorption spectra in CGO in situ, with and without an external electric field, coupled with theoretical modeling to characterize three-dimensional geometry of electromechanically active units.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Production of monodisperse cerium oxide microspheres with diameters near 100 µm by internal-gelation sol–gel methods

Cerium dioxide microspheres with uniform diameters between 65 – 211 µm were fabricated using internal gelation sol-gel methods. Although uniform microspheres are produced for nuclear fuel applications with diameters above 300 µm, sol-gel microspheres with diameters of 50 - 200 µm have historically been made by emulsion techniques and had poor size uniformity [1, 2]. An internal gelation, sol-gel apparatus was designed and constructed to accommodate the production of small, uniform microspheres whereby cerium-containing solutions were dispersed into flowing silicone oil and heated in a gelation column to initiate solidification [3, 4]. Problems with premature feed gelation and microsphere coalescence were overcome by equipment modifications unique among known internal gelation setups. Microspheres were fabricated and sized in batches as a function of dispersing needle diameter and silicone oil flow rate in the two-fluid nozzle in order to determine the range of sizes possible and corresponding degree of monodispersity. Initial experiments with poor size uniformity were linked to microsphere coalescence in the gelation column prior to solidification as well as excessive flow rates for the cerium feed solution. Average diameter standard deviations as low as 2.23% were observed after optimization of flow rates and minimization of coalescence reactions.

cerium oxide↗

Synthesis and characterization of magnesium doped cerium oxide for the fuel cell application

Cerium oxide has attained much attentions in global nanotechnology market due to valuable application for catalytic, fuel additive, and widely as electrolyte in solid oxide fuel cell. Doped cerium oxide has large oxygen vacancies that allow for greater reactivity and faster ion transport. These properties make cerium oxide suitable material for SOFCs application. Cerium oxide electrolyte requires lower operation temperature which shows improvement in processing and the fabrication technique. In our work, we synthesized magnesium doped cerium oxide by the co-precipitation method. With the magnesium doping catalytic reactivity of CeO{sub 2} was increased. Synthesized nanoparticle were characterized by the XRD and UV absorption techniques.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Water Promotion (or Inhibition) of Condensation Reactions Depends on Exposed Cerium Oxide Catalyst Facets

Nanoparticles with well-defined facets enable quantitative correlations between surface features and catalytic activity. In this work, we explore the role of geometric and acid–base properties in the mechanism of aldol condensation catalyzed by ceria nanoshapes. In the crucial C–C coupling step, the two carbonyl adsorbates are bound to two adjacent cations. On the CeO 2 (110) plane, all atoms lie on the same layer, favoring the interaction between adsorbates and facilitating the bimolecular C–C coupling. Thus, the initial unimolecular deprotonation is rate-limiting. In contrast, the (100) and (111) planes have an open structure with O on the top layer and Ce on the layer below. The former O layer interferes between adsorbates linked to Ce sites, making the C–C coupling rate-limiting. Water helps in overcoming this spatial hindrance by remote bond polarization via H-bonds. Therefore, water promotion is only observed on those planes for which the bimolecular step is rate-limiting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparison of the high-pressure behavior of the cerium oxides C e 2 O 3 and Ce O 2

We studied the high-pressure behavior of Ce 2 O 3 using angle-dispersive x-ray diffraction to 70 GPa and compared with that of CeO 2 . Up to the highest pressure Ce 2 O 3 remains in the hexagonal phase (space group 164, P ¯32/m1) typical for the lanthanide sesquioxides. We did not observe a theoretically predicted phase instability for 30 GPa. The isothermal bulk modulus and its pressure derivative for the quasihydrostatic case are B 0 = 111 ± 2 GPa, B' 0 = 4.7 ± 0.3, and for the case without pressure-transmitting medium B 0 = 104 ±4 GPa, B' 0 = 6.5 ± 0.4. Starting from ambient-pressure magnetic susceptibility measurements for both oxides in highly purified form,we find that the Ce atom in Ce 2 O 3 behaves like a trivalent Ce 3+ ion (2.57μB per Ce atom) in contrast to previously published data. Since x-ray emission spectroscopy of the Lγ (4d 3/2 → 2p 1/2 ) transition is sensitive to the 4f -electron occupancy, we also followed the high-pressure dependence of this line for both oxides up to 50 GPa. We observed no change of the respective line shape, indicating that the 4f -electron configuration is stable for both materials. We posit from this data that the 4f electrons do not drive the volume collapse of CeO 2 from the high-symmetry, low-pressure fluorite structure to the lower-symmetry orthorhombic phase.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Nanocrystalline cerium oxide materials for solid fuel cell systems

Disclosed are solid fuel cells, including solid oxide fuel cells and PEM fuel cells that include nanocrystalline cerium oxide materials as a component of the fuel cells. A solid oxide fuel cell can include nanocrystalline cerium oxide as a cathode component and microcrystalline cerium oxide as an electrolyte component, which can prevent mechanical failure and interdiffusion common in other fuel cells. A solid oxide fuel cell can also include nanocrystalline cerium oxide in the anode. A PEM fuel cell can include cerium oxide as a catalyst support in the cathode and optionally also in the anode.

30 DIRECT ENERGY CONVERSION↗

Evidence of the coexistence of multivalence cerium oxide nano-particles in a sodium borate glass

In this study a sodium borate glass containing both trivalent cerium oxide and tetravalent cerium oxide states nano particles of 2–5 nm in size was successfully prepared by doping the glass with varying amounts of cerium (IV) oxide with. X-ray absorption spectroscopy measurement was used to determine the coexistence of the multivalent state of cerium oxide in the borate glass. Significant changes in the trivalent and tetravalent cerium oxide concentrations were observed when the glass was melted using different melting parameters and different raw materials. Glass made with borax that contained of 0.05mols of CeO 2 and melted at 1100 °C for 3 h had the highest concentration of trivalent cerium oxide. Transmission electron micrographs confirmed the release of trivalent Ce 2 O 3 and tetravalent CeO 2 nanoparticles from the glassy matrix. Fourier transform Infrared measurements suggest that the CeO 2 in the glass acts as both a glass-former and glass modifier.

36 MATERIALS SCIENCE↗

Transformation of Cerium Oxide Nanoparticles from a Diesel Fuel Additive during Combustion in a Diesel Engine

Nanoscale cerium oxide is used as a diesel fuel additive to reduce particulate matter emissions and increase fuel economy, but its fate in the environment has not been established. Here, cerium oxide released as a result of the combustion of diesel fuel containing the additive Envirox TM , which utilizes suspended nanoscale cerium oxide to reduce particulate matter emissions and increase fuel economy, was captured from the exhaust stream of a diesel engine and was characterized using a combination of bulk analytical techniques and high resolution transmission electron microscopy. The combustion process induced significant changes in the size and morphology of the particles; ~15 nm aggregates consisting of 5 to 7 nm faceted crystals in the fuel additive became 50 to 300 nm, near-spherical, single crystals in the exhaust. Electron diffraction identified the original cerium oxide particles as cerium (IV) oxide (CeO 2 , standard FCC structure) with no detectable quantities of Ce(III), whereas in the exhaust the ceria particles had additional electron diffraction reflections indicative of a CeO 2 superstructure containing ordered oxygen vacancies. The surfactant coating present on the cerium oxide particles in the additive was lost during combustion, but in roughly 30% of the observed particles in the exhaust, a new surface coating formed, approximately 2 to 5 nm thick. The results of this study suggest 28 that pristine, laboratory-produced, nanoscale cerium oxide is not a good substitute for the cerium 29 oxide released from fuel borne catalyst applications and that future toxicity experiments and modeling will require the use/consideration of more realistic materials.

54 ENVIRONMENTAL SCIENCES↗

Fungus mediated synthesis of biomedically important cerium oxide nanoparticles

Graphical abstract: - Highlights: • First time biological synthesis of cerium oxide oxide nanoparticles using fungus Humicola sp. • Complete characterization of cerium oxide nanoparticles. • Biosynthesis of naturally protein capped, luminescent and water dispersible CeO{sub 2} nanoparticles. • Biosynthesized CeO{sub 2} nanoparticles can be used for many biomedical applications. - Abstract: Nanomaterials can be synthesized by chemical, physical and the more recently discovered biological routes. The biological routes are advantageous over the chemical and physical ones as unlike these, the biological synthesis protocols occur at ambient conditions, are cheap, non-toxic and eco-friendly. Although purely biological and bioinspired methods for the synthesis of nanomaterials are environmentally benign and energy conserving processes, their true potential has not been explored yet and attempts are being made to extend the formation of technologically important nanoparticles using microorganisms like fungi. Though there have been reports on the biosynthesis of oxide nanoparticles by our group in the past, no attempts have been made to employ fungi for the synthesis of nanoparticles of rare earth metals or lanthanides. Here we report for the first time, the bio-inspired synthesis of biomedically important cerium oxide (CeO{sub 2}) nanoparticles using the thermophilic fungus Humicola sp. The fungus Humicola sp. when exposed to aqueous solutions of oxide precursor cerium (III) nitrate hexahydrate (CeN{sub 3}O{sub 9}·6H{sub 2}O) results in the extracellular formation of CeO{sub 2} nanoparticles containing Ce (III) and Ce (IV) mixed oxidation states, confirmed by X-ray Photoemission Spectroscopy (XPS). The formed nanoparticles are naturally capped by proteins secreted by the fungus and thus do not agglomerate, are highly stable, water dispersible and are highly fluorescent as well. The biosynthesized nanoparticles were characterized by UV–vis spectroscopy, Photoluminescence spectroscopy (PL), Transmission Electron Microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD) and X-ray Photoemission Spectroscopy (XPS)

36 MATERIALS SCIENCE↗

A comprehensive investigation on the properties of nanostructured cerium oxide

The structural, optical, magnetic and electrical properties of cerium oxide (CeO{sub 2}) nanoparticles prepared by hydrothermal route are analyzed by subjecting them to characterization techniques such as Powder X-ray diffraction (PXRD), High resolution scanning electron microscope (HRSEM), High resolution transmission electron microscope (HRTEM), Energy Dispersive X-ray Analysis (EDAX), Fourier transform infra red spectroscopy (FTIR), Raman spectroscopy, Ultraviolet–Visible analysis, Vibrating sample magnetometer (VSM) analysis and Dielectric measurements. The PXRD, FTIR, Raman and EDAX analyses confirm the formation of CeO{sub 2} nanoparticles. The PXRD studies reveal that the cerium oxide nanoparticles have crystalline nature and have Face Centered Cubic structure. The average crystallite size, estimated using Scherrer formula, is 7 nm. The HRSEM and HRTEM images reveal that the CeO{sub 2} nanoparticles have spherical morphology with an average particle size of 23 nm. The optical band gap energy of the cerium oxide nanoparticles, calculated from UV–Vis studies, is 3.4 eV which could be due to the substantial concentration of Ce{sup 3+} ions in the ceria nanoparticles. The Ferromagnetic behavior of CeO{sub 2} at room temperature is implied from VSM studies. The Dielectric analysis divulge that the dielectric constant of cerium oxide nanoparticles decreases as the frequency and temperature increases. The electrical behaviour, activation energy and relaxation time of electrons of CeO{sub 2} nanoparticles are studied by plotting Nyquist plot, Arrhenius plot and Bode plot respectively.

77 NANOSCIENCE AND NANOTECHNOLOGY↗